JPH01272867A - Carbon fiber excellent in high-order processability - Google Patents
Carbon fiber excellent in high-order processabilityInfo
- Publication number
- JPH01272867A JPH01272867A JP10061988A JP10061988A JPH01272867A JP H01272867 A JPH01272867 A JP H01272867A JP 10061988 A JP10061988 A JP 10061988A JP 10061988 A JP10061988 A JP 10061988A JP H01272867 A JPH01272867 A JP H01272867A
- Authority
- JP
- Japan
- Prior art keywords
- sizing
- carbon fiber
- yarn
- sizing agent
- carbon fibers
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 title abstract description 48
- 239000004917 carbon fiber Substances 0.000 title abstract description 48
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 239000000835 fiber Substances 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 5
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004513 sizing Methods 0.000 abstract description 48
- 239000003795 chemical substances by application Substances 0.000 abstract description 29
- 239000011159 matrix material Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 10
- 239000011347 resin Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 3
- 229920001451 polypropylene glycol Polymers 0.000 abstract description 3
- 238000004804 winding Methods 0.000 abstract description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 238000012423 maintenance Methods 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 239000000839 emulsion Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- IVIDDMGBRCPGLJ-UHFFFAOYSA-N 2,3-bis(oxiran-2-ylmethoxy)propan-1-ol Chemical compound C1OC1COC(CO)COCC1CO1 IVIDDMGBRCPGLJ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011304 carbon pitch Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical group O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- -1 urethane compound Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は高次加工性の優れた炭素繊維に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to carbon fibers with excellent high-order processability.
［従来の技術］
従来、炭素繊維はその優れた比強度、比弾性率等の力学
的性質により航空、宇宙用材料、釣竿。[Prior Art] Conventionally, carbon fiber has been used as a material for aviation, space, and fishing rods due to its excellent mechanical properties such as specific strength and specific modulus.
テニスラケットおよびゴルフシャフトなど広い分野にお
いて複合材料として用いられている。It is used as a composite material in a wide range of fields such as tennis rackets and golf shafts.
しかし、この炭素繊維あるいは黒鉛繊維は本質的に剛直
で脆く、耐屈曲性や耐擦過性に乏しいために、その製造
工程乃至高次加工工程において毛羽を発生し易く、さら
には糸切れを生ずることにもなりかねず、加えて、該炭
素繊維は一般にマトリックスに対する接着性が不十分で
ある。However, carbon fibers or graphite fibers are inherently rigid and brittle, and have poor bending resistance and abrasion resistance, so they tend to generate fuzz and even breakage during manufacturing and advanced processing processes. In addition, the carbon fibers generally have poor adhesion to the matrix.
そこで、通常の炭素繊維には各種のサイジング剤が付与
され、このサイジングによって該炭素繊維に集束性を付
与し、耐屈曲性や耐擦過性を改良すると共に、マトリッ
クスに対する接着性がある程度改良されてきた。Therefore, various sizing agents are added to ordinary carbon fibers, and this sizing gives the carbon fibers cohesiveness, improves bending resistance and abrasion resistance, and improves adhesion to the matrix to some extent. Ta.
これら従来の炭素繊維用サイジング剤としては、炭素繊
維への均一な付着性、サイジング剤の溶液安定性並びに
マトリックス、特に各種マトリックス樹脂との相溶性お
よび接着性などの点から、有機溶剤系のエポキシ系ある
いはポリエステル系サイジング剤が一般に用いられてい
るが、この有機溶剤系のサイジング剤は、サイジング方
法工程における作業性、特に環境衛生上並びに火災等の
防災上の見地からは好ましくない。このような観点から
、最近では有機系樹脂を乳化剤により水に分散させた水
分散型エマルジョンのサイジング剤の開発も進められて
いる（例えば、特開昭５８−１３７８１号公報、特開昭
６０−２４６８７２号公報）。As these conventional sizing agents for carbon fibers, organic solvent-based epoxies are used because of their uniform adhesion to carbon fibers, solution stability of the sizing agent, and compatibility and adhesion with matrices, especially various matrix resins. Although sizing agents based on organic solvents or polyesters are generally used, these sizing agents based on organic solvents are not preferred from the viewpoint of workability in the sizing process, particularly from the viewpoint of environmental hygiene and disaster prevention such as fire. From this point of view, recent efforts have been made to develop sizing agents for water-dispersed emulsions in which organic resins are dispersed in water using emulsifiers (for example, JP-A-58-13781, JP-A-60-1999). 246872).
［発明が解決しようとする課題］
しかし、かかる従来のサイジング剤では、一般に炭素繊
維と金属との摩擦係数を下げる効果が小さく、また炭素
繊維の集束性も決して十分とは言えなかった。このため
、炭素繊維がプリプレグ化。[Problems to be Solved by the Invention] However, such conventional sizing agents generally have little effect on lowering the coefficient of friction between carbon fibers and metal, and the cohesiveness of carbon fibers has never been sufficient. For this reason, carbon fiber is turned into prepreg.
ドラムワインド等の高次加工において、ガイドバーやロ
ーラなどでしごかれた際に１毛羽ヤ糸切れが発生し、作
業性や品質を著しく低下させるという問題があった。特
にサイジング処理前の金属との摩擦係数の高い炭素繊維
において、この傾向は顕著であった。In high-order processing such as drum winding, there is a problem in that when the yarn is squeezed by a guide bar or roller, single fuzz or yarn breakage occurs, which significantly reduces workability and quality. This tendency was particularly noticeable in carbon fibers, which have a high coefficient of friction with metal before sizing treatment.
本発明の課題はサイジング処理により摩擦係数を著しく
低下させ、高次加工においてガイドバーやローラにしご
かれた際にも、毛羽や糸切れが発生し難い炭素繊維を提
供することにある。An object of the present invention is to provide a carbon fiber whose friction coefficient is significantly lowered through sizing treatment, and which is less likely to fluff or break even when squeezed by guide bars or rollers in high-order processing.
［課題を解決するための手段］
本発明の上記課題は、下式［Ｉ］、［ＩＩ］および［Ｉ
］から選ばれた少なくとも１種の化合物を０．１〜５．
０重量％（ｗｔ％）付着させてなる炭素繊維によって解
決することができる。[Means for Solving the Problems] The above problems of the present invention are solved by the following formulas [I], [II] and [I
] at least one compound selected from 0.1 to 5.
This problem can be solved by using carbon fibers deposited at 0% by weight (wt%).
ｍ、ｎは１〜４９．但しｍ＋ｎは１０〜５０である。m and n are 1 to 49. However, m+n is 10-50.
以下、本発明について詳細に説明する。The present invention will be explained in detail below.
本発明の炭素繊維はアクリル糸、ピッチ糸、セルロース
糸などの各種繊維を前駆体として公知の方法を用いて耐
炎化処理を行い、次いで不活性ガス雰囲気中で焼成した
。いわゆる炭化糸、黒鉛化糸のいずれも含まれるが、特
に表面が平滑で摩擦係数の高いアクリル糸の乾湿式紡糸
原糸を焼成して１ｑられる炭素繊維あるいはピッチ系の
炭素繊維が好適でおる。The carbon fibers of the present invention were made of various fibers such as acrylic threads, pitch threads, and cellulose threads as precursors, subjected to flame-retardant treatment using a known method, and then fired in an inert gas atmosphere. Although both so-called carbonized yarn and graphitized yarn are included, carbon fiber or pitch-based carbon fiber, which is produced by firing dry-wet-spun raw acrylic yarn with a smooth surface and a high coefficient of friction, or pitch-based carbon fiber is particularly suitable.
本発明における式［Ｉ］〜［ＩＩＩ］で示される化合物
（以下、単にサイジング剤という）は、その中のポリエ
チレンオキシドまたは／およびポリプロピレンオキシド
部が炭素繊維に平滑性を与え、摩擦係数を低下させる効
果がある。一方、ビスフェノールＡ部はマトリックス樹
脂との相溶性を向上させる効果がある。The compounds represented by formulas [I] to [III] in the present invention (hereinafter simply referred to as sizing agents) have polyethylene oxide and/or polypropylene oxide moieties that give smoothness to carbon fibers and reduce the coefficient of friction. effective. On the other hand, the bisphenol A part has the effect of improving compatibility with the matrix resin.
また、上記の各成分は共重合して用いることで、各々単
一成分を混合して用いる場合に比べて樹脂との相溶性を
維持し、摩擦係数を下げる効果を一層大きくすることが
できる。In addition, by copolymerizing the above components and using them, it is possible to maintain compatibility with the resin and further increase the effect of lowering the coefficient of friction, compared to when a single component is used as a mixture.
更に上記サイジング剤において、上記式中２ｍ十〇が１
０未満の化合物では、本発明の目的である炭素繊維の摩
擦係数を下げる効果が小さく好ましくない。またｍ ＋
、ｎが５０を越えるとマトリックス樹脂との相溶性が低
下し、マトリックス樹脂と炭素繊維との接着性が低下す
るので好ましくない。Furthermore, in the above sizing agent, 2m〇 in the above formula is 1
A compound having a molecular weight of less than 0 is not preferable because the effect of lowering the friction coefficient of carbon fibers, which is the object of the present invention, is small. Also m +
, n exceeding 50 is not preferred because the compatibility with the matrix resin decreases and the adhesion between the matrix resin and carbon fibers decreases.
サイジング剤の炭素繊維に対する付着割合は０．１〜５
．０ｗｔ％、好ましくは０．３〜３．０ｗｔ％の範囲内
にするのがよい。付着量が５．Ｑｗｔ％を越えると糸が
硬くなり、コンポジットとして用いるとき、マトリック
ス樹脂との含浸性や糸の拡がり性が低下するので好まし
くない。また、Ｑ、１ｗｔ％より低くなると、炭素繊維
の集束性が不十分で本発明の目的を達し得ず好ましくな
い。The adhesion ratio of the sizing agent to carbon fiber is 0.1 to 5.
．． The content is preferably 0 wt%, preferably within the range of 0.3 to 3.0 wt%. The amount of adhesion is 5. If it exceeds Qwt%, the yarn becomes hard and, when used as a composite, impregnation with the matrix resin and spreadability of the yarn decrease, which is not preferable. Furthermore, if Q is lower than 1 wt%, the carbon fibers will have insufficient cohesiveness and the object of the present invention cannot be achieved, which is not preferable.
なお、本発明の炭素繊維はマトリックス樹脂との接着性
を高めるために上記サイジング剤と共に。In addition, the carbon fiber of the present invention is used together with the above-mentioned sizing agent in order to improve adhesiveness with the matrix resin.
ビスフェノールＡ系などのエポキシ樹脂を混用すること
もできる。Epoxy resins such as bisphenol A-based epoxy resins can also be used in combination.
次に、炭素繊維に対するサイジング剤の付与手段として
は特に限定されるものではないが、例えば■ローラを介
してサイジング液にデイツプする方法、■サイジング液
の付着したローラに接する方法、■サイジング液を霧状
にして吹きつける方法などがある。Next, the means for applying the sizing agent to the carbon fibers is not particularly limited, but examples include: (1) dipping in the sizing liquid via a roller, (2) contacting a roller with the sizing liquid attached, and (2) applying the sizing agent to the carbon fiber. There are ways to spray it in the form of a mist.
この際、炭素繊維に対するサイジング剤の付着量が上記
規定範囲内で有効成分が均一に付着するように、サイジ
ング液濃度、温度、糸条張力などをコントロールするこ
とが好ましい。At this time, it is preferable to control the concentration of the sizing solution, temperature, thread tension, etc. so that the amount of the sizing agent attached to the carbon fibers is within the above specified range and the active ingredient is uniformly attached.
サイジング剤付与後の炭素繊維は引続き乾燥処理される
が、通常は１００〜２５０℃の範囲で乾燥するのがよい
。乾燥温度が２５０℃を越えるとサイジング剤の熱劣化
が生じ易くなるため好ましくない。またこの際の乾燥装
置としては乾燥効率が高く、低温で乾燥可能な熱風循環
型が望ましい。The carbon fibers to which the sizing agent has been applied are subsequently subjected to a drying process, and it is usually preferable to dry them at a temperature in the range of 100 to 250°C. If the drying temperature exceeds 250°C, the sizing agent tends to be thermally degraded, which is not preferable. Further, as the drying device at this time, a hot air circulation type that has high drying efficiency and can dry at low temperatures is desirable.
［実施例］ 以下、本発明を実施例により具体的に説明する。[Example] Hereinafter, the present invention will be specifically explained with reference to Examples.
なお、本例中の擦過毛羽数、摩擦係数および層間剪断強
度は次の測定方法を用いた。In this example, the number of rubbed fuzz, friction coefficient, and interlayer shear strength were measured using the following measurement method.
（１）擦過毛羽数
直径１０ｍのステンレス棒（クロムめっき、表面粗さ１
〜１．５３） ５本を５０ｍ間隔で各々平行に、かつそ
れらの表面を炭素繊維糸条が１２０゜の接触角で接触し
ながら通過し得るように棒をジグザクに配置した擦過装
置を用いた。この装置により炭素繊維糸条に１デニール
あたり０．０９９の入り側張力下、３ｍ／分の糸速で通
過させ、側面から繊維糸条に対し直角にレーザ光線を照
射し、毛羽数を毛羽検出装置で検出カウントし１個／ｍ
で表示する。(1) Stainless steel rod with a diameter of 10 m (chrome plating, surface roughness 1)
~1.53) A scraping device was used in which five rods were arranged in a zigzag pattern so that five rods were placed parallel to each other at 50 m intervals, and the carbon fiber threads could pass through their surfaces while contacting each other at a contact angle of 120°. . Using this device, the carbon fiber yarn is passed through at a yarn speed of 3 m/min under an entrance tension of 0.099 per denier, and a laser beam is irradiated from the side at right angles to the fiber yarn to detect the number of fuzz. The device detects and counts 1 piece/m.
Display in .
（２）摩擦係数
上記の擦過毛羽測定において、糸条入側と出側の張力の
比から次式より求めた。(2) Friction coefficient In the above-mentioned rubbing fluff measurement, the friction coefficient was determined from the ratio of the tension on the yarn entry side and the yarn exit side using the following formula.
Ｔ２ ：糸条出側張力
（３）層間剪断強度（ＩＬＳＳ）
マトリックスとして、油化シェル製エピコート８２８を
用い、ＡＳＴＭ Ｄ−２３４４に準じて測定した。T2: Yarn exit side tension (3) Interlaminar shear strength (ILSS) It was measured according to ASTM D-2344 using Epicoat 828 manufactured by Yuka Shell as a matrix.
実施例１
サイジング剤として［Ｉ］式において、Ｒ１＝Ｏ１１゜
Ｒ２−Ｈ、ｍ ＝１５． ｎ ＝１５ としたビスフ
ェノールＡエチレンオキサイド付加物誘導体のｌ’ｗｔ
％濃度水分散エマルジョンを調整した。このサイジング
エマルジョンに単糸繊度０．３６デニール、フィラメン
ト数１２，０００本からなる炭素繊維をデイツプローラ
を介して浸漬した後、熱風循環型乾燥機にて１５０°Ｃ
，１分間の乾燥を行った。Example 1 As a sizing agent, in formula [I], R1=O11°R2-H, m=15. l'wt of bisphenol A ethylene oxide adduct derivative with n = 15
% concentration water dispersion emulsion was prepared. Carbon fibers consisting of 12,000 filaments with a single yarn fineness of 0.36 denier were dipped into this sizing emulsion through a date roller, and then heated at 150°C in a hot air circulation dryer.
, and was dried for 1 minute.
得られたサイジング付着糸について、サイジング付着量
、擦過毛羽数、摩擦係数およびｌ ＬＳＳを調べ、その
結果を第１表に示した。The resulting sizing-adhesive yarn was examined for sizing-adhering amount, number of rubbed fuzz, friction coefficient, and l LSS, and the results are shown in Table 1.
実施例２
サイジング剤として［Ｉ］式において、 Ｒ１−０ＣＨ
ｐ−ＣＨＣＨ２，Ｒ２＝Ｈ、ｍ ＝１５． ｎ ＝１５
とした１Ｗｔχ玉マルジヨンを用いる他は、使用する炭
素繊維、サイジング付着方法などは実施例１と同様にし
てサイジング付着糸を得た。サイジング付着糸の評価結
果を第１表に示した。Example 2 In formula [I] as a sizing agent, R1-0CH
p-CHCH2, R2=H, m=15. n=15
A sizing-attached yarn was obtained in the same manner as in Example 1 except that the 1Wt x-ball multilayer was used, and the carbon fibers used and the sizing attachment method were the same as in Example 1. The evaluation results of the sizing-attached yarn are shown in Table 1.
実施例３
サイジング剤として［Ｉ］式において、Ｉ；Ｈゴ
ｎ＝１５とした１ｗｔ％エマルジョンを用いる他は、使
用する炭素繊維、サイジング付着方法などは実施例１と
同様にしてサイジング付着糸を１ｑた。サイジング付着
糸の評価結果を第１表に示した。Example 3 The carbon fibers used, the sizing attachment method, etc. were the same as in Example 1, except that in formula [I], a 1 wt% emulsion with I; H = 15 was used as the sizing agent. It was 1q. The evaluation results of the sizing-attached yarn are shown in Table 1.
実施例４
サイジング剤として［Ｉｆ］式において、 Ｒ１＝Ｈ，
Ｒ２＝Ｏｌｌ、 ｍ ＝１０． ｎ ＝１０とした１ｗ
ｔ％エマルジョンを用いる伯は、使用する炭素繊維、サ
イジング付着方法などは実施例１と同様にしてサイジン
グ付着糸を１ｑだ。サイジング付着糸の評価結果を第１
表に示した。Example 4 As a sizing agent, in the [If] formula, R1=H,
R2=Oll, m=10. 1w with n = 10
In the case of using t% emulsion, the carbon fiber used, the sizing attachment method, etc. were the same as in Example 1, and the sizing attachment yarn was 1q. The first evaluation result of the sizing adhesive yarn
Shown in the table.
実施例５
サイジング剤として［Ｉｆ１］式において、Ｒ＋＝ＯＨ
。Example 5 As a sizing agent, in the [If1] formula, R+=OH
.
Ｒ２＝ Ｈ，ｍ ＝１５． ｎ ＝１０とした１ｗｔ％
エマルジョンを用いる他は、使用する炭素繊維２サイジ
ング付着方法などは実施例１と同様にしてサイジング付
着糸を得た。サイジング付着糸の評価結果を第１表に示
した。R2=H,m=15. 1wt% with n = 10
A sizing-attached yarn was obtained in the same manner as in Example 1 except that an emulsion was used, and the carbon fiber 2 sizing attachment method used was the same as in Example 1. The evaluation results of the sizing-attached yarn are shown in Table 1.
比較例１
ヒドロキシル価１１２のポリプロピレングリコール２６
０ｇに２・４−／２・６−ドリレンジイソシアネートの
８０／２０異性体混合物８７ｇ、Ｎ−メチルジェタノー
ルベンジンアンモニウムクロライド３４．３ｇを加え窒
素雰囲気中、４０’Ｃで約２時間反応させイソシアネー
ｉ〜１２．２３ｗｔ％、第四級窒素０．５１３ｗｔ％を
含有するウレタン化合物を１ｑだ。これにグリセロール
ジグリシジルエーテル４１．３ｇ、ＤＭＦ３３５．４ｇ
を加え５０℃で約３時間イソシアネート基がなくなるま
で反応させた。反応生成物はオキシラン酸素０．７４３
ｗｔ％、第四級窒素０．４７６ｗｔ％を含有する水分散
性の良好なものであった。Comparative Example 1 Polypropylene glycol 26 with a hydroxyl value of 112
0 g, 87 g of 80/20 isomer mixture of 2,4-/2,6-lylene diisocyanate, and 34.3 g of N-methyljetanol benzine ammonium chloride were added and reacted at 40'C in a nitrogen atmosphere for about 2 hours to obtain isocyanate. 1q of a urethane compound containing i~12.23 wt% and 0.513 wt% of quaternary nitrogen. To this, 41.3 g of glycerol diglycidyl ether, 335.4 g of DMF
was added and reacted at 50° C. for about 3 hours until the isocyanate group disappeared. The reaction product is oxirane oxygen 0.743
It had good water dispersibility, containing 0.476 wt% of quaternary nitrogen.
得られた上記ポリウレタンにエポキシ当最が２２５〜２
８０１平均分子量が約４７０１比重が約１１のビスフェ
ノールＡジグリシジルエーテルタイプの液状エポキシ樹
脂（シェル化学社製゛エピコート゛’ ８４３）の３０
ｗｔ％のジメチルホルムアミド溶液を４対１の割合で添
加し、次いで水を添加し、１ｗｔ％エマルジョンをサイ
ジング剤として用いる他は、使用する炭素繊維、サイジ
ング付着方法などは実施例１と同様にしてサイジング付
着糸を得た。サイジング付着糸の評価結果を第２表に示
した。The resulting polyurethane has an epoxy content of 225 to 2
30 of bisphenol A diglycidyl ether type liquid epoxy resin ('Epicote' 843 manufactured by Shell Chemical Co., Ltd.) with an average molecular weight of about 4701 and a specific gravity of about 11.
The carbon fibers used, the sizing attachment method, etc. were the same as in Example 1, except that a wt% dimethylformamide solution was added at a ratio of 4:1, water was then added, and a 1wt% emulsion was used as a sizing agent. A sizing adhesive yarn was obtained. The evaluation results of the sizing-attached yarn are shown in Table 2.
比較例２
サイジング剤として［Ｉ］式において、Ｒ１＝０１１゜
Ｒ２＝ Ｈ，ｍ ＝１５． ｎ ＝１５としたＱ、１ｗ
ｔ％エマルジョンを用いる他は、使用する炭素繊維、サ
イジング付着方法などは実施例１と同様にしてサイジン
グ付着糸を得た。サイジング付着糸の評価結果を第２表
に示した。Comparative Example 2 As a sizing agent, in formula [I], R1=011°R2=H,m=15. Q with n = 15, 1w
A sizing-attached yarn was obtained in the same manner as in Example 1, except that the t% emulsion was used, and the carbon fibers used and the sizing attachment method were the same as in Example 1. The evaluation results of the sizing-attached yarn are shown in Table 2.
比較例３ サイジング剤として［Ｉ］式において、Ｒ１＝ＯＨ。Comparative example 3 In formula [I] as a sizing agent, R1=OH.
Ｒ２＝ Ｉｆ、 ｍ ＝１５． ｎ ＝１５としたｉｏ
ｗｔ％エチルセロソルブ溶液を用いる他は、使用する炭
素繊維。R2=If, m=15. io with n = 15
Carbon fiber used except wt% ethyl cellosolve solution.
サイジング付着方法などは実施例１と同様にしてサイジ
ング付着糸を得た。サイジング付着糸の評価結果を第２
表に示した。A sizing-attached yarn was obtained using the same sizing-attaching method as in Example 1. The second evaluation result of the sizing adhesive yarn
Shown in the table.
比較例４
サイジング剤として［Ｉ］式において、Ｒ＋ ＝ ＯＨ
。Comparative Example 4 In formula [I] as a sizing agent, R+ = OH
.
Ｒ２＝ Ｈ，ｍ＝ １．ｎ＝ １とした１ｗｔ％エマル
ジョンを用いる他は、使用する炭素繊維、サイジング付
着方法などは実施例１と同様にしてサイジング付着糸を
得た。サイジング付着糸の評価結果を第２表に示した。R2=H, m=1. A sizing-attached yarn was obtained in the same manner as in Example 1 except that a 1 wt % emulsion with n=1 was used, and the carbon fibers used and the sizing attachment method were the same as in Example 1. The evaluation results of the sizing-attached yarn are shown in Table 2.
比較例５ サイジング剤として［Ｉ］式において、Ｒ＋＝Ｏｔｌ。Comparative example 5 In the formula [I] as a sizing agent, R+=Otl.
Ｒ２＝ Ｈ，ｍ ＝３０． ｎ ＝３０とした１ｗｔ％
エマルジョンを用いる他は、使用する炭素繊維、サイジ
ング付着方法などは実施例１と同様にしてサイジング付
着糸を得た。サイジング付着糸の評価結果を第２表に示
した。R2=H,m=30. 1wt% with n = 30
A sizing-attached yarn was obtained in the same manner as in Example 1 except that an emulsion was used, and the carbon fibers used and the sizing-attaching method were the same as in Example 1. The evaluation results of the sizing-attached yarn are shown in Table 2.
（以下、余白）
［発明の効果］
本発明の炭素繊維は、特定のサイジング剤を用いたこと
により、特に金属との摩擦係数が低く、集束性に優れて
いる。またマトリックス樹脂との相溶性もよい。(Hereinafter, blank spaces) [Effects of the Invention] The carbon fiber of the present invention has a particularly low coefficient of friction with metal and excellent cohesiveness due to the use of a specific sizing agent. It also has good compatibility with the matrix resin.
このため、プリプレグ化、ドラムワインド等の炭素繊維
の高次加工において、擦過毛羽の発生や糸切れが防止で
きるなど、作業性２品質に優れた複合材料用炭素繊維が
提供できるという、顕著な効果を奏する。Therefore, in high-order processing of carbon fibers such as prepreg and drum winding, it is possible to provide carbon fibers for composite materials with excellent workability and quality, such as preventing the occurrence of abrasion fuzz and thread breakage. play.
Claims (1)
とも１種の化合物を０．１〜５．０重量％付着させてな
る高次加工性の優れた炭素繊維。 ▲数式、化学式、表等があります▼［ I ］ ▲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▼［III］ 上式中、Ｒ＿１はＨ、ＯＨ、▲数式、化学式、表等があ
ります▼、または▲数式、化学式、表等があります▼、
Ｒ＿２はＨまたはＯＨであり、 ｍ、ｎは１〜４９、但しｍ＋ｎは１０〜５０である。[Claims] Carbon with excellent high-order processability, which is made by adhering 0.1 to 5.0% by weight of at least one compound selected from the following formulas [I], [II], and [III]. fiber. ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[III] In the above formula, R_1 is H, OH, ▲ There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼,
R_2 is H or OH, m and n are 1 to 49, provided that m+n is 10 to 50.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63100619A JP2685221B2 (en) | 1988-04-22 | 1988-04-22 | Carbon fiber with excellent high-order processability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63100619A JP2685221B2 (en) | 1988-04-22 | 1988-04-22 | Carbon fiber with excellent high-order processability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01272867A true JPH01272867A (en) | 1989-10-31 |
| JP2685221B2 JP2685221B2 (en) | 1997-12-03 |
Family
ID=14278857
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63100619A Expired - Fee Related JP2685221B2 (en) | 1988-04-22 | 1988-04-22 | Carbon fiber with excellent high-order processability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2685221B2 (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0533263A (en) * | 1990-11-30 | 1993-02-09 | Petoca:Kk | Reinforcing fiber for carbon carbon composite material and production of composite material |
| JPH0797138A (en) * | 1993-09-29 | 1995-04-11 | Toray Ind Inc | Coreless package of carbon fiber |
| JPH07214551A (en) * | 1994-01-28 | 1995-08-15 | Toray Ind Inc | Carbon fiber reinforced resin composite material and prepreg |
| US5462799A (en) * | 1993-08-25 | 1995-10-31 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| JPH08188968A (en) * | 1995-01-09 | 1996-07-23 | Toray Ind Inc | Carbon fiber and method for producing same |
| JPH08296148A (en) * | 1995-04-26 | 1996-11-12 | Toray Ind Inc | Carbon fiber sheet-like 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 |
| 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 |
| JP2013127132A (en) * | 2011-12-19 | 2013-06-27 | Toray Ind Inc | Sizing agent-applied carbon fiber |
| 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 |
| WO2014084194A1 (en) | 2012-11-27 | 2014-06-05 | 三菱レイヨン株式会社 | Fiber-reinforced thermoplastic resin prepreg, molded body of same, and method for producing fiber-reinforced thermoplastic resin prepreg |
| US9149828B2 (en) | 2013-08-09 | 2015-10-06 | Uht Unitech Co., Ltd. | Carbon fiber surface oil changing device |
| KR20160055983A (en) | 2014-11-08 | 2016-05-19 | 주식회사 효성 | Sizing agent for carbon-fiber, and carbon-fiber manufactured by using the same |
| WO2017151701A1 (en) | 2016-03-03 | 2017-09-08 | Dow Global Technologies Llc | Carbon fiber sizing agents for improved interfacial shear strength |
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| JPS5352796A (en) * | 1976-10-19 | 1978-05-13 | Sanyo Chemical Ind Ltd | Surface treating resin composition for carbon fiber and composite carbon fiber material containing said treated fiber |
| JPS6128074A (en) * | 1984-07-12 | 1986-02-07 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
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1988
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5352796A (en) * | 1976-10-19 | 1978-05-13 | Sanyo Chemical Ind Ltd | Surface treating resin composition for carbon fiber and composite carbon fiber material containing said treated fiber |
| JPS6128074A (en) * | 1984-07-12 | 1986-02-07 | 竹本油脂株式会社 | Sizing agent for carbon fiber |
Cited By (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0533263A (en) * | 1990-11-30 | 1993-02-09 | Petoca:Kk | Reinforcing fiber for carbon carbon composite material and production of composite material |
| US5589055A (en) * | 1993-08-25 | 1996-12-31 | Toray Industries, Inc. | Method for preparing carbon fibers |
| US5462799A (en) * | 1993-08-25 | 1995-10-31 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| US5691055A (en) * | 1993-08-25 | 1997-11-25 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| US5587240A (en) * | 1993-08-25 | 1996-12-24 | Toray Industries, Inc. | Carbon fibers and process for preparing same |
| JPH0797138A (en) * | 1993-09-29 | 1995-04-11 | Toray Ind Inc | Coreless package of carbon fiber |
| JPH07214551A (en) * | 1994-01-28 | 1995-08-15 | Toray Ind Inc | Carbon fiber reinforced resin composite material and prepreg |
| JPH08188968A (en) * | 1995-01-09 | 1996-07-23 | Toray Ind Inc | Carbon fiber and method for producing same |
| JPH08296148A (en) * | 1995-04-26 | 1996-11-12 | Toray Ind Inc | Carbon fiber sheet-like 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 |
| 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 |
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| JP2013127132A (en) * | 2011-12-19 | 2013-06-27 | Toray Ind Inc | Sizing agent-applied carbon fiber |
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| 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 |
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| 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 |
| 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 |
| 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 |
| KR20150065912A (en) | 2012-11-27 | 2015-06-15 | 미쯔비시 레이온 가부시끼가이샤 | Fiber-reinforced thermoplastic resin prepreg, molded body of same, and method for producing fiber-reinforced thermoplastic resin prepreg |
| US9752002B2 (en) | 2012-11-27 | 2017-09-05 | Mitsubishi Chemical Corporation | Fiber-reinforced thermoplastic resin prepreg, molded body of same, and method for producing fiber-reinforced thermoplastic resin prepreg |
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| US9149828B2 (en) | 2013-08-09 | 2015-10-06 | Uht Unitech Co., Ltd. | Carbon fiber surface oil changing device |
| KR20160055983A (en) | 2014-11-08 | 2016-05-19 | 주식회사 효성 | Sizing agent for carbon-fiber, and carbon-fiber manufactured by using the same |
| WO2017151701A1 (en) | 2016-03-03 | 2017-09-08 | Dow Global Technologies Llc | Carbon fiber sizing agents for improved interfacial shear strength |
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|---|---|
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