201028508 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種表面已被改質之高強度纖維及其製 造方法，更詳言之，關於一種表面改質纖維及其製造方法， 其係與樹脂的接著性良好，適合作爲複合材料用資材。 【先前技術】 所謂特級纖維（super fiber)之高強度、高彈性率纖 φ 維已被泛用於預浸漬物、FRP等之補強纖維。爲了使補強 纖維所具有的力學物性反映至FRP等之物性，與樹脂的接 著性將變得重要，若接著性低的話，接著界面將成爲缺陷， 無法將補強纖維所具有的力學物性反映至FRP等之物性。 因而，隨著補強纖維高性能化發展，也同時要求接著性之 提高，已進行各種的探討。 例如，聚苯并哩（polybenzazole; PBZ)纖維係具有 現在所市售的特級纖維代表之聚對苯二甲醯對苯二胺纖維 〇 的強度與彈性率之2倍以上，期待作爲下世代之特級纖 維，另外，於PBZ纖維之中，已知聚對伸苯基苯并雙聘唑 (PBO )纖維具有最高的弾性率（例如，參照專利文獻1 )。 而且，隨著如此纖維之高性能化，有人進行接著性改 良之提案，例如藉由電暈處理而對纖維表面賦予有助於接 著性之官能基的纖維（例如，參照專利文獻2 )。然而， 在電暈處理中，由於能量低而無法充分地將官能基賦予表 面，因而能夠滿足的接著性則尙未得到。因此，爲了賦予 -4- 201028508 更多的官能基，有人已進行能量更高的大氣壓電漿處理的 探討（例如，參照專利文獻3 )。 但是，即使利用大氣壓電漿處理而賦予官能基，滿足 的接著性也尙未得到。因此，有人提案將官能基賦予表面， 同時也將微細之凹凸賦予纖維表面（例如，參照專利文獻 4)。然而，即使爲如此之表面改質纖維，迄今尙未得到使 PBO纖維所具有的力學物性得以充分發揮的接著性。 專利文獻1 :美國專利第5296 1 85號公報 專利文獻2 :日本專利特開平7- 1 02473號公報 專利文獻3:日本專利特開2003-221778號公報 專利文獻4:日本專利特開2003-201625號公報 【發明內容】 發明所欲解決之技術問題 本發明係有鑑於上述習用技術之現狀所發明，其目的 係提供一種具有優異接著性之高強度表面改質纖維及其製 〇 造方法，其係使補強纖維的優異力學物性反映至FRP等之 物性。 解決問題之技術手段 本發明人等爲了達成上述目的而鑽硏的結果，終於完 成本發明。 亦即，本發明中之第i項發明係一種纖維，其係具有 強度8cN/dtex以上之纖維，其特徵爲在纖維表面之原子間 力顯微鏡觀察視野範圍的纖維長軸方向4μιη><纖維矩軸方 201028508 向2μιη之面積中，於纖維矩軸方向連接Ο.ίμιη以上，且存 在20個以上之具有深度10〜lOOnm的裂紋狀凹部》 本發明之纖維的較佳形態係如下所述： (1) 平均剖面輪廓中之表面凹凸構造的表面粗糙度Ra爲 1 . 5 〜6 · Onm 〇 (2) 從纖維表面之原子間力顯微鏡觀察視野範圍的纖維長 軸方向4μιη><纖維矩軸方向2μιη，無規地切出3個剖面，剖 面通過凸部中心者之高度平均値的高低差爲20〜lOOnm。201028508 6. Technical Field of the Invention: The present invention relates to a high-strength fiber whose surface has been modified and a method for producing the same, and more particularly to a surface-modified fiber and a method for producing the same, It has good adhesion to the resin and is suitable as a material for composite materials. [Prior Art] The high-strength, high-elasticity fiber φ of the so-called super fiber has been widely used as a reinforcing fiber such as a prepreg or FRP. In order to reflect the physical properties of the reinforcing fiber to the physical properties such as FRP, the adhesion to the resin is important. If the adhesion is low, the interface becomes a defect, and the mechanical properties of the reinforcing fiber cannot be reflected to the FRP. Wait for the physical properties. Therefore, various developments have been made as the performance of the reinforcing fiber is developed and the adhesion is improved at the same time. For example, polybenzazole (PBZ) fiber has twice the strength and elastic modulus of polyparaphenylene terephthalamide fiber ray represented by the special fiber currently marketed, and is expected to be the next generation. In particular, among the PBZ fibers, polyparaphenylene benzobisazole (PBO) fibers are known to have the highest enthalpy ratio (for example, refer to Patent Document 1). In addition, as a result of the improvement of the performance of the fiber, there is a proposal for improving the adhesion, for example, a fiber which contributes to the functional group of the fiber surface by corona treatment (for example, see Patent Document 2). However, in the corona treatment, since the functional group is not sufficiently imparted to the surface due to low energy, the satisfactory adhesion is not obtained. Therefore, in order to impart more functional groups to -4-201028508, investigations have been conducted on higher-energy atmospheric piezoelectric slurry treatment (for example, refer to Patent Document 3). However, even if the functional group is imparted by the atmospheric piezoelectric slurry treatment, the satisfactory adhesion is not obtained. Therefore, it has been proposed to impart a functional group to the surface, and also to impart fine unevenness to the surface of the fiber (for example, refer to Patent Document 4). However, even in such a surface-modified fiber, the adhesion of the mechanical properties of the PBO fiber to the full extent has not been obtained so far. Patent Document 1: U.S. Patent No. 5,296,85, Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-221778. Patent Document 4: Japanese Patent Laid-Open No. 2003-201625 SUMMARY OF THE INVENTION The present invention has been made in view of the above-described state of the art, and an object thereof is to provide a high-strength surface-modified fiber having excellent adhesion and a method for producing the same. The excellent mechanical properties of the reinforcing fiber are reflected to the physical properties such as FRP. Means for Solving the Problems The inventors of the present invention have finally completed the invention in order to achieve the above object. That is, the invention according to the invention of the present invention is a fiber having a strength of 8 cN/dtex or more, which is characterized by an atomic force microscopic observation of the longitudinal direction of the fiber in the field of view of the fiber surface 4 μιη> The moment axis 201028508 is connected to 纤维.ίμιη in the direction of the fiber moment axis, and there are 20 or more crack-like recesses having a depth of 10 to 100 nm in the area of 2 μm η. The preferred form of the fiber of the present invention is as follows: (1) The surface roughness Ra of the surface uneven structure in the average profile profile is 1.5 to 6 · Onm 〇 (2) The fiber longitudinal direction of the field of view is observed from the surface of the fiber by the atomic force microscope 4 μιη><Fiber moment The axial direction is 2 μm, and three sections are randomly cut out, and the height difference of the height of the section passing through the center of the convex portion is 20 to 100 nm.
G 另外，本發明中之第2項發明係一種製造方法，其特 徵係在該纖維的表面，照射離子束而進行處理。 再者，本發明之纖維之製造方法的較佳形態係如下所 述： (1) 離子束之處理氣體爲氧、空氣、氮、氬或此等之混合 氣體。 (2) 將離子束處理之離子粒子能量設爲1(Γ2〜lO^KeV、處 φ 理壓力設爲0.1〜l.OPa、處理電力設爲50〜5000W、纖維 輸送速度設爲0.01〜lm/min而進行處理。 發明之效果 本發明之纖維係從其特異之表面構造’與習知之經表 面處理的纖維作一比較，具有高的接著性’與樹脂之緊貼 性極高。再者，由於本發明之纖維係根據表面形狀之特異 性而使接著性提高，所以無關於樹脂與纖維之相性’可以 得到高的接著性。另外，本發明之纖維係藉由將離子束照Further, the second invention of the present invention is a production method characterized in that an ion beam is irradiated onto the surface of the fiber for treatment. Further, preferred embodiments of the method for producing a fiber of the present invention are as follows: (1) The treatment gas for the ion beam is oxygen, air, nitrogen, argon or a mixed gas thereof. (2) The ion beam energy of the ion beam treatment is set to 1 (Γ2 to lO^KeV, the pressure is set to 0.1 to 1.OPa, the processing power is set to 50 to 5000 W, and the fiber transport speed is set to 0.01 to lm/ The effect of the invention. The fiber of the present invention has a high adhesion between the surface structure of the present invention and the surface-treated fiber of the prior art, and the adhesion to the resin is extremely high. Since the fiber of the present invention improves the adhesion according to the specificity of the surface shape, high affinity can be obtained regardless of the phase relationship between the resin and the fiber. Further, the fiber of the present invention is irradiated with an ion beam.
201028508 射於纖維表面而可以容易得到表面改質纖維。 【實施方式】 以下’詳細說明本發明之纖維及其製造方法 (纖維） 本發明之纖維係必須具有強度8cN/dtex以』 爲若爲如此強度之纖維的話，便能夠將其纖維性 映至FRP等之複合材料。雖然纖維強度之上限不 別之問題，但若超過70cN/dtex時，即使具有本 之表面構造，亦難以使纖維性能充分反映至複合 如此強度之纖維，例如，可列舉：強度特別 子量聚乙烯纖維等》本發明之纖維係單絲纖維直 8〜15 μπι。這是因爲若爲如此之纖維直徑的話， 分之表面積而能夠賦予許多個上述表面凹凸構造 面’因賦予凹凸部所造成的強度降低少。更佳的 直徑爲9〜13_μιη，進一'步更佳爲10〜12μιη。 本發明之纖維的特徵係在纖維表面之原子間 觀察視野範圍的纖維長軸方向4μηι><纖維矩軸方 面積中，連接0.1 μηι以上且存在20個以上之具 〜lOOnm的裂紋狀凹部。纖維矩軸方向係相對 方向直角的方向。習知之纖維所觀察到的表面E 之凹部爲圓形時，由於本發明之纖維係在與纖翁 直之方向爲裂紋狀，所以成爲表面上阻礙剪切 的接著性。上述裂紋狀之凹部係於上述面積中费 1。這是因 :能充分反 :會成爲特 :發明纖維 材料。 丨高的高分 :徑較佳爲 便具有充 i，另一方 (單絲纖維 丨力顯微鏡 向 2 μιη之 有深度10 >纖維長軸 ]凸構造中 I軸約略垂 ί發揮優異 芒佳爲存在 201028508 30個以上，更佳爲存在35個以上、100個以下。認爲若裂 紋狀凹部之深度低於l〇nm時，無法太過期待與樹脂接著性 之提高；若超過1〇〇 nm時，纖維表面將變得容易被破壞。 本發明之纖維係於平均剖面輪廓中之表面凹凸構造， 表面粗糙度Ra較佳爲1.5〜6.0nn^Ra更佳爲2.0nm以上， 進一步更佳爲2.5 nm以上。若Ra在此範圍的話，對纖維物 性降低之影響爲小的，另一方面，能夠發揮優異的錨定效 Α 果。另外，也能夠形成寬度大且在表面形成剪切強的凸部。 ❿ 本發明之纖維係從纖維表面之原子間力顯微鏡觀察視 野範圍的纖維長軸方向4 μιηχ纖維矩軸方向2 μιη，無規地切 出3個剖面，剖面通過凸部中心者之高度平均値的高低差 較佳爲20 nm〜100 nm。高低差更佳爲30 nm以上，進一步 更佳爲40nm以上。所謂本發明中之高低差係表示表面凹凸 構造的凸部之谷與頂點的高度差。若高低差落在此範圍的 話’對纖維物性降低之影響爲小的，另一方面，能夠發揮 〇 優異的錨定效果。 (製造方法） 另外，本發明之纖維之製造方法，例如，較佳藉由使 用具有強度8cN/dtex以上之纖維，在其表面照射離子束而 形成表面凹凸構造。在使用電漿處理、高頻濺鍍蝕刻處理 等之情形，若提高照射時間、照射能量時，則凹部本身開 始被削減’變得難以得到本發明之纖維。雖然藉由照射離 子束而可以得到如上述高低差大的凸部或裂紋狀凹部之理 201028508 由並未確定’但是推測係由於離子束在離子速度上具有方 向性，可以有效地得到高低差爲大的凸部。 爲了對纖維進行離子束處理，於紡絲或熱處理之後， 能夠採行以捲對捲（roll to roll)之方式進行捲出，利用 離子束處理裝置而進行連續式捲對捲處理之方法，或分批 式之方法’基於操作性之觀點，較佳爲捲對捲方式。除了 纖維素之外，被處理物也可以爲一種將纖維束解開成單絲 ❹ 纖維且使單向—致者或是一種織物。作爲用於將離子束照 射至纖維之離子槍，例如，能夠利用考夫曼（Kauffman)製 之閉合漂移離子源（closed drift ion source)，離子源能 夠利用DC放電、RF放電、微波放電等。尤其，於捲對捲 處理上，較佳爲使用線性離子源。 離子槍所使用的氣體，只要是可生成離子粒子者，任 何的氣體皆未被限制，例如，從氫 '氦、氧、氮氣、空氣、 氟、氖、氬、氪或N20與此等的混合物之中適當選擇而被 ® 使用。於此等氣體之中，尤其因爲氧、空氣在纖維表面形 成上述凸部時，同時也能夠賦予官能基而較佳。 若照射在纖維之離子束的種類或強度能夠將纖維表面 構造改質成上述範圍的話，便並未予以特別限定，通常， 構成離子束之離子粒子的能量係適當選擇離子槍之放電電 壓、放電電流、放電電力、射束氣體（beam gas)流量等而調 節至約1〇·2〜lO^KeV、放電電壓係調節至約295〜800W、 放電電流係調節至約0.1〜10A而予以照射。較佳爲處理時 201028508 壓力調節至約0.1〜l.OPa、纖維輸送速度調節至約〇.01〜 〇-3m/min而進行照射。 (接著性之評估方法） 纖維與樹脂的接著性評估法一般係採用液滴（droplet) 法或ILSS法。液滴法係利用從樹脂珠狀物抽出纖維時之應 力而進行評估之方法，由於均一形狀之樹脂珠狀物難以得 到，所以有精確度與效率之問題。另一方面，ILSS法係利 用藉由4點彎曲試驗而將剪切應力施加於埋入有纖維的樹 脂片時之界面剪切應力而進行評估的方法，由於容易受到 樹脂或纖維的強度特性之影響，精確度爲低的。 於與本發明之纖維樹脂的接著性評估中，採用利用將 纖維埋入樹脂、抽出纖維時之纖維拉張應力的衰減舉動而 進行評估之方法。於此評估法中，能夠得到一定形狀之試 驗片，再者，材料強度特性之影響爲少的，高精確度高效 率之評估爲可能的。 Q 第1圖係示意顯示試驗片作成方法的圖。具體而言， 採用以下之方法： (a)在長度12mm、寬度5mm、厚度3mm之電子顯微 鏡用嵌埋板所相向的二邊，利用單面刃劃入深度〇.〇 5〜 0.1mm之狹縫2，置於20cm正方形之基座上。基座較佳爲 玻璃板，但是要爲平坦且經得起6 0°C之加熱者的話，並未 予以特別限定。 (b )接著，從紗解開單絲纖維l(m〇n〇filament)，跨 -10- 201028508 越嵌埋板之方式來架設纖維，夾住在狹縫2而加以固定。 此時，樹脂外之單絲纖維1的一側長度係作成15〜20cm， 再者，以使單絲纖維1不鬆弛之方式來利用黏著膠帶而將 纖維之兩端固定於基座（矽橡膠製型框4)。 (c )接著，將62CC/10〇CC之熱硬化性環氧樹脂的基材 (LUVEAK 812 )與硬化劑（LUVEAK DDSA)進行調合而 保存於冷藏庫內者，於乾燥器內回復至常溫。利用直徑4mtn 之玻璃棒，添加10滴之硬化加速劑（LUVEAK - DMP30 )， 一面注意使氣泡不進入，一面攪拌1分鐘。調合液之保存 期限係設爲1個月。將該樹脂液3流入嵌埋板，以從嵌埋 板隆起約〇.5mm之方式來調節量，除去黏著膠帶，於60 °C 之烘箱中硬化1 2小時。 (d)於室溫放冷之後，注意使單絲纖維1不斷裂，從 嵌埋板取出樹脂片，得到由樹脂5與單絲纖維1而成之試 驗片。以在樹脂外之單絲纖維1的一側端夾住纖維之方式 〇 來折彎3 X 2cm之紙片，利用接著劑進行固定。 第2圖係示意顯示使用拉曼散射之應力分布測定方法 的圖》 將該試驗片裝設於顯微拉曼散射測定用試料台上，將 樹脂外之單絲纖維1架設於試料台端所附屬的輥上，利用 制動器（Stopper)而固定試驗片之前後。在裝設於樹脂外之 單絲纖維1的紙片上裝設載重（6) 15gf，藉由顯微拉曼散 射，以1 0 μπι間隔，沿著纖維軸而測定樹脂中之單絲纖維1 -11 - 201028508 的拉曼散射。由於拉曼散射之波數係 7所決定，使用檢量線，可以從拉曼 加應力7。 第3圖係示意顯示上述接著性評 圖。 於樹脂中，由於單絲纖維1係藉 對纖維所外加的拉張應力係越朝向ί ^ 即，可以得到沿著纖維軸之距離的函201028508 It is easy to obtain surface modified fibers when it is shot on the fiber surface. [Embodiment] Hereinafter, a fiber of the present invention and a method for producing the same (fiber) will be described in detail. The fiber system of the present invention must have a strength of 8 cN/dtex to be such a fiber, so that its fiber property can be reflected to FRP. Such as composite materials. Although the upper limit of the fiber strength is not a problem, if it exceeds 70 cN/dtex, even if it has the surface structure, it is difficult to sufficiently reflect the fiber properties to the fiber having such a strength, for example, a strength special amount of polyethylene Fiber, etc. The fiber-based monofilament fiber of the present invention is straight 8 to 15 μm. This is because if the fiber diameter is such a size, a large number of the surface uneven structure surfaces can be provided, and the strength reduction due to the uneven portion can be reduced. More preferably, the diameter is 9 to 13_μιη, and a step is more preferably 10 to 12 μm. The fiber of the present invention is characterized by having a crack-like recess of 0.1 μm or more and having 20 or more to 100 nm in the longitudinal direction of the fiber in the field of view of the fiber on the surface of the fiber. The direction of the fiber moment axis is the direction perpendicular to the direction of the direction. When the concave portion of the surface E observed by the conventional fiber is circular, since the fiber of the present invention has a crack shape in the direction perpendicular to the fiber, it becomes an adhesion hindering shear on the surface. The crack-like recess is charged to the above area by a fee of 1. This is because: It can be fully reversed: it will become special: the invention of fiber materials. The high score of the 丨 high: the diameter is better to have the charge i, the other side (the monofilament fiber force microscope to the depth of 2 μιη 10 > the long axis of the fiber) convex structure, the I axis is about a little drooping There are 30 or more 201028508, more preferably 35 or more, and 100 or less. It is considered that if the depth of the crack-like recess is less than 10 nm, the improvement in resin adhesion cannot be expected too much; if it exceeds 1 〇〇 nm When the fiber of the present invention is attached to the surface uneven structure in the average cross-sectional profile, the surface roughness Ra is preferably 1.5 to 6.0 nn, Ra is more preferably 2.0 nm or more, and further preferably When the Ra is in this range, the effect on the reduction of the physical properties of the fiber is small, and on the other hand, an excellent anchoring effect can be exhibited. Further, it is possible to form a large width and a strong shear on the surface. The fiber portion of the present invention is observed by an atomic force microscope on the surface of the fiber. The longitudinal direction of the fiber in the field of view is 4 μm χ χ 2 2 2 2 ι χ , , , , , χ χ χ χ 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无 无Highly flat The height difference of the uniform enthalpy is preferably from 20 nm to 100 nm, and the height difference is more preferably 30 nm or more, further preferably 40 nm or more. The height difference in the present invention means a valley and a vertex of the convex portion of the surface uneven structure. When the height difference is within this range, the influence on the decrease in the physical properties of the fiber is small, and on the other hand, an excellent anchoring effect can be exhibited. (Manufacturing method) Further, the method for producing the fiber of the present invention is, for example, Preferably, by using a fiber having a strength of 8 cN/dtex or more, an ion beam is irradiated on the surface thereof to form a surface uneven structure. In the case of using plasma treatment, high-frequency sputtering etching treatment, etc., if the irradiation time and the irradiation energy are increased, At this time, the concave portion itself is reduced. It becomes difficult to obtain the fiber of the present invention. Although the convex portion or the crack-like concave portion having a large height difference can be obtained by irradiating the ion beam, 201028508 is not determined, but the estimation system is Since the ion beam has directionality at the ion velocity, it is possible to effectively obtain a convex portion having a large height difference. In order to perform ion beam treatment on the fiber, in spinning or After the heat treatment, it is possible to perform a roll-to-roll method, a method of performing a continuous roll-to-roll process using an ion beam processing apparatus, or a batch method based on an operational viewpoint. Preferably, the roll-to-roll method. In addition to the cellulose, the object to be treated may be a fiber bundle which is untwisted into a monofilament fiber and made unidirectional or a fabric as an ion beam for irradiation to the fiber. The ion gun can, for example, utilize a closed drift ion source manufactured by Kauffman, which can utilize DC discharge, RF discharge, microwave discharge, or the like. In particular, in the roll-to-roll process, a linear ion source is preferably used. The gas used in the ion gun is not limited as long as it can generate ionic particles, for example, a mixture of hydrogen '氦, oxygen, nitrogen, air, fluorine, helium, argon, neon or N20. Among the appropriate choices are used by ®. Among these gases, in particular, when oxygen or air forms the above-mentioned convex portion on the surface of the fiber, it is preferable to impart a functional group. The type and intensity of the ion beam irradiated on the fiber can be modified to the above range, and is not particularly limited. Usually, the energy of the ion particles constituting the ion beam is appropriately selected from the discharge voltage and discharge of the ion gun. The current, the discharge electric power, the beam gas flow rate, and the like are adjusted to about 1 〇·2 to 10 Ω KeV, the discharge voltage is adjusted to about 295 to 800 W, and the discharge current is adjusted to about 0.1 to 10 A to be irradiated. Preferably, the treatment is performed at 201028508, the pressure is adjusted to about 0.1 to 1.0 pPa, and the fiber transport speed is adjusted to about 〇.01 to 〇-3 m/min. (Evaluation method of adhesion) The adhesion evaluation method of fiber and resin generally adopts a droplet method or an ILSS method. The droplet method is a method of evaluating the stress when the fiber is extracted from the resin beads, and since the resin beads of a uniform shape are hardly obtained, there is a problem of accuracy and efficiency. On the other hand, the ILSS method is a method of evaluating the interfacial shear stress when a shear stress is applied to a resin sheet embedded with a fiber by a 4-point bending test, and is easily subjected to the strength characteristics of the resin or the fiber. Impact, accuracy is low. In the evaluation of the adhesion to the fiber resin of the present invention, a method of evaluating the attenuation of the fiber tensile stress when the fiber is embedded in the resin and the fiber is extracted is used. In this evaluation method, a test piece of a certain shape can be obtained, and further, the influence of the material strength characteristics is small, and evaluation of high precision and high efficiency is possible. Q Fig. 1 is a view schematically showing a method of preparing a test piece. Specifically, the following method is used: (a) The two sides of the embedded plate for the electron microscope having a length of 12 mm, a width of 5 mm, and a thickness of 3 mm are separated by a single-sided blade to a depth of 〇.〇5 to 0.1 mm. Sew 2, placed on a 20 cm square base. The base is preferably a glass plate, but is not particularly limited as long as it is flat and can withstand heating of 60 °C. (b) Next, the monofilament fiber l is unwound from the yarn, and the fiber is placed over the -10-201028508, and the fiber is sandwiched and held in the slit 2. In this case, the length of one side of the monofilament fiber 1 outside the resin is set to 15 to 20 cm, and the both ends of the fiber are fixed to the base by the adhesive tape so that the monofilament fiber 1 does not relax. Form 4). (c) Next, a substrate (LUVEAK 812) of 62CC/10〇CC thermosetting epoxy resin and a curing agent (LUVEAK DDSA) are blended and stored in a refrigerator, and returned to normal temperature in a desiccator. Using a glass rod of 4 mtn in diameter, add 10 drops of the hardening accelerator (LUVEAK - DMP30), while keeping the bubbles out, and stirring for 1 minute. The storage period of the blending solution is set to 1 month. The resin liquid 3 was poured into the embedding plate, and the amount was adjusted so as to be about 5 mm from the embedding plate. The adhesive tape was removed and hardened in an oven at 60 ° C for 12 hours. (d) After cooling at room temperature, it is noted that the monofilament fiber 1 is not broken, and the resin sheet is taken out from the embedded plate to obtain a test piece comprising the resin 5 and the monofilament fiber 1. A sheet of 3 X 2 cm was bent by sandwiching the fibers at one end of the monofilament fiber 1 outside the resin, and fixed by an adhesive. Fig. 2 is a view schematically showing a method for measuring a stress distribution using Raman scattering. The test piece is mounted on a sample table for microscopic Raman scattering measurement, and the monofilament fiber 1 outside the resin is attached to the end of the sample stage. On the roller, use a stopper (Stopper) to fix the test piece before and after. A load (6) 15gf is placed on the paper sheet of the monofilament fiber 1 disposed outside the resin, and the monofilament fiber 1 in the resin is measured along the fiber axis by micro Raman scattering at intervals of 10 μm. 11 - 201028508 Raman scattering. Since the wave number of the Raman scattering is determined by the seventh, using the calibration curve, the stress can be increased from Raman. Fig. 3 is a view schematically showing the above-described adhesion evaluation. In the resin, since the tensile stress applied by the monofilament fiber 1 to the fiber is toward ί ^, a distance along the fiber axis can be obtained.
G 布。若增大外加應力時，從纖維進入 著界面之降伏，隨著外加應力變大，界 界面降伏區域係不同於完全接著區域 若接著性良好時，完全接著區域 界面降伏之應力的臨界値爲大的。因 域與完全接著區域之應力分布的反曲 距離、界面降伏點（xc)與應力、界 Q 評估接著性爲可能的。 第4圖係示意顯示上述接著界面 的圖。 針對本發明之纖維，作爲判斷與 接著界面強度標準之方法，能夠採用 予複合材料時之有無界面降伏區域的 張強度測定裝置，在以使2〜3mm之 形樹脂中長軸方向成爲平行之方式而 根據分子之外加應力 散射之波數而得到外 估法中之應力分布的 由樹脂所支撐，所以 If脂內部越衰減。亦 數所觀察時之應力分 樹脂之位置，發生接 .面降伏區域將擴大。 〇 爲廣的，再者，發生 而，利用界面降伏區 點中之沿著纖維軸的 面降伏應力（σ。）而 強度之標準判斷方法 樹脂的複合材料中之 以判斷將一定歪斜賦 方法。亦即，利用拉 ΡΒΖ單絲纖維與長方 完全埋入的試驗片， -12- 201028508 對長軸方向施加一定之歪斜。於施加歪斜之狀態下，依照 拉曼散射，利用阻抗應變計8而測定纖維之應力，由相對 於纖維軸之應力分布，確認有無界面降伏區域。 首先，本發明之纖維係藉由使裂紋狀凹部之個數、平 均剖面輪廓中之表面凹凸構造的表面粗糙度Ra、表面凹凸 構造之高低差具有如上述之値，使界面降伏應力（σ。）成 爲1.2 GPa以上、界面降伏點（X。）成爲0.1mm以下，於 ^ 上述接著界面強度之標準判斷方法中，樹脂爲環氧樹脂， 〇 歪斜0.8%之時，不會發生界面之降伏，可以得到足以信賴 性高的實用之複合材料。界面降伏應力之範圍較佳爲 1.5GPa以上，更佳爲1.7 GPa以上，另外，界面降伏點之 範圍較佳爲〇.〇9mm以下，更佳爲0.08mm以下。 實施例 以下，藉由實施例進一步詳細說明本發明，本發明並 不受此等實施例所限定。還有，各種特性之評估係採用下 Q 述之方法： (1 )拉張強度 於標準狀態（溫度：20±2°C、相對濕度（RH ) 65±2% ) 之試驗室內放置纖維24小時以上之後，依據JIS-L-1013 而利用拉張試驗機以測定纖維之拉張強度。 (2 )表面粗糙度Ra 纖維表面之凹凸構造係使用原子間力顯微鏡（AFM) 而進行評估。AFM係使用 SII NanoTechnology股份公司 -13- 201028508 (SII )之 SPA300。AFM探針係使用由 SII所販售的 DF-40P，限定使用新品之探針。掃描器係使用FS-20A。另 外，拍攝像素數係設爲520像素χ256像素。於觀察前，使 AFM探針接觸於試料表面的位置係設爲纖維短軸方向之中 心附近，掃描方向係設爲平行於纖維長軸。觀察視野範圍 係設爲（纖維長軸方向）x(纖維短軸方向）= 4μηιχ2μιη。 將觀察視野切出3 00個剖面，藉由平均剖面輪廓功能而解 析所得到的此等剖面之平均化像素的各表面粗糙度Ra。將 藉由此方法所得到的無規所切出的5個觀察視野中之Ra 値的平均値設爲表面粗糙度Ra。 (3 )高低差 纖維表面之凹凸構造係使用原子間力顯微鏡（AFM ) 而進行評估。AFM係使用 SII NanoTechnology股份公司 (SII )之 SPA3 00。AFM探針係使用由 SII所販售的 DF-40P，限定使用新品之探針。掃描器係使用FS-20A。於 φ 觀察前，使AFM探針接觸於試料表面的位置係設爲纖維短 軸方向之中心附近，掃描方向係設爲平行於纖維長軸。觀 察視野範圍係設爲（纖維長軸方向）χ(纖維短軸方向）= 4 μιη X 2 μιη。從觀察視野內無規地切出3個剖面，將剖面通 過凸部中心者之高度平均値設爲高低差。 (4)裂紋狀凹部之個數 纖維表面之凹凸構造係使用原子間力顯微鏡（AFM ) 而進行評估。AFM係使用 SII NanoTechnology股份公司 -14- 201028508 (SII )之 SP A3 00。AFM探針係使用由SII所販售的 DF-40P，限定使用新品之探針。掃描器係使用FS-20A。於 觀察前’使AFM探針接觸於試料表面的位置係設爲纖維短 軸方向之中心附近，掃描方向係設爲平行於纖維長軸。觀 察視野範圍係設爲（纖維長軸方向）χ(纖維短軸方向）= 4μιηχ2μιη。利用Image Metrology A/S公司製之掃描探針影 像處理器（Scanning Probe Image Processor)而解析觀察 影像。平行於纖維長軸方向，以0.02μπι間隔進行切片而切 出剖面，將於纖維短軸方向連接Ο.ΐμπι以上之凹部定義爲 裂紋狀凹部，測定觀察視野範圍4μιη><2μιη中之個數。 (5 )拉曼散射測定 拉曼散射光譜係利用下列方法而進行測定。拉曼測定 裝置（分光器）係使用R?nishaw公司之System 1 000而進 行測定。光源係氦-氖雷射（波長63 3 nm)。將纖維與樹脂 之試驗片裝設於顯微拉曼散射測定用試料台，將樹脂外之 Q 纖維架設於試料台端所附屬的輥上，利用制動器而固定試 驗片之前後》在裝設於樹脂外之纖維的紙片上裝設載重 15g，藉由顯微拉曼散射，以1 Ομπι間隔，沿著纖維軸而測 定樹脂中之纖維的拉曼散射。拉曼之測定係利用靜態模式 (St at icMode)而針對測定範圍970〜1810( cm·1)，採用 累積次數：64次、曝光時間：1秒、雷射強度：1、1〇、25、 50、100%之中的最適強度。解析所用之波峰（peak)係採用 芳香族環之伸縮振動所歸屬的1619cm·1之帶（band)。由於 -15- 201028508 基線之紊亂爲大的，波峰之形狀具有歪斜，所以不採用使 用高斯函數之曲線擬合（curve fit)，以目測決定波峰形 狀而推斷波峰中央（peakcenter)。使用拉曼帶波數與拉張應 力之檢量線而從所得到的拉曼帶頻率求出纖維之外加應 力，得到相對於沿著纖維軸之距離的應力分布。畫出所得 到的應力分布之近似線，決定完全接著區域與界面降伏區 域之反曲點。將沿著在反曲點之纖維軸的距離設爲界面降 伏點X。、將應力設爲界面降伏應力ac。 (實施例1〜4 ) 作爲所處理的纖維，係使用東洋紡績（股份）製ZyIon (註冊商標）HM (實施例1 ) 、ZyIon (註冊商標）AS (實 施例2) 、Dyneema (註冊商標）SK60(實施例3)，及 Toray Dupont製Kevlar (註冊商標）29 (實施例4)。從 纖維束而將此等纖維解開成單絲纖維，空出間隔而排列於 聚醯亞胺薄膜上，使用聚醯亞胺黏著膠帶而貼附。於真空 〇 槽中，—面使輥行進，一面利用離子槍而進行將氧離子照 射於此薄膜上，處理該纖維之表面。離子束處理裝置係一 種捲對捲方式之裝置，一面使薄膜從輥而向捲出室、濺鍍 室、預備室、捲取室移動，一面依序進行表面處理，其後， 被輥所捲取。 各室之間係藉狹縫而予以槪略隔開。於離子槍室中， 薄膜係接觸於冷卻輥，藉由冷卻輥之溫度（-5 °c)而被冷 卻，以使輥寬方向得以均一離子照射之方式來使用寬度廣 -16- 201028508 的離子槍。離子槍係使用Advanced Energy Industries公 司之38CMLIS。作爲導入離子槍之氣體係使用氧，於放電 電壓540V、放電電流0.5 6A、放電電力295W、射束氣體流 量45sccm、處理壓力hlOdpa下，從距離薄膜與纖維4cm 之位置照射離子束。薄膜係使用250mm寬度者，輥輸送速 度係設爲〇_〇5m/min。氧並不進行從離子槍以外之導入。將 實施例1〜4所得到的纖維之詳細內容與評估結果顯示於 翁 表1 ° (實施例5、6 ) 作爲所處理的纖維係使用東洋紡績（股份）製ZyIon (註冊商標）HM(實施例5)與Zylon (註冊商標）AS (實 施例6)。爲了使單位面積所施加的能量降低，除了使輥 輸送速度設爲〇.25m/min以外，進行相同於實施例1〜4之 方式而實施離子束處理。將實施例5、6所得到的纖維之詳 細內容與評估結果顯示於表1。 Ο (比較例1 ) 作爲所處理的纖維係使用東洋紡績（股份）製Zylon (註冊商標）AS，但不進行離子束處理。將以比較例1所 得到的纖維之詳細內容與評估結果顯示於表1。 (比較例2〜5)本東洋紡績（股份）製Zy Ion (註冊 商標）HM (比較例3 )、Zylon (註冊商標）AS (比較例2、 6)、〇丫1^61113(註冊商標）81^60(比較例 5)，及 TorayDupont 製Kevlar (註冊商標）29(比較例4)。從纖維束而將此 -17- 201028508 等纖維解開成單絲纖維，空出間隔而排列於A4大小之pE 薄膜製框（框架寬度2cm)上，使用聚醢亞胺黏著膠帶而 予以貼附。將此薄膜框設置於2個電漿產生電極間，進行 氧離子束照射，真空電漿處理該纖維之表面。於放電電力 3 000W、氣體流量5000sccm、處理壓力400mTorr下進行處 理。將比較例2〜5所得到的纖維之詳細內容與評估結果顯 示於表1。 ^ (比較例6 )本東洋紡績（股份）製Zylon (註冊商標） AS、將纖維輸送速度設爲0.0 1 m/min以外，利用相同於比 較例2〜5之方法，進行真空電漿處理。將以比較例6所得 到的纖維之詳細內容與評估結果顯示於表1。 ❿ -18- 201028508G cloth. If the applied stress is increased, the fiber will enter the interface, and as the applied stress becomes larger, the boundary of the interface is different from that of the complete boundary. If the adhesion is good, the critical threshold of the stress at the full interface boundary is large. of. It is possible to evaluate the recurve distance of the stress distribution of the domain and the fully connected region, the interface drop point (xc) and the stress, and the boundary Q. Fig. 4 is a view schematically showing the above-described subsequent interface. With regard to the fiber of the present invention, as a method for determining the strength of the interface strength, it is possible to use a tensile strength measuring device for the presence or absence of the interface declining region in the case of the composite material, in such a manner that the long axis direction of the resin having a shape of 2 to 3 mm is parallel. On the other hand, the stress distribution in the external evaluation method is supported by the resin according to the wave number of the stress-scattering of the molecules, so that the inside of the If fat is attenuated. Also, when the stress is observed, the position of the resin is divided, and the area where the surface is lowered is enlarged. 〇 〇 , 再 再 再 再 再 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用 利用That is, a test piece which is completely embedded by pulling the monofilament fiber and the rectangular shape, -12-201028508 applies a certain skew to the direction of the long axis. In the state where the skew is applied, the stress of the fiber is measured by the impedance strain gauge 8 in accordance with Raman scattering, and the presence or absence of the interface relief region is confirmed by the stress distribution with respect to the fiber axis. First, the fiber of the present invention has an interface undulation stress (σ) by setting the number of the crack-like recesses, the surface roughness Ra of the surface uneven structure in the average cross-sectional profile, and the height difference of the surface uneven structure as described above. ) is 1.2 GPa or more, and the interface drop point (X.) is 0.1 mm or less. In the above-mentioned standard method for judging the interface strength, the resin is epoxy resin, and when the skew is 0.8%, the interface does not fall. A practical composite material with high reliability can be obtained. The range of the interface lodging stress is preferably 1.5 GPa or more, more preferably 1.7 GPa or more, and the range of the interface drop point is preferably 〇.〇9 mm or less, more preferably 0.08 mm or less. EXAMPLES Hereinafter, the present invention will be described in further detail by way of examples, which are not limited by the examples. Also, the evaluation of various characteristics is carried out by the method described in the following Q: (1) The tensile strength is placed in a test chamber of a standard state (temperature: 20 ± 2 ° C, relative humidity (RH) 65 ± 2%) for 24 hours. After the above, a tensile tester was used in accordance with JIS-L-1013 to measure the tensile strength of the fiber. (2) Surface roughness Ra The uneven structure of the fiber surface was evaluated using an atomic force microscope (AFM). AFM uses the SPA300 of SII NanoTechnology AG -13- 201028508 (SII). The AFM probe uses a DF-40P sold by SII to limit the use of new probes. The scanner uses the FS-20A. In addition, the number of shot pixels is set to 520 pixels χ 256 pixels. Before the observation, the position at which the AFM probe was brought into contact with the surface of the sample was set to the vicinity of the center of the short-axis direction of the fiber, and the scanning direction was set to be parallel to the long axis of the fiber. The observation field of view is set to (fiber longitudinal axis direction) x (fiber short axis direction) = 4μηιχ2μιη. The observed field of view was cut out of 300 sections, and the surface roughness Ra of the averaged pixels of the obtained sections was analyzed by the average profile function. The average 値 of Ra 値 in the five observation fields cut out by the random method obtained by this method was defined as the surface roughness Ra. (3) Height difference The uneven structure of the fiber surface was evaluated using an atomic force microscope (AFM). AFM uses SPA3 00 from SII NanoTechnology AG (SII). The AFM probe uses a DF-40P sold by SII to limit the use of new probes. The scanner uses the FS-20A. Before the observation of φ, the position at which the AFM probe was brought into contact with the surface of the sample was set to be near the center of the short axis direction of the fiber, and the scanning direction was set to be parallel to the long axis of the fiber. The viewing field of view is set to (fiber long axis direction) χ (fiber short axis direction) = 4 μιη X 2 μιη. Three sections were randomly cut out from the observation field, and the height of the section passing through the center of the protrusion was set to a height difference. (4) Number of crack-like recesses The uneven structure of the fiber surface was evaluated using an atomic force microscope (AFM). AFM uses SP A3 00 from SII NanoTechnology AG -14- 201028508 (SII). The AFM probe uses a DF-40P sold by SII to limit the use of new probes. The scanner uses the FS-20A. Before the observation, the position at which the AFM probe was brought into contact with the surface of the sample was set to the vicinity of the center in the short axis direction of the fiber, and the scanning direction was set to be parallel to the long axis of the fiber. The viewing field of view was set to (fiber longitudinal axis direction) χ (fiber short axis direction) = 4 μιη χ 2 μιη. The observation image was analyzed using a Scanning Probe Image Processor manufactured by Image Metrology A/S. Parallel to the longitudinal direction of the fiber, the slice was cut at intervals of 0.02 μm, and the cross section was cut out. The concave portion connected to the 短.ΐμπι or more in the short-axis direction of the fiber was defined as a crack-like concave portion, and the number of observation fields of view 4 μιη><2 μιη was measured. . (5) Raman scattering measurement The Raman scattering spectrum was measured by the following method. The Raman measuring device (beam splitter) was measured using R?nishaw's System 1 000. The light source is a 氦-氖 laser (wavelength 63 3 nm). The test piece of the fiber and the resin was mounted on a sample rack for micro-Raman scattering measurement, and the Q fiber outside the resin was placed on a roller attached to the end of the sample stage, and the test piece was fixed by a brake before and after being attached to the resin. The paper of the outer fiber was loaded with a load of 15 g, and the Raman scattering of the fiber in the resin was measured along the fiber axis by micro Raman scattering at intervals of 1 μm. The measurement of Raman uses the static mode (St icMode) for the measurement range 970~1810 (cm·1), the cumulative number of times: 64 times, the exposure time: 1 second, the laser intensity: 1, 1 〇, 25, 50, the optimum intensity among 100%. The peak used for the analysis is a band of 1619 cm·1 to which the stretching vibration of the aromatic ring belongs. Since the -15-201028508 baseline disorder is large and the shape of the peak is skewed, the curve fit is determined without using a Gaussian function, and the peak shape is inferred by visually determining the peak shape. The stress is applied to the fiber from the obtained Raman band frequency using the Raman band wave number and the tensile stress line, and the stress distribution with respect to the distance along the fiber axis is obtained. Draw the approximate line of the resulting stress distribution and determine the inflection point of the fully following region and the interface relief region. The distance along the fiber axis at the inflection point is taken as the interface drop point X. The stress is set as the interface relief stress ac. (Examples 1 to 4) As the fiber to be treated, ZyIon (registered trademark) HM (Example 1), ZyIon (registered trademark) AS (Example 2), and Dyneema (registered trademark) manufactured by Toyobo Co., Ltd. were used. SK60 (Example 3), and Kevlar (registered trademark) 29 manufactured by Toray Dupont (Example 4). These fibers were unwound from the fiber bundle into monofilament fibers, which were placed on a polyimide film at intervals, and adhered using a polyimide tape. In the vacuum sump, the surface is caused to travel by the roller, and oxygen ions are irradiated onto the film by an ion gun to treat the surface of the fiber. The ion beam processing apparatus is a roll-to-roll type device that moves a film from a roll to a take-out chamber, a sputtering chamber, a preliminary chamber, and a take-up chamber while performing surface treatment in sequence, and then is rolled by a roll. take. The chambers are separated by a slit. In the ion gun chamber, the film is contacted with a cooling roll and cooled by the temperature of the cooling roll (-5 °c) to use ions of a wide width -16 - 201028508 by uniform ion irradiation in the roll width direction. gun. The ion gun system uses 38CMLIS from Advanced Energy Industries. Oxygen was used as a gas system introduced into the ion gun, and the ion beam was irradiated from a position 4 cm away from the film and the fiber at a discharge voltage of 540 V, a discharge current of 0.56 A, a discharge electric power of 295 W, a beam gas flow rate of 45 sccm, and a treatment pressure hlOdpa. For the film system, a roll width of 250 mm was used, and the roll conveyance speed was set to 〇_〇 5 m/min. Oxygen is not introduced from outside the ion gun. The details and evaluation results of the fibers obtained in Examples 1 to 4 are shown in Table 1 (Examples 5 and 6). As the fiber to be treated, ZyIon (registered trademark) HM (produced by Toyobo Co., Ltd.) was used. Example 5) and Zylon (registered trademark) AS (Example 6). In order to reduce the energy per unit area, ion beam treatment was carried out in the same manner as in Examples 1 to 4 except that the roll transport speed was set to 〇25 m/min. The details of the fibers obtained in Examples 5 and 6 and the evaluation results are shown in Table 1.比较 (Comparative Example 1) Zylon (registered trademark) AS manufactured by Toyobo Co., Ltd. was used as the fiber system to be treated, but ion beam treatment was not performed. The details of the fibers obtained in Comparative Example 1 and the evaluation results are shown in Table 1. (Comparative Examples 2 to 5) Zy Ion (registered trademark) HM (Comparative Example 3), Zylon (registered trademark) AS (Comparative Example 2, 6), 〇丫1^61113 (registered trademark) of Toyobo Co., Ltd. 81^60 (Comparative Example 5), and Kevlar (registered trademark) 29 manufactured by Toray Dupont (Comparative Example 4). From the fiber bundle, the fibers such as -17-201028508 were untwisted into monofilament fibers, and placed in a P4 film frame (frame width of 2 cm) of A4 size at intervals, and adhered using a polyimide adhesive tape. The film frame was placed between two plasma generating electrodes, subjected to oxygen ion beam irradiation, and the surface of the fiber was treated by vacuum plasma. The treatment was carried out at a discharge electric power of 3 000 W, a gas flow rate of 5000 sccm, and a treatment pressure of 400 mTorr. The details of the fibers obtained in Comparative Examples 2 to 5 and the evaluation results are shown in Table 1. (Comparative Example 6) A vacuum plasma treatment was carried out by the same method as Comparative Examples 2 to 5 except that Zylon (registered trademark) AS manufactured by Toyobo Co., Ltd. was used, and the fiber transport speed was set to 0.01 m/min. The details of the fibers obtained in Comparative Example 6 and the evaluation results are shown in Table 1. ❿ -18- 201028508
Λ ^ a 1.85 1.77 1.90 2.01 κη yn 0.69 cs 4A 1.08 1.10 0.87 Xc mm 0.07 0.08丨 0.06 0.04 0.10 0.09 1 0.15 0.12 0.12 o 0.12 0.13 8 I 11 雜皿 45.3 40.5 42.1 46.3 25.3 21.6 Ο 16.2 5 iri o 2 高低差 nm 63.78 59.41 61.85 64.26 25.11 23.56 4.01 10.96 1 17.95 12.31 15.43 8.26 Ra run 2.972 3.105 2.702 3.280 1.891 1.852 0.118 1.242 1.331 1.226 1.354 0.985 纖維輸送 速度 m/min 0.05 0.05, 0.05 0.05 0.25 0.25 1 0.05 1 0.05 0.05 0.05 0.01 電力 W 295 ON κη σ\ CN On (S On <S 1 3000 1 3000 3000 3000 3000 拉張 強度 cN/dtex 卜 m 卜 m 20.3 VO cs ?； P； P； P； 20.3 <N P； 纖度 dtex 卜 卜 \q 1.15 278 卜 處理方法 離子槍 離子槍 離子槍 離子槍 離子槍 離子槍 未處理 真空電漿 i- 真空電漿 真空電漿 真空電漿 真空電漿 纖維 Zylon® AS Zylon® HM Kevla® 29 j Dyneema® SK60 Zylon® AS Zylon® HM Zylon® AS Zylon® AS Zylon® HM Kevla r ® 29 Dyneema® SK60 Zylon® AS 實施例1 實施例2 實施例3 實施例4 實施例5 實施例ό 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 201028508 產業上之利用可能性 由於本發明之表面改質纖維係具有作爲複合材料之實 用的接著性，能夠於複合材料中充分發揮纖維之高彈性 率。例如，用以封裝矽晶片之高密度高性能電路基板（核 心基板）用途係理所當然的，也能夠使用於遍及電纜、電 線或光纖等之張力構件；繩子等之緊張材；火箭絕緣材、 火箭外殼、壓力容器、太空裝之繩帶、行星探測氣球等之 航空、宇宙資材、耐彈材等之耐撞撃用構件：手套等之耐 0 切割用構件；消防衣、耐熱氈、工廠用墊圈、耐熱織物、 各種密封材、耐熱緩衝墊、濾器等之耐熱耐燃構件；帶狀 物、輪胎、鞋底、繩索、水管等之橡膠補強劑；釣魚線、 釣竿、網球拍、桌球拍、羽球拍、高爾夫球桿、高爾夫球 桿頭、腸線（gut)、弦、厚蓬帆布、跑鞋、馬拉松鞋、釘 鞋、溜冰鞋、籃球鞋、排球鞋等之運動鞋；競技（走）用 自行車及其車輪、公路車、賽車、越野車、複合輪、圓盤 輪、張力圓盤、輪輻、制動線、變速機線、競技（走）用 0 輪椅及其車輪、護具、賽車連身服、雪靴、滑雪杖、安全 帽、降落傘等之運動關係資材；無級變速器（A vance )帶、 離合器用紡織面料等之耐摩擦材；各種建築材料用補強劑 及其他之騎士服裝、揚聲器錐、重量輕之嬰兒車、重量輕 之輪椅、重量輕之看護用床、救生圈、救生衣等廣泛之用 途。 【圖式簡單說明】 第1圖係示意顯示本發明所採用的使用拉曼散射之接著 性評估法中之試驗片作成方法的圖。 -20- 201028508 第2圖係示意顯示本發明所採用的使用拉曼散射之接著 性評估法中之應力分布測定方法的圖。 第3圖係示意顯示本發明所採用的使用拉曼散射之接著 性評估法中之應力分布與接著性評估指標的圖。 第4圖係本發明所採用的用於接著界面強度之標準判斷 方法的試驗片示意圖。 【主要元件符號說明】 1 2 ❹ 3 4 5 6 7 8 單絲纖維 狹縫 熱硬化性環氧樹脂 矽橡膠製型框 樹脂 載重 外加應力 阻抗應變計 ❹ -21-Λ ^ a 1.85 1.77 1.90 2.01 κη yn 0.69 cs 4A 1.08 1.10 0.87 Xc mm 0.07 0.08丨0.06 0.04 0.10 0.09 1 0.15 0.12 0.12 o 0.12 0.13 8 I 11 Miscellaneous 45.3 40.5 42.1 46.3 25.3 21.6 Ο 16.2 5 iri o 2 Height difference Nm 63.78 59.41 61.85 64.26 25.11 23.56 4.01 10.96 1 17.95 12.31 15.43 8.26 Ra run 2.972 3.105 2.702 3.280 1.891 1.852 0.118 1.242 1.331 1.226 1.354 0.985 Fiber transport speed m/min 0.05 0.05, 0.05 0.05 0.25 0.25 1 0.05 1 0.05 0.05 0.05 0.01 Power W 295 ON κη σ\ CN On (S On <S 1 3000 1 3000 3000 3000 3000 tensile strength cN/dtex 卜 m 卜 m 20.3 VO cs ?; P; P; P; 20.3 <NP; denier dtex \q 1.15 278 Bu treatment method Ion gun ion gun ion gun ion gun ion gun ion gun untreated vacuum plasma i- vacuum plasma vacuum plasma vacuum plasma vacuum plasma fiber Zylon® AS Zylon® HM Kevla® 29 j Dyneema ® SK60 Zylon® AS Zylon® HM Zylon® AS Zylon® AS Zylon® HM Kevla r ® 29 Dyneema® SK60 Zylon® AS Example 1 Example 2 Example 3 Example 4 Example 5 Example ό Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 201028508 Industrial Applicability The surface-modified fiber of the present invention has practical adhesion as a composite material. It is possible to fully utilize the high elastic modulus of the fiber in the composite material. For example, the high-density high-performance circuit board (core substrate) used for packaging the germanium wafer can be used for tension members such as cables, wires, or optical fibers. ; tension materials such as ropes; rocket insulation materials, rocket casings, pressure vessels, space ropes, planetary probe balloons, etc., aviation, cosmic materials, elastic materials, and other crash-resistant components: gloves, etc. Components; fire-resistant garments, heat-resistant felts, factory gaskets, heat-resistant fabrics, various sealing materials, heat-resistant cushions, filters, etc.; heat-resistant and flame-resistant members; rubber reinforcements for belts, tires, soles, ropes, water pipes, etc.; , fishing rods, tennis rackets, table tennis rackets, badminton rackets, golf clubs, golf club heads, guts, strings, canvas, Running shoes, marathon shoes, spike shoes, skates, basketball shoes, volleyball shoes, etc.; sports (walking) bicycles and their wheels, road cars, racing cars, off-road vehicles, composite wheels, disc wheels, tension discs, spokes , brake line, transmission line, competitive (walking) with 0 wheelchairs and their wheels, protective gear, racing suits, snow boots, ski poles, helmets, parachutes and other sports relations materials; continuously variable transmission (A vance) Friction-resistant materials such as textile fabrics for belts and clutches; reinforcing materials for various building materials and other knight clothing, speaker cones, lightweight baby strollers, lightweight wheelchairs, lightweight nursing beds, lifebuoys, life jackets, etc. Use. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view schematically showing a test piece preparation method in the adhesion evaluation method using Raman scattering used in the present invention. -20- 201028508 Fig. 2 is a view schematically showing a method of measuring the stress distribution in the adhesion evaluation method using Raman scattering used in the present invention. Fig. 3 is a view schematically showing the stress distribution and the adhesion evaluation index in the adhesion evaluation method using Raman scattering employed in the present invention. Fig. 4 is a schematic view showing a test piece used in the present invention for the standard judgment method of the interface strength. [Description of main component symbols] 1 2 ❹ 3 4 5 6 7 8 Monofilament fiber Slit Thermosetting epoxy resin 矽Rubber frame Resin Load capacity Stress strain gauge ❹ -21-