JP2005105465A - Functionalized fiber and method for producing functionalized fiber - Google Patents
Functionalized fiber and method for producing functionalized fiber Download PDFInfo
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- JP2005105465A JP2005105465A JP2003340892A JP2003340892A JP2005105465A JP 2005105465 A JP2005105465 A JP 2005105465A JP 2003340892 A JP2003340892 A JP 2003340892A JP 2003340892 A JP2003340892 A JP 2003340892A JP 2005105465 A JP2005105465 A JP 2005105465A
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- Prior art keywords
- fiber
- liquid
- functionalized
- functionalized fiber
- manufacturing
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- 238000000034 method Methods 0.000 claims abstract description 21
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Images
Abstract
Description
本発明は、機能化繊維の製造方法および機能化繊維に関する。さらに詳しくは、繊維表面に所定の化合物を付着せしめ、繊維表面を改質する機能化繊維の製造方法および機能化繊維に関する。 The present invention relates to a method for producing a functionalized fiber and a functionalized fiber. More specifically, the present invention relates to a functionalized fiber manufacturing method and a functionalized fiber in which a predetermined compound is adhered to the fiber surface to modify the fiber surface.
繊維は、衣料用のみならず、産業用としてその素材や諸性質をニーズに合わせて様々に変えることによって極めて広範に用いられているが、中でも高性能あるいは高付加価値が求められる領域においては、その表面性状の制御あるいは表面加工は重要な位置を占めている。例えば、衣料用のポリエステル繊維に、親水性を導入して吸湿性や吸水性あるいは防汚性や制電性を付与したり、低屈折率性を付与したり表面凹凸を付与したりして高発色性を発現させたりする等、多岐に及ぶ加工がなされているが、さらに高機能を付与することによる新たな用途への応用も期待されている。 Fiber is used not only for clothing but also for industrial use by changing its materials and properties in various ways according to needs, but especially in areas where high performance or high added value is required, Control of surface properties or surface processing occupies an important position. For example, by introducing hydrophilicity into polyester fibers for clothing to impart hygroscopicity, water absorption, antifouling properties, antistatic properties, low refractive index properties, or surface irregularities, Various processings such as developing color development have been made, but application to new applications by further providing high functionality is also expected.
また、産業用として、繊維を強化材とし、熱硬化性樹脂や熱可塑性樹脂などのマトリックス樹脂で固めた複合材料に用いる場合には、目的や用途に応じて様々な繊維とマトリックス樹脂が組み合わせられているが、いずれにしても複合材料として、繊維の弾性率や強度を有効に利用するために、マトリックス樹脂と強固に接着するための表面加工が施されている。例えば、比強度、比弾性率に優れた炭素繊維を用いた複合材料の場合、特にポリアクリロニトリル系前駆体繊維を出発原料とした炭素繊維の場合、炭素繊維の製造工程の仕上げとして酸化処理を施して炭素繊維表面に官能基を付与することが一般的である。しかしながら、炭化温度を高くして弾性率を上げていくと、炭素繊維と樹脂との接着が悪くなるという現象が認められる。この原因は炭化温度を上げるに従って、炭素繊維のグラファイト構造の結晶が大きくなり、酸化され難くなる。これに伴い、樹脂との接着に十分な官能基が付与されにくくなるためと推定される。このようなことから、弾性率の高い炭素繊維ほど、より強い酸化処理が必要となるが、酸化処理だけでは十分な樹脂との接着力が得られにくいという問題があった。 In addition, when used in a composite material made of fiber as a reinforcing material and hardened with a matrix resin such as a thermosetting resin or a thermoplastic resin for industrial use, various fibers and matrix resins can be combined depending on the purpose and application. However, in any case, in order to effectively use the elastic modulus and strength of the fiber as a composite material, surface processing is performed to firmly adhere to the matrix resin. For example, in the case of a composite material using carbon fibers having excellent specific strength and specific elastic modulus, particularly in the case of carbon fibers starting from polyacrylonitrile-based precursor fibers, an oxidation treatment is applied as a finishing step for the production process of carbon fibers. In general, a functional group is imparted to the carbon fiber surface. However, when the carbonization temperature is raised and the elastic modulus is increased, a phenomenon that the adhesion between the carbon fiber and the resin is deteriorated is recognized. The cause of this is that as the carbonization temperature is raised, the crystals of the carbon fiber graphite structure become larger and are less likely to be oxidized. In connection with this, it is estimated that it becomes difficult to provide a functional group sufficient for adhesion to the resin. For this reason, a carbon fiber having a higher elastic modulus requires a stronger oxidation treatment, but there is a problem that it is difficult to obtain a sufficient adhesive force with a resin only by the oxidation treatment.
また、上記例のように、炭素繊維をそのまま複合材料に適用した場合は、マトリックス樹脂の耐熱性が上限となるためあまり問題にならないが、航空・宇宙用途等の温度面で厳しい環境下で使用される繊維またはその複合材料は、炭素繊維では充分ではなく、シリコンカーバイド繊維等が用いられることもあるが高コストであり、本質的には炭素繊維の表面に十分な耐熱性や耐酸化性と、複合材料として用いる場合は、マトリックスとなる金属やセラミックス等との接着性とが改善されれば、より低コストな炭素繊維を用いることも可能である。これに対して、特許文献１にはシラン誘導体を原料ガスとし、プラズマ気相合成法によりシリコンカーバイドを炭素繊維表面に形成させる方法が開示されている。しかしながら、マトリックスとのより高い接着性発現のためにはこれだけでは十分とは言えない。このように、繊維表面の特性を制御する技術は多岐にわたる応用が試みられているものの、これらを自在に制御できる技術は見いだされていないのが現状である。
本発明の課題は、上記のような現状に鑑み、繊維表面に種々の化合物を付着せしめ、各種機能を有する機能化繊維を効率よく製造できる技術を提供することにある。 In view of the current situation as described above, an object of the present invention is to provide a technique capable of efficiently producing functionalized fibers having various functions by attaching various compounds to the fiber surface.
上記課題を解決するために、本発明に係る機能化繊維の製造方法は、繊維を液体に浸漬し、該液体中で気泡を発生させるとともに、該液体中に電磁波を照射することにより、前記液体に起因した化合物を繊維に付着せしめることを特徴とする方法からなる。 In order to solve the above-described problem, the method for producing a functionalized fiber according to the present invention includes immersing a fiber in a liquid, generating bubbles in the liquid, and irradiating the liquid with electromagnetic waves. The method is characterized by adhering a compound derived from the above to the fiber.
この機能化繊維の製造方法においては、上記液体中での気泡の発生は、例えば超音波照射により行うことができる。また、上記一連の処理を、減圧下で行うことができる。また、必要に応じて液体を加熱することが好ましい。さらに、必要に応じて液体に浸漬せしめる繊維も加熱することができる。 In this method for producing a functionalized fiber, the generation of bubbles in the liquid can be performed by, for example, ultrasonic irradiation. Further, the above series of treatments can be performed under reduced pressure. Moreover, it is preferable to heat a liquid as needed. Furthermore, the fiber immersed in the liquid can be heated as necessary.
上記液体に浸漬せしめる繊維としては、例えば炭素繊維を用いることができる。液体としては、炭素を有する化合物を含む液体、有機化合物を含む液体、炭化水素またはアルコールを含む液体等を用いることができる。さらに、珪素を有する化合物を含む液体、シリコーンを含む液体等を用いることができる。これらの液体は、水を含むものであってもよい。 As the fiber immersed in the liquid, for example, carbon fiber can be used. As the liquid, a liquid containing a compound having carbon, a liquid containing an organic compound, a liquid containing hydrocarbon or alcohol, or the like can be used. Furthermore, a liquid containing a compound containing silicon, a liquid containing silicone, or the like can be used. These liquids may contain water.
また、本発明に係る機能化繊維の製造方法においては、上記液体に浸漬した繊維を一定の速度で動かすことにより、繊維を連続処理するようにすることもできる。また、液体に起因した化合物を繊維に付着せしめた後、該繊維を必要に応じて酸化処理するようにすることもできる。 Moreover, in the manufacturing method of the functionalized fiber which concerns on this invention, a fiber can also be made to process continuously by moving the fiber immersed in the said liquid at a fixed speed | rate. In addition, after the compound derived from the liquid is adhered to the fiber, the fiber may be oxidized as necessary.
上記液体に起因した化合物としては、例えば、アモルファス性炭素やシリコンカーバイドを挙げることができる。 Examples of the compound derived from the liquid include amorphous carbon and silicon carbide.
本発明に係る機能化繊維は、上記のような方法によって製造されたものである。この機能化繊維は、とくに、表面に凹凸を有することが好ましい。 The functionalized fiber according to the present invention is produced by the method as described above. This functionalized fiber preferably has irregularities on the surface.
より具体的な本発明に係る機能化繊維は、例えば、アモルファス性炭素が付着してなり、表面が凹凸を有する機能化繊維からなる。この機能化繊維においては、ラマン分光法により求められるラマンスペクトルのＧバンドに対するＤバンドの強度比が０．２以上であることが好ましい。 More specifically, the functionalized fiber according to the present invention is made of, for example, a functionalized fiber to which amorphous carbon is attached and whose surface has irregularities. In this functionalized fiber, the intensity ratio of the D band to the G band of the Raman spectrum obtained by Raman spectroscopy is preferably 0.2 or more.
また、本発明に係る機能化繊維は、例えば、Ｘ線光電子分光法から求められる炭素原子数に対する硅素原子数の比が０．３〜３の範囲内にあり、表面が凹凸を有する機能化繊維からなる。 In addition, the functionalized fiber according to the present invention is, for example, a functionalized fiber in which the ratio of the number of silicon atoms to the number of carbon atoms determined by X-ray photoelectron spectroscopy is in the range of 0.3 to 3, and the surface is uneven. Consists of.
また、本発明に係る機能化繊維は、例えば、シリコンカーバイドが付着してなり、表面が凹凸を有する機能化繊維からなる。 In addition, the functionalized fiber according to the present invention is made of functionalized fiber having, for example, silicon carbide attached and a surface having irregularities.
さらに、本発明に係る機能化繊維は、例えば、Ｘ線光電子分光法から求められる炭素原子数に対する酸素原子数の比が０．０１〜１の範囲内にあり、表面が凹凸を有する機能化繊維からなる。 Furthermore, the functionalized fiber according to the present invention is, for example, a functionalized fiber in which the ratio of the number of oxygen atoms to the number of carbon atoms determined by X-ray photoelectron spectroscopy is in the range of 0.01 to 1, and the surface has irregularities. Consists of.
本発明によれば、以下に詳述するように、繊維に炭素性物質や耐熱性物質等を効率良く付着または蒸着でき、その表面が凹凸であるため、表面積を大きくすることも可能である。また、そのような表面積の大きい繊維は、例えば繊維強化複合材料にした場合に、良好な接着性が得られ、ひいては複合材料の力学物性が向上する。さらに、付着せしめる化合物を選択することにより吸着能を付与することもできる。このように、要求機能に応じた機能化繊維が確実に得られるようになる。 According to the present invention, as described in detail below, a carbonaceous material, a heat-resistant material, or the like can be efficiently attached or deposited on the fiber, and the surface thereof is uneven, so that the surface area can be increased. Further, when such a fiber having a large surface area is made into a fiber-reinforced composite material, for example, good adhesiveness is obtained, and as a result, the mechanical properties of the composite material are improved. Furthermore, adsorption ability can be imparted by selecting a compound to be adhered. Thus, the functionalized fiber according to a required function comes to be obtained reliably.
以下に、本発明の望ましい実施の形態を、図面も参照しながら実施例とともに説明する。
本発明に係る機能化繊維の製造方法は、繊維を液体に浸漬し、該液体中で気泡を発生させるとともに、該液体中に電磁波を照射することにより、前記液体に起因した化合物を繊維に付着せしめるものである。ここで用いる液体は、特に限定されないが、目的に応じて炭素を有する化合物、珪素を有する化合物、水または水溶液をそれぞれ単独もしくは混合して用いるのが好ましい。それぞれの液体の詳細については後述するが、いずれの液体においても、本発明では、液体中で気泡を発生させるとともに、該液体中に電磁波を照射することにより、該液体に起因した化合物を繊維に付着せしめる。例えば液体として炭素を有する化合物を用いた場合、炭素性物質が繊維に付着または蒸着されることになる。この際、公知のＣＶＤ法などの気相プラズマで得られる炭素性物質の膜は実質的に平滑であるのに対し、本発明による炭素性物質の付着または蒸着の形態は、凹凸を有する特異的なものとなるため、マトリックス樹脂との接触面積が増大し、更にはマトリックス樹脂の炭素性物質へのアンカー効果も発現し、接着力が非常に向上する。使用する液体が珪素を有する化合物では、繊維に耐酸化性及び／または耐熱性物質が付着または蒸着されることになるが、炭素を有する化合物の場合と同様に凹凸を有する特異的な表面となり、セラミックスや金属への接着が強固になる。使用する液体が水単独の場合は、繊維に付着または蒸着されるものはないが、繊維がエッチングされて凹凸を有する表面になると共に親水性官能基が導入されるので、やはりマトリックス樹脂との接着性は高くなる。なお、本発明で言う凹凸を有する表面としては、凸部の頂点と凹部の底との高低差が０．０１〜５００μｍの範囲内であるのが好ましく、０．０５〜２００μｍの範囲内であるのがより好ましく、０．１〜１００μｍの範囲内であるのが更に好ましい。０．０１μｍ以下では、凹凸による接着性向上や比表面積増大による各種分子等の高吸着性等があまり発現せず、５００μｍ以上にしても効果は飽和する。接着性向上の場合については、むしろ５０μｍ以下が好ましく、１０μｍ以下が更に好ましい。これらは、数十倍〜数万倍程度の拡大倍率の走査型電子顕微鏡（ＳＥＭ）や、試料の断面をミクロトーム等で超薄切片化して切り出し、透過型電子顕微鏡（ＴＥＭ）で観察することによって、容易に判別できる。ＴＥＭによる断面観察の場合は、少なくとも２つの凸部の頂点に接する外接円の半径と、少なくとも２つの凹部の底に接する内接円の半径との差から、凹凸の高低差を求めることができる。
Hereinafter, preferred embodiments of the present invention will be described together with examples with reference to the drawings.
The method for producing a functionalized fiber according to the present invention includes immersing a fiber in a liquid, generating bubbles in the liquid, and irradiating an electromagnetic wave in the liquid, thereby attaching a compound derived from the liquid to the fiber. It is what you want to do. The liquid used here is not particularly limited, but it is preferable to use a carbon-containing compound, a silicon-containing compound, water, or an aqueous solution, either alone or as a mixture, depending on the purpose. Although details of each liquid will be described later, in any liquid, the present invention generates bubbles in the liquid and irradiates the liquid with an electromagnetic wave, whereby the compound resulting from the liquid is applied to the fiber. Adhere. For example, when a compound having carbon as a liquid is used, a carbonaceous substance is attached to or deposited on the fiber. At this time, the film of carbonaceous material obtained by a vapor phase plasma such as a known CVD method is substantially smooth, whereas the form of carbonaceous material deposition or vapor deposition according to the present invention is unique with irregularities. Therefore, the contact area with the matrix resin is increased, and further, the anchor effect of the matrix resin to the carbonaceous material is exhibited, and the adhesive force is greatly improved. In the case where the liquid used is a compound having silicon, oxidation resistance and / or heat-resistant substances are attached to or deposited on the fiber, but as with the compound having carbon, it becomes a specific surface having irregularities, Adhesion to ceramics and metals is strengthened. When the liquid used is water alone, nothing adheres to or is deposited on the fibers, but the fibers are etched to form uneven surfaces and hydrophilic functional groups are introduced. Sexuality increases. In addition, as a surface which has the unevenness | corrugation said by this invention, it is preferable that the height difference of the peak of a convex part and the bottom of a recessed part exists in the range of 0.01-500 micrometers, and it exists in the range of 0.05-200 micrometers. Is more preferable, and it is still more preferable that it exists in the range of 0.1-100 micrometers. When the thickness is 0.01 μm or less, improvement in adhesion due to unevenness and high adsorptivity of various molecules due to increase in specific surface area do not appear so much, and the effect is saturated even when the thickness is 500 μm or more. In the case of improving adhesiveness, it is preferably 50 μm or less, and more preferably 10 μm or less. These can be obtained by scanning electron microscopes (SEM) with magnifications of several tens to tens of thousands of times, or by slicing and cutting out the cross section of a sample with a microtome or the like and observing with a transmission electron microscope (TEM). Can be easily identified. In the case of cross-sectional observation by TEM, the height difference of the unevenness can be obtained from the difference between the radius of the circumscribed circle in contact with the vertices of at least two convex portions and the radius of the inscribed circle in contact with the bottoms of at least two concave portions. .
以下、本発明の機能化繊維の製造方法に用いる各液体について更に詳しく説明する。
本発明に使用できる前記炭素性物質の原料となる液体は、炭素原子を含む化合物、好ましくは有機化合物を含んでいれば、その種類は特に限定されない。炭素原子を含む化合物として、好ましくは、炭素原子と水素分子のみからなる脂肪族系及び芳香族系の飽和炭化水素、不飽和炭化水素や、それらの１つ以上の水素を水酸基に置換したアルコール類が用いることができるが、カルボニル基やエーテル結合、エステル結合、カルボキシル基、アミノ基、４級アミン、アミド結合、スルホン酸基等が含まれていても構わない。これらは、液体として単独で用いる場合には、液体として存在できる温度、即ち融点より高く、かつ沸点より低い温度領域で本発明に利用できるが、より簡便に本発明を実施するためには常温（１５〜２５℃）で液体状であるのが好ましい。従って、より好ましい一例として、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、シクロペンタン、シクロヘキサン、シクロヘプタン、シクロオクタン、シクロノナン、シクロペンテン、シクロヘキセン、シクロヘプテン、シクロヘキサジエン、シクロペンタジエン、シクロヘキシルベンゼン、シクロオクタテトラエン、イソプレン、ベンゼン、トルエン、キシレン、エチルトルエン、ジエチルベンゼン、ジビニルベンゼン、ジメチルビフェニル、メタノール、エタノール、プロパノール、ブチルアルコール、イソペンチルアルコール、ヘプタノール、オクタノール、ｏ−エチルフェノール、シクロペンタノール、アリルアルコール、ウルシオール、ウンデカノール、スチレン、アセトン、メチルエチルケトン、メチルイソブチルケトン、酢酸、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、アクリルアミド、ポリオキシエチレンを親水部とし、アルキル基に代表される炭化水素類やポリオキシアルキレン（ポリオキシ（メ）エチレンを除く）を疎水部とする界面活性剤、等が挙げられる。
Hereafter, each liquid used for the manufacturing method of the functionalized fiber of this invention is demonstrated in more detail.
The liquid used as a raw material for the carbonaceous material that can be used in the present invention is not particularly limited as long as it contains a compound containing a carbon atom, preferably an organic compound. The compound containing a carbon atom is preferably an aliphatic or aromatic saturated hydrocarbon or unsaturated hydrocarbon consisting of only a carbon atom and a hydrogen molecule, or an alcohol in which one or more of these hydrogens are substituted with a hydroxyl group. May be used, but may contain a carbonyl group, an ether bond, an ester bond, a carboxyl group, an amino group, a quaternary amine, an amide bond, a sulfonic acid group, or the like. When used alone as a liquid, these can be used in the present invention at a temperature range that can exist as a liquid, that is, in a temperature range that is higher than the melting point and lower than the boiling point. 15 to 25 ° C.) and is preferably liquid. Accordingly, as a more preferred example, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, pentadecane, hexadecane, heptadecane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclopentene, cyclohexene, cycloheptene, Cyclohexadiene, cyclopentadiene, cyclohexylbenzene, cyclooctatetraene, isoprene, benzene, toluene, xylene, ethyltoluene, diethylbenzene, divinylbenzene, dimethylbiphenyl, methanol, ethanol, propanol, butyl alcohol, isopentyl alcohol, heptanol, octanol, o-Ethylphenol, cyclopentanol, allyl alcohol, urushi , Undecanol, styrene, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetic acid, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, acrylamide, polyoxyethylene Examples of the hydrophilic part include hydrocarbons typified by alkyl groups and surfactants having polyoxyalkylene (excluding polyoxy (me) ethylene) as a hydrophobic part.
これらの中でも、炭素収率が高い炭化水素類や、電磁波や超音波の減衰が抑制されるように、使用する温度における粘度が低いものは特に好ましく用いられる。この一例としては、ドデカンやベンゼン、メタノール、エタノールが挙げられる。これらの炭素を含む化合物は、単独または混合で用いるのが、プラズマに対して原料供給濃度が最も高い状態となり好ましいが、上記例のように炭素を有する化合物自体が液体である場合に加え、炭素を有する化合物が個体または気体である場合には、各種液状媒体に溶解した溶液や水溶液、各種液状媒体に乳化または分散させた乳化液、分散液、水系乳化液、水系分散液も用いることができる。上記で発生する炭素性物質は、プラズマの諸条件によって、ダイアモンドや黒鉛等の結晶性炭素や、実質的に完全なアモルファスやダイアモンド状炭素（ＤＬＣ；Ｄｉａｍｏｎｄ Ｌｉｋｅ Ｃａｒｂｏｎ）等のアモルファス性炭素、それらの混合物が得られ、繊維上に不均一に付着し、凹凸表面を形成したものとなる。マトリックス樹脂との接着性を高めるため、及び酸化処理するためには、アモルファス性炭素の方が好ましい。アモルファス性炭素として好ましい状態は、ラマン分光法により求められるラマンスペクトルのＧバンドに対するＤバンドの比（以下、Ｄ／Ｇ比という）が０．２以上であることが好ましく、０．５以上であることがより好ましく、０．７以上であることが更に好ましい。上限は特に限定されず、実質的にＧバンドの強度が０の場合には、理想的なアモルファス状態でありＤ／Ｇ比は∞となる。ここでＤ／Ｇ比とは、１３５０ｃｍ-1付近のＤバンドピークと１５８０ｃｍ-1付近のＧバンドピークとを波形解析し、それぞれの面積の比から算出することができる。なお、ラマン分光測定及びＤ／Ｇ比の測定は、例えば日本電子（株）製ＪＲＳ−ＳＹＳＴＥＭ １０００を用い、Ａｒレーザー、波長５１４ｎｍ、スポット径１μｍ、露光時間１０秒、ラマンスペクトル測定領域０〜２０００ｃｍ-1、の条件で測定することができ、得られたラマンスペクトルにおいて、ＤバンドピークとＧバンドピークの間に存在する１４５０〜１５００ｃｍ-1付近の最低強度部と１０００〜１３００ｃｍ-1の間にフィッティング良くベースラインを引き、そのベースラインとＤバンドピークで囲まれた領域の面積を、前記ＤバンドピークとＧバンドピークの間の最低強度部と１６５０〜１７００ｃｍ-1の間にフィッティング良くベースラインを引き、そのベースラインとＧバンドピークで囲まれた領域の面積で割ることによってＤ／Ｇ比を算出できる。 Among these, hydrocarbons having a high carbon yield and those having a low viscosity at the used temperature are particularly preferably used so that attenuation of electromagnetic waves and ultrasonic waves is suppressed. Examples of this include dodecane, benzene, methanol, and ethanol. These carbon-containing compounds are preferably used alone or in a mixture because the raw material supply concentration is highest with respect to plasma, but in addition to the case where the carbon-containing compound itself is liquid as in the above example, carbon In the case where the compound having a solid is a solid or a gas, a solution or an aqueous solution dissolved in various liquid media, an emulsion, a dispersion, an aqueous emulsion, or an aqueous dispersion emulsified or dispersed in various liquid media can also be used. . The carbonaceous material generated above may be crystalline carbon such as diamond or graphite, amorphous carbon such as substantially complete amorphous or diamond-like carbon (DLC), depending on various plasma conditions. A mixture is obtained, which adheres unevenly on the fibers and forms an uneven surface. Amorphous carbon is preferred for enhancing the adhesion to the matrix resin and for oxidizing treatment. A preferable state as amorphous carbon is that the ratio of the D band to the G band of the Raman spectrum obtained by Raman spectroscopy (hereinafter referred to as the D / G ratio) is preferably 0.2 or more, and more preferably 0.5 or more. Is more preferable, and it is still more preferable that it is 0.7 or more. The upper limit is not particularly limited, and when the intensity of the G band is substantially 0, it is an ideal amorphous state and the D / G ratio is ∞. Here, the D / G ratio, it is possible to waveform analysis and G band peak near D band peak and 1580 cm -1 in the vicinity of 1350 cm -1, is calculated from the ratio of the respective areas. In addition, the Raman spectroscopic measurement and the measurement of D / G ratio are, for example, JRS-SYSTEM 1000 manufactured by JEOL Ltd., Ar laser, wavelength 514 nm, spot diameter 1 μm, exposure time 10 seconds, Raman spectrum measurement region 0 to 2000 cm. -1 it can be measured at the conditions, in the Raman spectrum obtained during the 1450～1500Cm -1 near the minimum strength part and 1,000 to -1 existing between the D band peak and G band peak Draw a base line with a good fitting, and the area of the region surrounded by the base line and the D band peak is a base line with a good fit between the lowest intensity part between the D band peak and the G band peak and 1650-1700 cm -1. And divide by the area surrounded by the baseline and the G band peak. Thus, the D / G ratio can be calculated.
一方、ダイアモンドが主となる皮膜が所望の場合は、炭化水素、例えばドデカンを用いると、アモルファスやグラファイトを還元して排除できるため、好ましく用いることができる。 On the other hand, when a film mainly composed of diamond is desired, use of a hydrocarbon such as dodecane can be preferably used because amorphous or graphite can be reduced and eliminated.
本発明に使用できる前記耐酸化性及び／または耐熱性物質の原料となる液体は、珪素原子を含む化合物、好ましくは珪素原子と炭素原子を含んでいれば、その種類は特に限定されない。その例としては、メチルハイドロジェンポリシロキサンやジメチルポリシロキサン等のジオルガノポリシロキサンやそれらのアミノ変性やエポキシ変性やポリエーテル変性等の各種変性物に代表されるシロキサン骨格を有するシリコーン類、各種シラン等が挙げられる。これらを原料としてプラズマ処理すると、繊維上に凹凸表面のシリコンカーバイド等の耐酸化性及び／または耐熱性物質が得られる。ここで、本発明の機能化繊維は、Ｘ線光電子分光法（ＥＳＣＡまたはＸＰＳ）により求められる炭素原子数に対する硅素原子数の比（以下、Ｓｉ／Ｃ比という）が０．３〜３の範囲内にあることが好ましく、０．５〜２の間がより好ましく、０．７〜１．５の間が更に好ましい。また、シリコンカーバイドが機能化繊維の表層を形成していることがなかんずく好ましい。Ｓｉ／Ｃ比が０．３未満であると、シリコンカーバイド等の耐酸化性及び／または耐熱性物質による被覆が十分ではなく、耐熱性向上等の機能化効果が不十分な場合がある。一方、Ｓｉ／Ｃ比が３を超えると、硅素原子が多くなりすぎて、かえって耐熱性が低下する場合がある。 The liquid used as a raw material for the oxidation-resistant and / or heat-resistant substance that can be used in the present invention is not particularly limited as long as it contains a compound containing a silicon atom, preferably a silicon atom and a carbon atom. Examples include diorganopolysiloxanes such as methylhydrogenpolysiloxane and dimethylpolysiloxane, silicones having a siloxane skeleton typified by various modified products such as amino-modified, epoxy-modified and polyether-modified, and various silanes. Etc. When these materials are used as a raw material, an oxidation-resistant and / or heat-resistant substance such as silicon carbide on the uneven surface is obtained on the fiber. Here, in the functionalized fiber of the present invention, the ratio of the number of silicon atoms to the number of carbon atoms determined by X-ray photoelectron spectroscopy (ESCA or XPS) (hereinafter referred to as Si / C ratio) is in the range of 0.3 to 3. It is preferably within the range, more preferably between 0.5 and 2, and even more preferably between 0.7 and 1.5. Moreover, it is preferable that silicon carbide forms the surface layer of the functionalized fiber. When the Si / C ratio is less than 0.3, the coating with an oxidation resistance and / or heat resistant material such as silicon carbide is not sufficient, and the functionalization effect such as improvement in heat resistance may be insufficient. On the other hand, if the Si / C ratio exceeds 3, the amount of silicon atoms becomes excessive and the heat resistance may be lowered.
ここでＳｉ／Ｃ比はＸ線光電子分光法により、Ｘ線源として、ＡｌＫα１，２あるいはＭｇＫα１，２を用いて測定することができる。尚、測定時の帯電に伴うピークの補正は、Ｃ１ｓの主ピークの結合エネルギー値Ｂ．Ｅ．を２８４．６ｅＶに合わせることで実施できる。次いで、Ｃ１ｓピーク面積［Ｃ１ｓ］は、２８０〜２９０ｅＶの範囲で直線のベースラインを引くことにより求め、Ｓｉ２ｐピーク面積［Ｓｉ２ｐ］は９４〜１１０ｅＶの範囲で直線のベースラインを引くことにより求める。 Here, the Si / C ratio can be measured by X-ray photoelectron spectroscopy using AlKα1,2 or MgKα1,2 as the X-ray source. In addition, the correction of the peak accompanying charging at the time of measurement is the binding energy value B.B. E. To 284.6 eV. Next, the C1s peak area [C1s] is obtained by drawing a straight base line in the range of 280 to 290 eV, and the Si2p peak area [Si2p] is obtained by drawing a straight base line in the range of 94 to 110 eV.
したがって、Ｓｉ／Ｃ比は、上記Ｓｉ２ｐピーク面積［Ｓｉ２ｐ］、Ｃ１ｓピーク面積［Ｃ１ｓ］の比、及び装置固有の感度補正値より、次式により求めることができる。
Ｓｉ／Ｃ＝（［Ｓｉ２ｐ］／［Ｃ１ｓ］）／（感度補正値）
なお、測定する機能化繊維にサイジング剤等の後処理剤が付着している場合は、塩化メチレン、メチルエチルケトン、アセトン、エタノールなどの溶媒で洗浄し、蒸留水で洗い流し、必要に応じて超音波洗浄するなどしてサイジング剤などを除去後、適当な長さにカットしてステンレス製の試料支持台上に拡げて並べた後、上記条件にて測定できるものである。また、バインダーなどと混合されている機能化繊維について測定する場合は、塩化メチレン、メチルエチルケトン、アセトン、エタノールなどの溶媒で樹脂を除去して機能化繊維を取り出し同様の方法で測定できるものである。
Therefore, the Si / C ratio can be obtained from the ratio of the Si2p peak area [Si2p], the C1s peak area [C1s], and the sensitivity correction value unique to the apparatus by the following equation.
Si / C = ([Si2p] / [C1s]) / (sensitivity correction value)
If a post-treatment agent such as a sizing agent is attached to the functionalized fiber to be measured, wash it with a solvent such as methylene chloride, methyl ethyl ketone, acetone, or ethanol, wash it off with distilled water, and ultrasonically wash it if necessary. After removing the sizing agent and the like by cutting, it is cut to an appropriate length, spread and arranged on a stainless steel sample support, and then measured under the above conditions. Moreover, when measuring about the functionalized fiber mixed with the binder etc., resin can be removed with solvents, such as a methylene chloride, methyl ethyl ketone, acetone, ethanol, and it can take out and measure by the same method.
本発明に使用できる前記耐酸化性及び／または耐熱性物質の原料となる液体は、単独または混合で用いるのが、原料供給濃度が最も高い状態となり好ましいが、上記例のように化合物自体が液体である場合に加え、珪素を有する化合物が個体または気体である場合には、各種液状媒体に溶解した溶液や水溶液、各種液状媒体に乳化または分散させた乳化液、分散液、水系乳化液、水系分散液も用いることができる。 The liquid used as a raw material for the oxidation-resistant and / or heat-resistant substance that can be used in the present invention is preferably used alone or in combination because the raw material supply concentration is the highest, but the compound itself is liquid as in the above example. In addition, when the silicon-containing compound is a solid or a gas, a solution or an aqueous solution dissolved in various liquid media, an emulsion emulsified or dispersed in various liquid media, a dispersion, an aqueous emulsion, an aqueous system Dispersions can also be used.
本発明における液体に水を用いた場合には、繊維のエッチング及び／または水酸基やカルボニル基、カルボキシル基、過算基等の親水性官能基の付与が行え、マトリックス樹脂との向上に寄与する。上述したように、炭素を有する化合物が水に溶解または乳化または分散させた場合には、繊維に炭素性物質が生成されると共にその表面に親水性官能基も導入されるので、マトリックス樹脂との接着性は非常に高くなる。衣料用繊維に適用した場合には、吸湿性や吸水性、制電性、ＳＲ（Ｓｏｉｌ Ｒｅｌｅａｓｅ）性等が発現し、エッチング状態が凹凸を有する形態であれば、黒や有彩色でも高発色化が可能になる。また、水溶液の媒質として、銅や鉄やチタンやアルミニウム等の種々の金属化合物がイオンとして溶解していたり、乳化または分散していても、それぞれに応じた金属を有する皮膜が繊維に形成される。例えば、硫酸銅水溶液を用いた場合には、銅の被膜が繊維に形成され、導電性に優れた繊維を製造できる。液体として水を用いた場合には、Ｘ線光電子分光法により求められる炭素原子数に対する酸素原子数の比（以下、Ｏ／Ｃ比という）が０．０１〜１の範囲内にあることが好ましく、０．１〜１がより好ましい。かかるＯ／Ｃが０．０１未満であると、接着性が充分に向上しない場合があり、１を超えても接着性向上は飽和しており、場合によっては水分保持を起こして接着不良や加水分解等の悪影響を及ぼす場合がある。 When water is used as the liquid in the present invention, the fiber can be etched and / or hydrophilic functional groups such as hydroxyl groups, carbonyl groups, carboxyl groups, and excess groups can be added, which contributes to improvement of the matrix resin. As described above, when a compound having carbon is dissolved or emulsified or dispersed in water, a carbonaceous material is generated in the fiber and a hydrophilic functional group is also introduced on the surface thereof. Adhesion is very high. When applied to textiles for clothing, hygroscopicity, water absorption, antistatic properties, SR (Soil Release) properties, etc. are manifested, and if the etching state is uneven, high color is produced even in black and chromatic colors Is possible. Further, even when various metal compounds such as copper, iron, titanium, and aluminum are dissolved as ions or emulsified or dispersed as an aqueous medium, a film having a metal corresponding to each of them is formed on the fiber. . For example, when an aqueous copper sulfate solution is used, a copper film is formed on the fiber, and a fiber having excellent conductivity can be produced. When water is used as the liquid, the ratio of the number of oxygen atoms to the number of carbon atoms determined by X-ray photoelectron spectroscopy (hereinafter referred to as O / C ratio) is preferably in the range of 0.01 to 1. 0.1 to 1 is more preferable. If the O / C is less than 0.01, the adhesiveness may not be sufficiently improved. If the O / C exceeds 1, the improvement in adhesiveness is saturated. May have adverse effects such as decomposition.
ここでＯ／Ｃ比は、前記Ｓｉ／Ｃ比と同様の手法により求められる。なお、Ｏ１ｓピーク面積［Ｏ１ｓ］は５２８〜５４０ｅＶの範囲で直線のベースラインを引くことにより求める。Ｏ／Ｃ比は、上記Ｏ１ｓピーク面積［Ｏ１ｓ］、Ｃ１ｓピーク面積［Ｃ１ｓ］の比、及び装置固有の感度補正値より、次式により求めることができる。
Ｏ／Ｃ＝（［Ｏ１ｓ］／［Ｃ１ｓ］）／（感度補正値）
Here, the O / C ratio is obtained by the same method as the Si / C ratio. The O1s peak area [O1s] is obtained by drawing a straight base line in the range of 528 to 540 eV. The O / C ratio can be obtained from the ratio of the O1s peak area [O1s], the C1s peak area [C1s], and the sensitivity correction value unique to the apparatus according to the following equation.
O / C = ([O1s] / [C1s]) / (sensitivity correction value)
本発明に用いられる繊維は、特に限定されず、ポリエチレンやポリプロピレン等の炭化水素系、ポリエチレンテレフタレート等のポリエステル、ナイロン−６やナイロン−６，６等のポリアミド、アラミド系、ポリイミド系、ポリフェニレンサルファイド系、ポリパラフェニレンベンズオキサゾール等のポリベンズアゾール、ガラス、シリコンカーバイド系、ボロン系、アルミナ系、各種金属、各種ウィスカー、等の素材からなる各種繊維、ポリアクリロニトリル系ポリマーやピッチ等を主な原料とする炭素繊維、各種の気相中または固相中で合成されるナノ炭素繊維やカーボンナノチューブ等、木綿や絹や獣毛等の天然繊維、アセテートやレーヨン等の半合成繊維、等の各種素材を用いることができる。これらの中で、炭素との親和性または接着性が高いものは特に好ましく用いられる。その一例としては、炭化水素系繊維、炭素繊維、ナノ炭素繊維、カーボンナノチューブが挙げられる。この中でも、比強度、比弾性率に優れており、かつ取扱性にも優れるという総合的なバランスが取れているポリアクリロニトリル系ポリマーを原料とする炭素繊維は好適に使用できる。また、本発明に使用する繊維の形態は限定されず、単繊維、それらが束になった繊維束、単繊維または繊維束からなる不織布、織物、編物等の布帛またはシートまたはフィルム状、３次元以上の織物、編物等が適用し得る。この中で、プロセス性として特に好ましいのは、繊維束状のものである。 The fibers used in the present invention are not particularly limited, but are hydrocarbons such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate, polyamides such as nylon-6 and nylon-6,6, aramids, polyimides, and polyphenylene sulfides. Main materials are polybenzazoles such as polyparaphenylene benzoxazole, various fibers made of materials such as glass, silicon carbide, boron, alumina, various metals, various whiskers, polyacrylonitrile polymers, pitches, etc. Various materials such as carbon fibers, nano carbon fibers and carbon nanotubes synthesized in various gas phases or solid phases, natural fibers such as cotton, silk and animal hair, semi-synthetic fibers such as acetate and rayon, etc. Can be used. Among these, those having high affinity or adhesion to carbon are particularly preferably used. Examples thereof include hydrocarbon fibers, carbon fibers, nanocarbon fibers, and carbon nanotubes. Among these, carbon fibers made from a polyacrylonitrile-based polymer, which is excellent in specific strength and specific elastic modulus and has a comprehensive balance of excellent handling properties, can be suitably used. Moreover, the form of the fiber used for this invention is not limited, Single fiber, the fiber bundle which bundled them, the nonwoven fabric which consists of a single fiber or a fiber bundle, textiles, sheets, or films, such as a woven fabric and a knitted fabric, three-dimensional The above woven fabrics, knitted fabrics and the like can be applied. Of these, fiber bundles are particularly preferable as processability.
本発明において、液体中で気泡を発生させる方法は特に限定されないが、超音波を液体中に照射する方法、少なくとも液体の存在する場を減圧する方法、液体を加熱する方法、および繊維を加熱する方法、のいずれか１つ、または２つ以上を組み合わせることによって達成できる。超音波を照射する場合、その出力は１００Ｗ以上が好ましく、５００Ｗ以上がより好ましい。上限は基本的には大出力の方が気泡の多量発生のために好ましいが、あまり大出力過ぎると、繊維の分子や構造を破壊することもあるので、２０００Ｗ以下、より好ましくは１５００Ｗ以下がバランスが取れており好ましい。周波数は、特に限定されないが、１８〜５０ｋＨｚのものが好ましい。減圧する場合、その好ましい減圧度は液体によって異なるため一慨には言えないが、必ずしも超高真空領域にする必要はなく、液体が処理を実施する温度領域で沸騰を始めれば充分である。おおまかではあるが、具体的には１０〜５×１０4Ｐａが好ましく、１×１０2〜２×１０4Ｐａがより好ましい。超音波による気泡の内部は、超高圧高温でプラズマを生成して液体を加熱する場合、使用する液体の沸点まで加熱すれば充分である。繊維を加熱する場合、繊維は、導電性ではあるが、適度な比抵抗を示すと、通電することによって発熱させることができるので、炭素繊維等は好ましく用いられる一例である。この場合においても、その目的とするところは、確実に繊維付近で液体から気泡を発生させて高効率に炭素性物質を繊維に付着または蒸着させることにあるので、繊維の発熱温度は、液体を加熱する場合に準ずる。 In the present invention, the method for generating bubbles in the liquid is not particularly limited, but a method of irradiating ultrasonic waves into the liquid, a method of reducing the pressure at least in the presence of the liquid, a method of heating the liquid, and heating the fiber Any one of the methods, or a combination of two or more can be achieved. When irradiating with ultrasonic waves, the output is preferably 100 W or more, and more preferably 500 W or more. The upper limit is basically preferable for large output because of the generation of a large amount of bubbles. However, if the output is too large, the molecular and structure of the fiber may be destroyed, so 2000 W or less, more preferably 1500 W or less is balanced. Is preferable. The frequency is not particularly limited, but is preferably 18 to 50 kHz. When the pressure is reduced, the preferred degree of pressure reduction differs depending on the liquid, so it cannot be said at a glance. However, it is not always necessary to use the ultrahigh vacuum region, and it is sufficient if the liquid starts boiling in the temperature region where the treatment is performed. Specifically, it is preferably 10 to 5 × 10 4 Pa, more preferably 1 × 10 2 to 2 × 10 4 Pa. When the liquid is heated by generating plasma at an ultra-high pressure and high temperature, it is sufficient to heat the inside of the bubbles by ultrasonic waves up to the boiling point of the liquid to be used. In the case of heating the fiber, the fiber is conductive, but if it exhibits an appropriate specific resistance, it can be heated by energization, so carbon fiber is an example that is preferably used. Even in this case, the purpose is to reliably generate bubbles from the liquid in the vicinity of the fiber and deposit or deposit the carbonaceous material on the fiber with high efficiency. Same as when heating.
本発明の機能化繊維の製造方法では、気泡が発生したところに電磁波を照射することにより液体に起因した化合物を原材料繊維に付着せしめるものである。ここでその機構は定かではないが、気泡が発生したところに電磁波を照射することによりプラズマが発生し、このような化合物の繊維への付着が起こるものと思われる。なお、照射する電磁波の周波数は、目的や繊維、液体に応じて適宜決めれば良いが、１３Ｍ〜３００ＧＨｚが好ましく、１００Ｍ〜３０ＧＨｚがより好ましく、１Ｇ〜３ＧＨｚがさらに好ましい。最も手近な電磁波発生装置としては、２．４５ＧＨｚを発生するマグネトロンが挙げられる。電磁波の出力は、１０〜５０００Ｗが好ましく、５０〜３０００Ｗがより好ましい。なお、水系を液体とする場合には、２．４〜２．６ＧＨｚでは液体も発熱するため、それを目的とする場合は好ましく用いられるが、液体全体を常温に保ち、気泡だけを発生させ、その中でプラズマを発生させることを目的とする場合には、前記周波数帯は避けた方が良く、２ＧＨｚ以下が好ましい。 In the method for producing a functionalized fiber of the present invention, a compound derived from a liquid is adhered to a raw material fiber by irradiating an electromagnetic wave where bubbles are generated. Although the mechanism is not clear here, it is considered that plasma is generated by irradiating electromagnetic waves where bubbles are generated, and adhesion of such compounds to fibers occurs. The frequency of the electromagnetic wave to be irradiated may be appropriately determined according to the purpose, fiber, and liquid, but is preferably 13M to 300GHz, more preferably 100M to 30GHz, and further preferably 1G to 3GHz. The most convenient electromagnetic wave generator is a magnetron that generates 2.45 GHz. The output of the electromagnetic wave is preferably 10 to 5000 W, and more preferably 50 to 3000 W. When the aqueous system is a liquid, the liquid also generates heat at 2.4 to 2.6 GHz, so it is preferably used for that purpose, but the entire liquid is kept at room temperature and only bubbles are generated, When the purpose is to generate plasma, the frequency band should be avoided and 2 GHz or less is preferable.
繊維に液体から起因する化合物を付着せしめる処理は、バッチ法でも連続処理法でも構わないが、工業的により有効なのは、連続処理であり、実質的に繊維を液体中で一定の速度で動かすことが好ましい。その速度は、目的や処理液体などの諸条件によって適宜変わるので一慨に言えないが、基本的には、高い効率及び速度で炭素性物質を生成させて繊維に付着または蒸着させられる程、連続処理の速度は上げられる。この処理の後、更に、マトリックス樹脂との接着性を高めるため、繊維を酸化処理するのも好ましい。酸化処理方法は、特に限定されず、いずれの公知の方法も用いることができる。例えば特開２００３−１３３３０号公報に記載の方法なども好ましく用いることができる。 The treatment for adhering a compound derived from a liquid to a fiber may be a batch method or a continuous treatment method, but industrially more effective is a continuous treatment, in which a fiber is moved substantially in a liquid at a constant speed. preferable. The speed varies depending on the purpose and various conditions such as the treatment liquid, so it cannot be said at a glance. However, basically, the carbon material is generated with high efficiency and speed so that the carbon material is deposited or deposited on the fiber. Processing speed is increased. After this treatment, it is also preferable to subject the fibers to an oxidation treatment in order to enhance the adhesion with the matrix resin. The oxidation treatment method is not particularly limited, and any known method can be used. For example, the method described in JP-A-2003-13330 can be preferably used.
以上のようにして得られた機能化繊維は、繊維強化複合材料に好適に用いられるが、有害物質の吸着除去や所望する物質の分離回収、水素等の気体の吸蔵等に用いる吸着／吸蔵材、酵素や抗体等の有用タンパク質の固定化・分離、微生物の培地、電磁波遮蔽材等にも好ましく用いられる。繊維が炭素繊維の場合には、通常炭素繊維を賦活処理することによって製造される活性炭素繊維の代替にもなる。これらは、特に比表面積が大きいアモルファス性炭素の場合に好ましく適用できる例である。 The functionalized fiber obtained as described above is suitably used for a fiber-reinforced composite material. However, the adsorption / occlusion material used for adsorption removal of harmful substances, separation and recovery of desired substances, occlusion of gas such as hydrogen, etc. It is also preferably used for immobilization / separation of useful proteins such as enzymes and antibodies, microbial media, electromagnetic shielding materials, and the like. When the fiber is a carbon fiber, it is also an alternative to the activated carbon fiber that is usually produced by activating the carbon fiber. These are examples that can be preferably applied particularly to amorphous carbon having a large specific surface area.
また、本発明においては、繊維を微粒子やフィルムや各種成形体に置き換えることも可能であり、その効果は上述と同様であるため、用途や目的に応じて微粒子やフィルムや各種成形体の繊維に準ずる素材や形状等を適宜選択することができる。 In the present invention, it is also possible to replace the fibers with fine particles, films, and various molded articles, and since the effect is the same as described above, the fibers of fine particles, films, and various molded articles are used depending on the purpose and purpose. The corresponding material and shape can be selected as appropriate.
以下、実施例により本発明をさらに具体的に説明するが、実施例によって本発明が制限されることはない。
なお、繊維強化複合材料の強さは、圧縮強度で評価した。その概略は、実施例及び比較例で得られた各繊維束を用い、プリプレグ及び繊維強化複合材料を作製し、ＡＳＴＭＤ６９５の評価方法に従って、繊維複合複合材料の圧縮強度を測定した。本発明において用いた評価方法の詳細及びプリプレグ及び繊維強化複合材料の作製方法は次の通りである。
EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited by an Example.
The strength of the fiber reinforced composite material was evaluated by compressive strength. The outline was that each fiber bundle obtained in Examples and Comparative Examples was used to prepare a prepreg and a fiber reinforced composite material, and the compressive strength of the fiber composite material was measured according to the evaluation method of ASTM D695. The details of the evaluation method used in the present invention and the method for producing the prepreg and the fiber-reinforced composite material are as follows.
（繊維表面凹凸の測定方法）
後述でも明らかになるが、以下の実施例ではＳＥＭで充分に凹凸を認識できるものであったので、（株）日立製作所製Ｓ−４０００を用い、加速電圧２０ｋＶにて、５千〜１万倍の倍率で撮影した画像から評価した。
(Measurement method of fiber surface irregularities)
As will be apparent from the description below, in the following examples, the unevenness could be sufficiently recognized by SEM. Therefore, S-4000 manufactured by Hitachi, Ltd. was used, and the acceleration voltage was 20 kV. It evaluated from the image | photographed with the magnification of.
（ラマン分光法）
ラマンスペクトルは、日本電子（株）製ＪＲＳ−ＳＹＳＴＥＭ １０００を用い、Ａｒレーザー、波長５１４ｎｍ、スポット径１μｍ、露光時間１０秒、ラマンスペクトル測定領域０〜２０００ｃｍ-1、の条件で測定した。得られたラマンスペクトルにおいて、ＤバンドピークとＧバンドピークの間に存在する１４５０〜１５００ｃｍ-1付近の最低強度部と１０００〜１３００ｃｍ-1の間にフィッティング良くベースラインを引き、そのベースラインとＤバンドピークで囲まれた領域の面積を、前記ＤバンドピークとＧバンドピークの間の最低強度部と１６５０〜１７００ｃｍ-1の間にフィッティング良くベースラインを引き、そのベースラインとＧバンドピークで囲まれた領域の面積で割ることによってＤ／Ｇ比を算出した。
(Raman spectroscopy)
The Raman spectrum was measured using JRS-SYSTEM 1000 manufactured by JEOL Ltd. under the conditions of Ar laser, wavelength 514 nm, spot diameter 1 μm, exposure time 10 seconds, Raman spectrum measurement region 0 to 2000 cm −1 . In the obtained Raman spectrum, pull the fitting well baseline between 1450～1500Cm -1 near the minimum strength part and 1,000 to -1 existing between the D band peak and G band peak, the base line and D The area surrounded by the band peak is drawn with a good fit between the lowest intensity part between the D band peak and the G band peak and 1650-1700 cm -1 and surrounded by the base line and the G band peak. The D / G ratio was calculated by dividing by the area of the region obtained.
（Ｘ線光電子分光法）
ＸＰＳにおけるＣ１ｓ、Ｓｉ２ｐ、Ｏ１ｓの各スペクトルは、米国Ｓｕｒｆａｃｅ Ｓｃｉｅｎｃｅ社製ＳＳＸ−１００を用い、励起Ｘ線単色ＡｌＫα１，２線（１４８６．６ｅＶ）、Ｘ線径１ｍｍ、Ｘ線出力１０ｋＶ、２０ｍＡ、真空度２．８×１０-10 Ｔｏｒｒの条件で、測定を行った。測定範囲は、Ｃ１ｓでは２７８〜２９０ｅＶ、Ｓｉ２ｐでは９４〜１１０ｅＶ、Ｏ１ｓでは５２４〜５３８ｅＶとした。得られた各ピークの面積は、測定範囲の中で適切なベースラインを引き、ガウシアン分布を用いて良好なフィッティングカーブを得、ピーク面積を求めた。得られた各ピーク面積の比及び感度補正値を用いて、Ｓｉ／Ｃ比またはＯ／Ｃ比を算出した。
(X-ray photoelectron spectroscopy)
Each spectrum of C1s, Si2p, and O1s in XPS uses SSX-100 manufactured by Surface Science, Inc., USA, excitation X-ray monochromatic AlKα1,2 wire (1486.6 eV), X-ray diameter 1 mm, X-ray output 10 kV, 20 mA, vacuum The measurement was performed under the condition of a degree of 2.8 × 10 −10 Torr. The measurement range was 278 to 290 eV for C1s, 94 to 110 eV for Si2p, and 524 to 538 eV for O1s. For the area of each peak obtained, an appropriate baseline was drawn within the measurement range, a good fitting curve was obtained using a Gaussian distribution, and the peak area was determined. The Si / C ratio or O / C ratio was calculated using the ratio of each peak area and the sensitivity correction value.
（プリプレグ及び繊維強化複合材料の作製方法）
Ａ．次に示す原料樹脂を混合し、３０分攪拌して樹脂組成物を得た。
・ビスフェノールＡジグリシジルエーテル樹脂（”エピコート”（登録商標）１００１、ジャパンエポキシレジン（株）製）、３０重量％
・ビスフェノールＡジグリシジルエーテル樹脂（”エピコート”８２８、ジャパンエポキシレジン（株）製）、３０重量％
・フェノールノボラックポリグリシジルエーテル樹脂（”エピクロン”（登録商標）−Ｎ７４０、大日本インキ化学工業（株）製）、２７重量％
・ポリビニルホルマール樹脂（”ビニレック”（登録商標）Ｋ、チッソ（株）製、登録商標）、５重量％
・ジシアンジアミド（ＤＩＣＹ７、ジャパンエポキシレジン（株）製）、４重量％
・３，４ジクロロフェノール−１ジメチルウレア（ＤＣＭＵ−９９、保土ヶ谷化学（株）製、硬化剤）、４重量％
次に、前記樹脂組成物をシリコーンを塗布した離型紙にコーティングして得られた樹脂フィルムを円周約２．７ｍの６０〜７０℃に温調した鋼製ドラムに巻き付けた。
この上に炭素繊維をクリールから巻きだしトラバースを介して配列する。更にその上から、前期樹脂フィルムで再度覆い、ロールで回転しながら、加圧し樹脂を繊維束内に含浸せしめ、幅３００ｍｍ、長さ２．７ｍの一方向プリプレグを作製した。ここで、プリプレグの繊維目付はドラムの回転数とトラバースの送り速度を変化させ、１９０ｇ／ｍ2とした。またプリプレグの樹脂含有率は約３５重量％とした。
このプリプレグを繊維方向を一方向に揃えて積層し、温度１３０℃、圧力０．３ＭＰａで２時間硬化させ、厚さが１ｍｍの積層板（繊維強化複合材料）を成形した。
(Preparation method of prepreg and fiber reinforced composite material)
A. The following raw material resins were mixed and stirred for 30 minutes to obtain a resin composition.
-Bisphenol A diglycidyl ether resin ("Epicoat" (registered trademark) 1001, manufactured by Japan Epoxy Resins Co., Ltd.), 30% by weight
-Bisphenol A diglycidyl ether resin ("Epicoat" 828, manufactured by Japan Epoxy Resin Co., Ltd.), 30% by weight
Phenol novolac polyglycidyl ether resin (“Epiclon” (registered trademark) -N740, manufactured by Dainippon Ink and Chemicals, Inc.), 27% by weight
Polyvinyl formal resin ("Vinylec" (registered trademark) K, manufactured by Chisso Corporation, registered trademark), 5% by weight
・ Dicyandiamide (DICY7, manufactured by Japan Epoxy Resin Co., Ltd.), 4% by weight
・ 3,4 dichlorophenol-1dimethylurea (DCMU-99, manufactured by Hodogaya Chemical Co., Ltd., curing agent), 4% by weight
Next, a resin film obtained by coating the resin composition on a release paper coated with silicone was wound around a steel drum whose temperature was adjusted to 60 to 70 ° C. with a circumference of about 2.7 m.
On top of this, carbon fibers are unrolled from the creel and arranged through a traverse. Further, it was covered again with a resin film in the previous period, pressed while rotating with a roll, and impregnated with resin in a fiber bundle to prepare a unidirectional prepreg with a width of 300 mm and a length of 2.7 m. Here, the fiber basis weight of the prepreg was set to 190 g / m 2 by changing the rotational speed of the drum and the traverse feed speed. The resin content of the prepreg was about 35% by weight.
This prepreg was laminated with the fiber direction aligned in one direction and cured at a temperature of 130 ° C. and a pressure of 0.3 MPa for 2 hours to form a laminated plate (fiber reinforced composite material) having a thickness of 1 mm.
（圧縮強度の測定）
前記積層板から被破壊部分が中心になるように、厚さ１±０．１ｍｍ、幅１２．７±０．１３ｍｍ、長さ８０±０．０１３ｍｍ、ゲージ部長さ５±０．１３ｍｍの試験片を切り出した。
この試験片よりＡＳＴＭ Ｄ６９５に示される圧縮治具を使用し、歪み速度を１．２７ｍｍ／分の条件で測定し、繊維体積分率６０％に換算して繊維強化複合材料の圧縮強度を得た。
(Measurement of compressive strength)
A test piece having a thickness of 1 ± 0.1 mm, a width of 12.7 ± 0.13 mm, a length of 80 ± 0.013 mm, and a gauge portion length of 5 ± 0.13 mm so that the part to be broken is centered from the laminated plate. Was cut out.
From this test piece, the compression jig shown in ASTM D695 was used, the strain rate was measured under the condition of 1.27 mm / min, and the compressive strength of the fiber reinforced composite material was obtained in terms of the fiber volume fraction of 60%. .
実施例１
図１に、繊維を連続処理するための装置の概略構成を示す。繊維１は、図示を省略した送り出しリールから送り出され、フリーローラーからなるガイドローラー６によって図の左方向から右方向に一定速度で導かれ、図示を省略した巻き取りリールに巻き取られる。液体２に浸った繊維１は、超音波発生装置４によって液体２中で発生した気泡５に、電磁波発生装置３から電磁波を照射し、気泡５中にプラズマを発生させる。繊維１はそのプラズマ中をくぐり抜け、連続処理されるようになっている。超音波発生装置４と電磁波発生装置３の各先端間の距離は４ｍｍで、繊維１はその中央を通過するようにしてある。本実施例では、繊維１には１２，０００本の束からなる引張弾性率が３７０ＧＰａのポリアクリロニトリル系炭素繊維を用い、糸速０．１ｍ／分で、液体２にドデカンを用いた。超音波発生装置４の出力は１９．５ｋＨｚ、６００Ｗ、電磁波発生装置３の出力は２．５４ＧＨｚ、１２０Ｗである。
Example 1
FIG. 1 shows a schematic configuration of an apparatus for continuously processing fibers. The fiber 1 is delivered from a delivery reel (not shown), guided at a constant speed from the left to the right in the drawing by a
得られた繊維は、凹凸表面を有し、炭素性物質が付着していた。図２に走査型電子顕微鏡で観察した繊維の表面を示す。図より、凸部の頂点と凹部の底との差は、少なく見積もっても０．３μｍを下回らないことは明らかであった。続いて、得られた繊維を濃度０．１モル／ｌの硫酸水溶液を電解液として電解表面処理し、水洗、１５０℃で乾燥処理した後、サイジング剤を付与した。この繊維を用いた繊維強化複合材料の圧縮強度を評価した結果、１．６ＧＰａと高い値を示した。 The obtained fiber had an uneven surface, and a carbonaceous material was adhered. FIG. 2 shows the surface of the fiber observed with a scanning electron microscope. From the figure, it was clear that the difference between the top of the convex portion and the bottom of the concave portion was not less than 0.3 μm even if estimated to be small. Subsequently, the obtained fiber was subjected to electrolytic surface treatment using an aqueous sulfuric acid solution having a concentration of 0.1 mol / l as an electrolytic solution, washed with water and dried at 150 ° C., and then a sizing agent was applied. As a result of evaluating the compressive strength of the fiber reinforced composite material using this fiber, it showed a high value of 1.6 GPa.
実施例２
実施例１において気泡発生手段として用いた超音波発生装置の代わりに、繊維を処理する系を減圧できるよう、図３に概略を示すように、系全体を真空チャンバー７で囲って真空装置８で減圧できる状態にした。繊維の入口と出口は、フリーローラー６とニップローラー６’で減圧効果が極力失われないようにしてある。真空チャンバー７内の圧力を真空装置８で１００００Ｐａまで減圧した他は、繊維１、糸速、液体２、電磁波発生装置３の出力は、実施例１に準じた。気泡５、５’は、液体２のいたるところで発生するが、プラズマが発生するのは電磁波発生装置３の先端部付近のみ（気泡５部分のみ）であった。
Example 2
Instead of the ultrasonic generator used as the bubble generating means in Example 1, the entire system is surrounded by a vacuum chamber 7 so as to reduce the pressure of the fiber processing system as shown in FIG. The pressure was reduced. The inlet and outlet of the fiber are set so that the pressure reduction effect is not lost as much as possible by the
得られた繊維は、凹凸表面を有し、炭素性物質が付着しており、図２と示したのと実質的に同等の様態であった。この繊維を実施例１と同様に電解処理及びサイジング剤処理し、得られた繊維を用いた繊維強化複合材料の圧縮強度を評価した結果、１．６ＧＰａであった。 The obtained fiber had a concavo-convex surface and a carbonaceous material adhered, and was in a state substantially equivalent to that shown in FIG. The fiber was subjected to electrolytic treatment and sizing agent treatment in the same manner as in Example 1. The result of evaluating the compressive strength of the fiber-reinforced composite material using the obtained fiber was 1.6 GPa.
実施例３
実施例２と同様に気泡発生手段として１００００Ｐａに減圧すると同時に、実施例１で用いた条件で超音波発生装置も併用した上で、液体としてメチルハイドロジェンポリシロキサン（東レ・ダウ・コーニング（株）製ＳＨ１１０７）を用い、電磁波出力を２．５４ＧＨｚ、２００Ｗとして繊維の処理を行った。
得られた繊維は、図２に示したものと実質的に同様な形態の凹凸表面を有するものであった。得られた繊維のＸＰＳによるＳｉ／Ｃ比は、０．９５であった。
Example 3
In the same manner as in Example 2, the pressure was reduced to 10000 Pa as the bubble generating means, and at the same time the ultrasonic generator was used in combination with the conditions used in Example 1, and then the liquid was methylhydrogenpolysiloxane (Toray Dow Corning Co., Ltd.). Using SH1107), the fiber was processed with an electromagnetic wave output of 2.54 GHz and 200 W.
The obtained fiber had a concavo-convex surface having a form substantially similar to that shown in FIG. The Si / C ratio by XPS of the obtained fiber was 0.95.
実施例４
実施例１において、液体として東レ（株）製トレピュアＬＶ−１０Ｔにより製造した比抵抗１８ＭΩ・ｃｍの超純水を用い、電磁波出力を２．００ＧＨｚ、２００Ｗとし、図１における２個の金属製フリーローラー６を介して繊維に１０Ｗの直流電流が流れるようにして処理を行った。
得られた繊維は、ＳＥＭ観察の結果、図２によく似た不均一な凹凸が生じており、凸部頂点と凹部の底との差は、少なくとも０．１μｍを下回らなかった。この繊維のＸＰＳによるＯ／Ｃ比は０．７であった。
Example 4
In Example 1, ultrapure water with a specific resistance of 18 MΩ · cm manufactured by Toray Pure LV-10T manufactured by Toray Industries, Inc. was used as the liquid, the electromagnetic wave output was set to 2.00 GHz, 200 W, and the two metal free in FIG. The treatment was carried out in such a way that a direct current of 10 W was passed through the fiber via the
As a result of SEM observation, the obtained fiber had uneven unevenness similar to that shown in FIG. 2, and the difference between the top of the convex portion and the bottom of the concave portion was not less than at least 0.1 μm. The O / C ratio by XPS of this fiber was 0.7.
比較例１
実施例１において、超音波も電磁波も与えずに繊維を処理し、実質的に処理を施さない状態の繊維を得た。この繊維を用いて繊維強化複合材料を作製し、圧縮強度を測定した結果、１．３ＧＰａであり、これは実施例１の装置を通す前の繊維から作製した繊維強化複合材料が示す圧縮強度と同じ値であった。
Comparative Example 1
In Example 1, the fiber was processed without applying ultrasonic waves or electromagnetic waves, and a fiber in a state where it was not substantially processed was obtained. A fiber reinforced composite material was produced using this fiber, and the compression strength was measured. As a result, it was 1.3 GPa. This is the compressive strength indicated by the fiber reinforced composite material produced from the fiber before passing through the apparatus of Example 1. It was the same value.
本発明は、各種機能が求められるあらゆる機能化繊維の製造に適用でき、例えば、繊維強化複合材料用強化繊維、衣料用繊維のみならず、あらゆる用途の機能化繊維に適用可能である。また、本発明に係る技術思想は、繊維だけでなく、微粒子、フィルム、成形体などにも応用することが可能であり、さらにその応用範囲を、これらに限定することなく、さらに広い範囲にまで展開可能である。 The present invention can be applied to the production of any functionalized fiber that requires various functions. For example, the present invention can be applied not only to a reinforcing fiber for fiber-reinforced composite materials and a fiber for clothing, but also to a functionalized fiber for all uses. Further, the technical idea according to the present invention can be applied not only to fibers but also to fine particles, films, molded bodies, and the like, and further, the application range is not limited to these, but to a wider range. It can be deployed.
１ 繊維
２ 液体
３ 電磁波発生装置
４ 超音波発生装置
５ 気泡及びプラズマ
５’ 気泡
６ フリーローラーからなるガイドローラー
６’ ニップローラー
７ 真空チャンバー
８ 真空装置
DESCRIPTION OF SYMBOLS 1 Fiber 2 Liquid 3 Electromagnetic wave generator 4
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Cited By (4)
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| WO2006104043A1 (en) * | 2005-03-25 | 2006-10-05 | Mitsubishi Rayon Co., Ltd. | Method of surface treatment and surface-treated article |
| JP2017036531A (en) * | 2015-08-07 | 2017-02-16 | デクセリアルズ株式会社 | Insulated coated carbon fiber, method for manufacturing insulated coated carbon fiber, carbon-fiber-containing composition, and heat-conducting sheet |
| WO2017026428A1 (en) * | 2015-08-07 | 2017-02-16 | デクセリアルズ株式会社 | Insulated coated carbon fiber, method for manufacturing insulated coated carbon fiber, carbon-fiber-containing composition, and heat-conducting sheet |
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| CN102628212A (en) * | 2012-04-06 | 2012-08-08 | 武汉理工大学 | Carbon fiber surface treatment method based on ultrasonic strengthening |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2006104043A1 (en) * | 2005-03-25 | 2006-10-05 | Mitsubishi Rayon Co., Ltd. | Method of surface treatment and surface-treated article |
| US20080210664A1 (en) * | 2005-03-25 | 2008-09-04 | Mitsubishi Rayon Co., Ltd. | Method of Surface Treatment and Surface-Treated Article |
| JP2017036531A (en) * | 2015-08-07 | 2017-02-16 | デクセリアルズ株式会社 | Insulated coated carbon fiber, method for manufacturing insulated coated carbon fiber, carbon-fiber-containing composition, and heat-conducting sheet |
| WO2017026428A1 (en) * | 2015-08-07 | 2017-02-16 | デクセリアルズ株式会社 | Insulated coated carbon fiber, method for manufacturing insulated coated carbon fiber, carbon-fiber-containing composition, and heat-conducting sheet |
| KR20180004831A (en) * | 2015-08-07 | 2018-01-12 | 데쿠세리아루즈 가부시키가이샤 | Insulated coated carbon fiber, method of producing insulated coated carbon fiber, carbon fiber containing composition and thermally conductive sheet |
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| KR102117549B1 (en) | 2015-08-07 | 2020-06-01 | 데쿠세리아루즈 가부시키가이샤 | Insulation-coated carbon fiber, method for producing insulating-coated carbon fiber, carbon fiber-containing composition and thermally conductive sheet |
| CN113445321A (en) * | 2015-08-07 | 2021-09-28 | 迪睿合株式会社 | Insulation-coated carbon fiber, method for producing insulation-coated carbon fiber, carbon fiber-containing composition, and heat conductive sheet |
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