200533627 玖、發明說明： 【發明所屬之技術領域】 本發明係關於與水泥漿（c e m e n t m a t r i X )間之黏著性優 越，且砂漿（mortar)與混凝土等補強效果均優越的水泥強 化用聚丙烯纖維，以及使用此水泥強化用聚丙烯纖維之纖 維補強水泥成形體，暨使用此水泥強化用聚丙烯纖維之混 凝土構造物的施工方法，和使用此水泥強化用聚丙烯纖維 之噴塗混凝土工法。 【先前技術】 從前，便有採用砂漿或混凝土的水泥成形品，或者建造 建築物外牆、隨道内壁、邊坡面（slope face)等，該等若 是成形體的脆性偏大，且若拉張強度（tensile strength) 、資曲耐力、彎·曲韋刃性、对衝擊性等物性不足的話，將因 壁面的劈裂，而有發生漏水、或外壁剝落掉下意外等危險 性的情況。所以，在該等水泥成形品的補強材方面，近年 便有採用鋼纖維、聚乙烯醇樹脂、聚烯烴樹脂、聚丙烯腈 樹脂、聚醯胺樹脂等合成樹脂纖維（例如參照日本公開專利 公報特開昭6 3 - 3 0 3 8 7 7號、同公報特開平8 - 2 1 8 2 2 0號、同 特開平9-8 6 9 84號、日本公告專利公報特公平1 -4 0 7 8 6號）。 但是，摻混著鋼纖維的混凝土，因為鋼纖維比重重達 7. 8，因而在材料的搬運或摻混作業方面較為困難，而且在 噴塗混凝土中，將有發生踏到因噴塗時的反彈而掉落的鋼 纖維造成受傷的虞慮，甚至亦有指出鋼纖維生鏽等缺點。 摻混著聚乙烯醇纖維的混凝土則潛在有：纖維本身已具 5 312/發明說明_補件)/93-06/93109393 200533627 有吸水性，且若纖維在鹼中達高溫狀態的話，將引發加水 分解現象，而且在相較於未摻混纖維的情況下，有坍落 (s 1 ump )明顯降低的傾向，為確保喷塗時所必要的坍落，因 而必須增加單位水量等等不良狀況。 再者，混凝土成形品的養護，在尺寸穩定性提昇、養護 時間縮短等目的之下，近年已有增加使用壓熱器 (a u t 〇 c 1 a v e )養護的現象，當施行此種壓熱器養護之情況 時，除聚烯烴系之外的纖維，將因耐鹼性不足而造成劣化 現象，導致出現無法使用為補強纖維的問題。 此外，聚烯烴樹脂則因為在分子構造内，幾乎未存在有 親水性基、或對與水泥間之黏著性有助益的官能基，因而 在與水泥漿間之黏著性將極為差劣，若破壞經聚烯烴樹脂 纖維補強過之水泥成形體的話，纖維將容易遭拔除，即便 發現因纖維的拔除抗力而造成衝擊強度或彎曲破壞能增 加，卻仍無法達到大幅提昇彎曲強度。 為改良相關聚烯烴系纖維在與水泥間的親和性，便有提 案將各種無機微粒子、或聚醋酸乙烯酯等親水性高分子物 質，添加於纖維中的方法，但是因為整體樹脂纖維中摻混 著異物，因而將損及延伸性，除無法獲得充分地纖維強度 之外，對樹脂纖維表面部分中除改質劑以外的部分，並無 法發生提昇親和性的作用，無法於添加量比例上獲得充分 改質效果。 另一方面，纖度1 0 0 d t以下、纖維長度5 m m以下的單紗 或集束紗、或由撕裂紗（s p 1 i t y a r η )系短纖維所構成聚嫦 312/發明說明書(補件)/93-06/93109393 200533627 烴系纖維，該等的纖維形狀，將發生纖維球之類的纖維塊， 且形成蓬鬆並較難均句分散於水泥中，尚且若為改良分散 性而將纖度變粗的話，因為在與水泥間的黏著性將惡化， 因而若施加彎曲應力的話，將發生纖維被拉除等情況，無 法達充分地補強效果。 相對於此，雖有提案針對將經對纖維截面賦予特定平均 平坦率凹凸的單紗纖度2 0 0 d t以上之粗纖維絲，切斷為纖 維長度5mm以上的聚丙稀纖維，施行由聚氧化伸烧基垸基 苯醚磷酸酯與聚氧化伸烷基脂肪酸酯所構成界面活性劑等 等各種塗布的方法（參照日本公開專利公報特開平 1 1 - 1 1 6 2 9 7號），但是，因為此界面活性劑在與聚烯烴系樹 脂纖維之間並無黏著性，因而即便與水泥漿黏著，可是在 聚烯烴系樹脂纖維與水泥漿之間並無法獲得充分地黏著 力，無法提昇水泥成形物的彎曲韌性。 本發明乃為解決如上述先前技術的問題點而所構思，其 目的在於提供一種可對聚烯烴系纖維賦予親水性，在與水 泥間之分散性、物理結合均良好，且與水泥漿間之黏著性 優越，可提升水泥成形物之彎曲強度、衝擊強度、或彎曲 韌性的水泥強化用聚丙烯纖維，以及使用此水泥強化用聚 丙烯纖維的纖維補強水泥成形體，暨使用此水泥強化用聚 丙烯纖維的混凝土構造物施工方法，和使用此水泥強化用 聚丙烯纖維的噴塗混凝土工法。 【發明内容】 本發明基本上係對聚烯烴樹脂，調配特定量之特定複合 312/發明說明書(補件)/93-06/93109393 200533627 構造接枝共聚物的界面活性劑而形成纖維。即，將相對於 ♦丙烯1 0 〇重量份，含有由乙烯-醋酸乙烯酯共聚物鏈段 5〇〜90重量％、與乙烯系聚合物鏈段5〇〜ι〇重量％所構成複 合構造接枝共聚物1〜10重量份的組成物，進行紡紗，而形 成水泥強化用聚丙烯纖維。藉此，便可對聚丙烯纖維與水 泥間的界面賦予優越的親和性，可形成與水泥漿間之黏著 性優越，且彎曲強度、衝擊強度均優越的水泥成形物製造 狀態。 此情況下，藉由將對經如上述紡紗過的纖維表面，賦予 凹凸形狀且單紗纖度2 0 0 d t以上的單紗，切斷為纖維長度 5ηυη以上’便可彌補一般在較粗纖維中所發生與水泥間之 接觸面積減少的缺點’在與水泥間之物理性結合將呈良好 狀態，可製造具優越彎曲韌性的水泥形成物。 再者，本發明的乙烯系聚合物係將不飽和羧酸、或其不 飽和羧酸S旨中之丨種或2種以上，施行聚合而獲得的聚合 物，例如將曱基丙烯酸、及其甲基丙烯酸甲酯施行聚合而 獲得的聚合物。 再者，本發明係屬於從將如上述所構成的聚丙烯纖雉適 量，添加於含有水泥、細骨材、及水的砂漿混合物中之水 泥組成物，所製得的纖維補強水泥成形體。 再者，本發明係從將如上述所構成的聚丙烯纖維一定 量，添加於含有水泥、細骨材、粗骨材及水的混凝土混合 物中，並進行製造的混凝土構造物之施工方法。 再者，本發明係將如上述所構成的聚丙烯纖維適量，添 8 312/發明說明 IK 補件)/93-06/93109393 200533627 加於含有水泥、細骨材、粗骨材及水的混凝土混合物中， 並將該等混合物在待施工面上噴射一定厚度尺寸的噴塗混 凝土工法。 【實施方式】 在本發明中，纖維原料中所使用的聚丙烯樹脂，可使用 丙烯單聚物、乙烯-丙烯嵌段共聚物、或無規共聚物等聚丙 烯共聚物、或該等的混合物。該等之中，就要求高強度、 耐熱性的水泥強化用而言，最好使用丙烯單聚物，特別以 選擇等規五元組分率（isotactic pentad fraction)。· 95 以上者為佳。此處所謂「等規五元組分率」係指A. Zambel 1 i 等在 Macromolecules 6925(1973)中所發表，使用 i3C-NMR 進行測得的聚丙烯分子内之五元組單位的等規分率 (isotactic fraction) ° 此聚丙烤系樹脂的熔融流率（m e 11 f 1 〇 w r a t e )(以下簡稱 「M F R」），就連續穩定生產性佳之觀點而言，最好在 0.卜5 0g/10分範圍内，尤以選擇在1〜10g/10分範圍内為 佳。 在聚丙烯系樹脂中，於紡紗過程中，配合需要亦可添加 聚烯烴。此處所謂「其他聚烯烴」，有如：高密度聚乙烯、 直鏈狀低密度聚乙烯、低密度聚乙烯、乙烯-醋酸乙烯酯共 聚物、乙烯-丙烯酸烷酯共聚物等聚乙烯系樹脂、聚丁烯-1 等等。 其次，針對複合構造接枝共聚物進行說明。 此接枝共聚物係由乙烯-醋酸乙烯酯共聚物鏈段（以下簡 312/發明說明書(補件)/93-06/93109393 200533627 稱「A鏈段」）5 0〜9 0重量°/◦，及乙烯系聚合物鏈段（以下簡 稱「B鏈段」）5 0〜1 0重量％所構成。通常A鏈段係構成接枝 共聚物的主鏈，B鏈段則構成接枝共聚物的側鏈。 構成上述A鏈段的乙烯-醋酸乙烯酯共聚物係醋酸乙烯 酯含量在1 0重量％以上，最好在1 〇〜8 0重量％範圍内，尤以 在2 0〜5 ◦重量％範圍内為佳。若醋酸乙烯酯含量低於1 〇重 量％的話，親水性將嫌不足，最好避免。上述乙烯-醋酸乙 烯酯共聚物的重量平均分子量，係1 0 0 0〜1 0 0萬，最好 5 0 0 0〜6 0萬。若重量平均分子量低於1 0 0 0之情況時，因為 耐熱性將降低，因而最好避免。反之，若重量平均分子量 超過1 0 0萬的話，因為成形加工性將降低，所以最好不要。 其次，形成接枝共聚物之B鏈段的乙烤系聚合物，係將 不飽和羧酸、或該等不飽和羧酸酯之其中1種或2種以上 進行聚合而獲得。 不飽和羧酸類可舉例如：丙烯酸、曱基丙烯酸、順丁烯二 酸、反丁烯二酸、順丁烯二酸酐等α，/?-不飽和羧酸、及 其金屬鹽。 再者，不飽和羧酸酯可舉例如：丙烯酸曱酯、丙烯酸正丁 酯、丙烯酸丁酯、曱基丙烯酸曱酯、曱基丙烯酸乙酯、甲 基丙烯酸丁酯等之α，/3 -不飽和羧酸酯等。 該等之中，以甲基丙烯酸與其甲基丙烯酸甲酯的組合較 為恰當。 再者，乙歸系聚合物聚合物的重量平均分子量係 1，0 0 0〜1 0 0萬，最好5，0 0 0〜5 0萬。當重量平均分子量低於 10 312/發明說明書(補件)/93-06/93109393 200533627 1，0 0 0之情況時，因為在與待改質樹脂間的相溶性將降 低，因而最好避免。反之，若超過100萬之情況時，因為 理由相同，所以最好迴避。 在複合構造接枝共聚物中，Α鏈段所佔比率係5 0〜9 0重 量％，最好6 0〜8 0重量％。所以，在複合構造接枝共聚物中， B鏈段所佔比率便為5 0〜1 0重量％，最好4 0〜2 0重量％。若A 鏈段比率低於5 0重量％的話，因為乙烯-醋酸乙烯酯共聚物 的改良效果將嫌不足，因而最好不要。反之，若A鏈段超 過9 0重量％的話，因為在與水泥漿間的黏著性將降低無法 提昇水泥成形物之衝擊強度及彎曲強度，所以最好避免。 所分散聚合物的粒徑係0 . 0 0 1〜1 0 μΐϋ，最好0 . 0 1〜5 μιιι。 若分散粒徑低於0. 0 0 1 μιη、或超過1 0 μιη的話，因為分散性 將降低，將發生如所獲得成形品外觀惡化、或機械物性降 低的狀況。 製造複合構造接枝共聚物之際的接枝化法，雖可為一般 所皆知的鏈轉移法、電離性輻射線照射法等任何方法，但 是最好採用下述方法。換句話說，此乃因為不致因接枝效 率較高，而因熱造成二次性凝聚情況，所以可更有效率的 突顯出性能，且製造方法較為簡單的緣故所致。 其次，針對複合相構造接枝共聚物的製造方法進行具體 說明。首先，將乙烯-醋酸乙烯酯共聚物1 0 0重量份懸浮於 水中，在並其中添加下述混合溶液，該混合溶液係至少在 1種的乙烯系單體1〜4 0 0重量份中，溶解著相對於該乙烯 系單體1 0 0重量份，為0. 1〜2 0重量份之1種或2種以上自 11 312/發明說明書(補件)/93-06/93109393 200533627 由基聚合性有機過氧化物的混合物，以及相對於乙烯系單 體與自由基聚合性有機過氧化物總計10 0重量份，為 0 . 0卜5重量份之可獲得1 0小時半衰期的分解溫度為4 0〜9 0 °c的聚合起始劑。 其次，在實質上不致引發聚合起始劑分解的條件下進行 加熱，俾使乙烯系單體、自由基聚合性有機過氧化物、及 聚合起始劑，含潤於乙烯-醋酸乙烯酯共聚物中，接著，使 此水性懸浮液的溫度上升。然後，使乙烯系單體、與自由 基聚合性有機過氧化物，在乙烯-醋酸乙烯酯共聚物中進行 共聚合，而獲得接枝化前驅物。 藉由將此接枝化前驅物在溶融下進行混練，便可獲得複 合構造接枝共聚物。此時，在接枝化前驅物中，混合乙烯-醋酸乙烯酯共聚物，並在溶融下進行混練，亦可獲得複合 構造接枝共聚物。 上述自由基聚合性有機過氧化物最好使用如：碳酸過氧 化第三丁基異丙苯基丙烯醯氧基乙酯、碳酸過氧化第三戊 基異丙苯基丙烯醯氧基乙酯、碳酸過氧化第三己基丙烯醯 氧基乙酯、碳酸1，1，3, 3 -四曱基過氧化丁基丙烯醯氧基乙 酯、碳酸過氧化異丙苯基丙烯醯氧基乙酯、碳酸對異丙基 過氧化異丙笨基丙烯醯氧基乙酯、碳酸過氧化第三丁基曱 基丙烯醯氧基乙酯、碳酸過氧化第三戊基異丙笨基甲基丙 烯醯氧基乙酯、碳酸過氧化第三己基曱基丙烯醯氧基乙 酯、碳酸過氧化第三丁基烯丙酯、碳酸過氧化第三丁基曱 基炼丙酷等。 12 312/發明說明書(補件)/93-06/93109393 200533627 上述複合構造接枝共聚物的MFR( 1 90°C、2 1 60g荷重、J IS K 6 9 2 2 - 1 )，係在0. 1〜20g/10分範圍内，最好在0. 5〜10 g/10 分範圍内。 本發明的水泥強化用聚丙烯纖維在相對於聚丙烯1 0 0重 量份之下，複合構造接枝共聚物為1〜10重量份，最好在 卜5重量份範圍内。若複合構造接枝共聚物的調配比率低 於1重量份的話，因為對聚烯烴樹脂纖維賦予親水性的效 果將降低，且在與水泥漿間之黏著性改良效果亦降低，因 而最好不要。反之，若超過10重量份之情況時，因為對聚 烯烴樹脂纖維的機械強度將降低，所以最好迴避。 在上述聚丙烯組成物中，隨使用目的在不脫逸本發明主 旨範疇下，亦可調配如：抗氧化劑、潤滑劑、紫外線吸收劑、 抗靜電劑、無機填充材、有機填充材、交聯劑、發泡劑、 核劑等添加劑。 在本發明中進行紡紗的聚丙烯纖維，構成主體的纖維形 狀，係將任意粗度的單紗進行切斷後的短纖維，其製造方 法並無特別限制，可採取從圓形、橢圓形、變形、或鏈紗 狀模具中擠出單紗的製造技術。 例如可採用公知溶融紡紗方法，或採用可進行高倍率延 伸處理的鏈紗狀模具進行紡紗。此情況下，從鏈紗狀模具 中熔融擠出聚丙烯，接著將經擠出的鏈紗狀帶直接施行延 伸處理而形成纖維。 鏈紗狀模具係具有至少將2個噴嘴串聯連接的形狀，通 常為連結5〜2 0個，最好1 0〜1 5個噴嘴的形狀。 13 312/發明說明書(補件)/93-06/93109393 200533627 再者，本發明的單紗亦可為將較粗單紗切斷的短纖 此情況下，除如上述的單層紗之外，亦可使用以聚丙 融點成分為芯層，且以聚丙烯低融點成分為鞘層的複 紗。此製造方法係將各層聚丙烯利用擠出機施行熔融 練，並從在略同心圓上設置著2層吐出孔的模具中心 孔，供應著由高融點成分所構成的芯層，在其外面擠 覆著由低融點成分所構成鞘層，而獲得複合單紗。 此情況下，因為實質的強力乃依存於芯層物性，所 融點成分最好使用如：丙稀單聚物、等規聚丙烯等，而 點成分則最好使用如：丙烯-乙烯嵌段共聚物與無規共 物、間規聚丙烯等。藉由使用依此所獲得的複合單紗 可抑制在混凝土成形時的加熱養護中發生聚丙烯纖維 化現象。 其次，上述單紗係施行熱延伸與熱鬆弛處理，藉由 處理而提高紗的剛性，可獲得延伸較小之水泥強化用 佳聚丙烯單紗。該熱延伸係在聚丙烯的融點以下、軟 以上的溫度下進行，通常延伸溫度為9 0〜1 5 0 °C ，延/ 率通常為5〜1 2倍，最好為7〜9倍，熱延伸法可採用女 輥式、熱板式、紅外線照射式、熱風烤箱式、熱水式 式。 經延伸過的聚丙烯紗的拉張強度係在5g/dt以上， 在6 g / d t以上。此外，拉張伸度在2 0 %以下，最好在 以下。若拉張強度、拉張伸度超越該等範圍的話，水 化用聚丙烯纖維的強力將嫌不足，最好避免。 312/發明說明書(補件)/93-06/93109393 維， 合單 混 吐出 出被 以南 低融 聚 ，便 熱劣 此熱 的較 化點 I中倍 口 ：熱 等方 最好 15% 泥強 14 200533627 依上述方法所形成的聚丙烯單紗之單紗纖度係 5〜1 0, 0 0 0分德士（dec it ex)(以下簡稱「dt」），最好在 1 0〜6 , 5 0 0 d t範圍内。此時，較細的單紗纖度5〜1 0 0 d t乃切 斷為如纖維長3〜3 0 m m，最好5〜1 5 m m的短纖維，而較粗的 單紗纖度2 0 0〜1 0，0 0 0 d t範圍者，則切斷為5〜1 0 0 _，最好 20〜70mn〗。若纖維長低於3mm的話，將發生從水泥中脫落的 不良情況，反之，若超越1 0 〇mn〗的話，分散性將變不良， 所以最好不要。 若上述單紗纖度低於5 d t的話，將因纖維過細而使在混 凝土混合物中的分散呈不均勻狀態，容易形成纖維球，在 施工性或補強性方面將出現問題，反之，若單紗纖度超過 2 0 0 d t的話，纖維與混凝土混合物間之接觸面積將減少， 且對彎曲應力將變為容易拉除狀態，補強效果惡化，因而 最好避免，所以在本發明中，對此單紗纖度2 0 0 d t以上的 較粗者，便必須在紡紗、熱延伸的後續步驟中，對表面賦 予凹凸形狀。藉此，便將增加纖維與混凝土間之接觸面積， 可抑制混凝土硬化後的纖維拉除情況，俾能提高補強效 果。此對表面賦予凹凸形狀的方法，可如對單紗施行壓花 加工。壓花加工係在將單紗進行延伸前或延伸後，藉由通 過壓花輥而實施，藉此便可在單紗長度方向上連續地形成 凹凸。 其中，壓花的長度與深度等形狀可為任意，但是必須設 定為利用擠壓崩潰而使纖維截面平均平坦率在1 . 5 / 1〜7 / 1 的範圍内。此平均平坦率係指經賦形多樣形狀的纖維戴面 15 3丨2/發明說明書(補件)/93-06/93109393 200533627 中，表示寬度與高度之平均比率的數值，若平均平坦率低 於1 . 5 /1的話，因為對纖維表面的凹凸賦形偏少，因而將 無法顯現出與平滑表面纖維間有補強效果的差異存在，反 之，若平均平坦率超過7 /1的話，將因賦形而造成強度明 顯劣化，且上述既定纖度的纖維對混凝土的分散性將有惡 化的傾向，將構成問題點。 本發明的水泥強化用聚丙烯纖維係混合於砂漿或混凝土 中，並可依各種實施態樣使用。 例如將聚丙烯纖維混合於水泥或混凝土中，再利用成形 而製造水泥成形品的方法；或者摻混聚丙烯纖維，經灌漿、 塗布而施工製造砂漿構造物或混凝土構造物的方法；或者 將聚丙烯纖維混入砂漿或混凝土中，經噴射而施工製造砂 漿構造物或混凝土構造物的方法等。 當將聚丙烯纖維混合於砂漿中之情況時，可調配於水 泥、細骨材、水、及適量混合材中再供使用。 再者，當將聚丙烯纖維混合於混凝土中之情況時，可調 配於水泥、細骨材、粗骨材、水及適量混合劑中再供使用。 其中，水泥可代表性舉例如：卜特蘭水泥（ρ 〇 r 11 a n d c e in e η t )、高爐水泥、氧化石夕水泥、飛灰水泥（f 1 y a s h c e m e n t)、白色卜蘭特水泥、氧化紹水泥等水硬性水泥 (h y d r a u 1 i c c e m e n t)，或如石膏、石灰等氣硬性水泥等水 泥類；而細骨材則可代表性舉例如：河砂、海砂、山砂、矽 砂、玻璃砂、鐵砂、灰砂、及其他人工砂等，另外，粗骨 材則可代表性舉例如：礫石、砂礫、碎石、爐渣、各種人工 16 31W發明說明書(補件)/93-06/93109393 200533627 輕量骨材等。 當製造水泥成形品之際，將聚丙烯纖維混合於混凝土中 的方法，可採用如：在水泥粉體中分散著聚丙烯纖維的方 法，或如在水泥漿中分散著聚丙烯纖維的預混法，或如同 時喷射出水泥、聚丙烯纖維、及水的噴塗法等公知方法。 聚丙烯纖維調配量在相對於水泥，係0 · 1〜10重量％，最 好0. 5〜5重量％。若調配量低於0. 1重量％的話，補強效果 將劣化，反之，若在1 0重量％以上的話，除較難均勻分散 之外，因為彎曲強度亦將降低，因而最好不要。 將依此所獲得水泥漿，依照用途而依循如造紙成形法、 擠出成形法、注入成形法等公知成形法而成形，藉由在常 溫中於大氣中或水中放置數十天的自然養護法，或者在常 溫中放置2〜3天後，再於1 0 0〜2 0 0 °C溫度中施行處理的壓 熱器養護法，便可形成經養護硬化的水泥成形品。 採用本發明聚丙烯纖維所製得水泥成形品的用途，乃橫 跨所有水泥製品，可使用如建物壁材、地板材混凝土、粉 光砂漿、防水混凝土、石棉浪板屋頂材等方面，或土木關 聯組件之如道路、跑道等的舖設、道路標誌、側溝等道路 構件，或如下水道、電纜管道等管路類；或如魚礁、防波 堤塊、菱形塊等，或其他各種建構物之如枕木、長椅、花 盆等方面。 再者，當將本發明聚丙烯纖維使用於砂漿構造物施工之 情況時，可在將水泥、細骨材、水、適量混合劑一起同時（或 在混練砂漿之狀態下）摻混入聚丙烯纖維，經攪拌，藉由將 17 312/發明說明書(補件)/93-06/93 ] 09393 200533627 其施行灌漿、塗布，而施工製造砂漿構 施工製造混凝土構造物之際，可在將水 材、水、適量混合劑一起同時（或在混会 摻混入聚丙烯纖維，經攪拌，藉由將其 而施工製造混凝土構造物。 再者，當將本發明聚丙烯纖維使用於 際，調配量乃相對於由水泥、細骨材、 成混凝土混合物1 m3之下，調配分散聚I 最好6〜1 4 k g，乃屬重要的一環。此乃因 調配量超過1 9kg，纖維仍無法均勻地分 而·彎曲I：刃性並未增加，反之，若調配量 噴射時的反彈將變大，且硬化後的補強 此情況時的混合方法，最好採行投入 粗骨材、水等所構成的混凝土混合物而 (b a s e c ο n c r e t e )之後，再將此混凝土底 投入聚丙烯纖維而實施混練的方法。混 次的混合量而異，一般而言，混凝土底 秒，在投入聚丙烯纖維後的混練亦設為 恰當。 此外，在喷塗混凝土工法中，當本發 述調配量使用的情況時，最好將i丹落範 範圍内。此乃因為若i丹落低於8cm的話 難，反之，若超過2 1 c m的話，反彈將變力 供依此種坍落範圍實施噴塗混凝土工法 3丨2/發明說明書(補件)/93-06/93109393 造物。此外，當在 泥、細骨材、粗骨 良混凝土之狀態下） 施行灌漿、塗布， 噴塗混凝土工法之 粗骨材、水等所構 两烯纖維4〜1 9kg， 為即便聚丙烯纖維 布於混凝土中，因 少於4kg的話，再 效果較小。 由水泥、細骨材、 形成混凝土底漿 漿進行混練之後， 練時間乃依平均一 漿的混練係4 5〜9 ◦ 4 5〜9 0秒範圍較為 明聚丙烯纖維依上 圍調整為8〜21cin ，噴射作業將變困 k，因而最好避免。 的噴射噴嘴，將喷 18 200533627 嘴配置成與噴射面呈直角狀態，且將噴嘴與噴射面間之距 離設為0 . 5〜1 . 5 η】，將屬較有效狀態。 依此，將混合著本發明聚丙烯纖維的混凝土混合物，在 使用為喷射混凝土時，將可使用於如隧道（包括斜井、直井 在内）、大空洞構造物的被覆工程、坡面、斜面、或防止壁 面風化、剝離/剝落、或隧道、水塌及橋樑的修補、補強工 程等方面。 以下，藉由實施例說明本發明聚丙烯纖維的有效性。 實施例1 : (1 )纖維之製造 複合構造接枝共聚物係使用乙烯-醋酸乙烯酯共聚物、與 曱基丙烯酸酯-曱基丙烯酸的接枝共聚物（乙烯-醋酸乙烯 酯共聚物/甲基丙烯酸酯/曱基丙烯酸=8 0 / 1 0 / 1 0組成比 率），且 MFR(190°C、21.18N 荷重、JISK6922-1)為 2.0g/10 分的共聚物。其中，乙烯-醋酸乙烯酯共聚物中的醋酸乙烯 酯含有量為28重量％。 將相對於聚丙烯（MFR = 1. 0g/10inin. )100重量份，經調配 上述複合構造接枝共聚物4重量份的混合物，供應給擠出 機，在樹脂溫度2 3 0 °C中，從2 m m $ X 1 0孔的鏈紗狀噴嘴 中擠出，再依熱板接觸式延伸法，在延伸溫度1 3 0 °C、退 火溫度1 3 5 °C、延伸倍率1 2倍的條件下進行延伸。所獲得 延伸紗的單紗纖度為5 0 d t。 將上述延伸紗切斷為1 0 m m長度，獲得短纖維。 水泥成形品的成形係依據J I SR 5 2 0 1實施。換句話說，將 19 312/發明說明書(補件)/93-06/93109393 200533627 卜特蘭水泥1 0 0重量份與標準砂2 0 0重量份充分混合，並 添加上述調配物5重量份，且添加水6 5重量份，經混練為 整體呈均勻狀態之後，流入4 0 m m X 4 0丨n m X 1 6 0 ni in的模框中， 在大氣中，於常溫下放置4 8小時之後，在於壓熱器中，於 1 6 5 °C下施行2 0小時養護。 所獲得成形物的彎曲強度23. 0MPa，夏丕氏衝擊（Charpy impact)強度為8. 5KJ/m2，分散性呈良好狀態。 另外，上述評估係依照下述試驗方法而實施。 (1 )MFR :依據 J ISK 6 9 2 2 -1 (2) 彎曲強度：依據JISA 1408 (3) 夏丕氏衝擊強度：依據JISB7 72 2 (4 )分散性評估：將聚丙烯纖維與水泥進行混練而製成水 泥漿，依目視評估表面狀態。 實施例2 : 除複合構造接枝共聚物使用乙烯-醋酸乙烯酯共聚物、與 甲基丙炼酸酯-曱基丙稀酸的接枝共聚物（乙烤-醋酸乙稀 酯共聚物/曱基丙烯酸酯/曱基丙烯酸=7 0 / 2 0 / 1 0組成比 率），且相對於聚丙烯1 0 0重量％調配著2重量％之外，其餘 均如同實施例1般的實施。 所獲得成形物的彎曲強度為25. 0MPa，夏丕氏衝擊強度 為8. 8K J/n〗2，分散性呈不良狀態。 比較例1 : 除在聚丙烯中完全未調配複合構造接枝共聚物之外，其 餘均如同實施例1般的實施。 20 312/發明說明書(補件)/93-06/93109393 200533627 所獲得成形物的彎曲強度為1 6 . 5MPa，夏丕氏衝擊強度 為2. 8KJ/m2，分散性呈不良狀態。 比較例2 : 除複合構造接枝共聚物使用乙烯-醋酸乙烯酯共聚物、與 丙烤腈-苯乙烤共聚物的接枝共聚物（乙稀-醋酸乙烤酯共 聚物/丙烯腈-苯乙烯共聚物=7 0 / 3 0組成比率），且相對於 聚丙烯1 0 0重量％調配著4重量％之外，其餘均如同實施例 1般的實施。 所獲得成形物的彎曲強度為1 7. 0 MPa，夏丕氏衝擊強度 為3. 5KJ/m2，分散性呈不良狀態。 實施例3 : 將相對於聚丙烯（MFR = 4. 0g/10分、Tm=163°C )100重量 份，經調配實施例1之複合構造接枝共聚物4重量份的混 合物，投入於擠出機中，再從圓形喷嘴中進行紡紗，經冷 卻後，利用熱風烤箱式延伸法，在熱延伸溫度11 5 °C、熱 鬆弛溫度1 2 0 °C、延伸倍率7〜8倍條件下進行延伸，而形 成數種纖度的單紗。接著，採用斜格花紋壓花輥與硬質橡 膠棍，改變壓花線壓（e in b 〇 s s n i p p r e s s u r e )，獲得對平均 平坦率亦不同的表面賦予凹凸形狀的聚丙烯單紗之後，將 其切斷為纖維長3 0 mm狀態的聚丙烯纖維。 (2 )評估試驗 針對所獲得聚丙烯纖維，利用下述方法施行混凝土補強 效果試驗。結果如表1所示。 ①使用材料與調配比率 21 312/發明說明書(補件)/93-06/93109393 200533627 水泥：早強卜特蘭水泥（h i g h e a r 1 y s t r e n g t h P o r 11 a n d c e m e n t)(比重=3 . 1 2 ) 4 3 0 k g / in3 細骨材：木更津產山砂（面乾狀態比重=2. 6 0 ) 1 1 2 3kg/in3 粗骨材：青梅產碎石1 5 0 5 (面乾狀態比重=2. 6 5 ) 4 9 1 kg/m3 水：自來水2 1 5 k g / m3 纖維：容積1 % ② 混凝土之混練方法 使用混練容量i 00升的強制式灰漿攪拌機，依i批次6〇 升的條件實施。混凝土混練攪拌時的溫度約2〇t。混練方 法ίτ、杈入、、’田月材、水泥、水、粗骨材，經施行4 5秒的混練 之後，一邊旋轉攪拌機一邊添加補強纖維，經㈤秒鐘混練 後再排放出。 ③ 試體之製成 依據土木學會基準「鋼纖維補強混凝土強度與韌性試驗 用試體製作方法」（JSCEF552_ 1 983 )。此外，試體係經24 小時後再脫模，並實施水中養護直到材齡7天為止。 ④ 試驗方法 依據土木學會基準Γ鋼纖維補強混凝土壓縮強度與壓縮 韌性試驗方法」（JSCE G55l — 1 9 8 3 )、及土木學會基準「鋼 纖維補強混凝土彎曲強度與彎曲韌性試驗方法」（JSCE G552-1983) ° 實施例4、5及6 : 除將聚丙烯纖維纖度與平坦率，如表丨所示進行改變之 外，其餘均如同實施例3般的實施。結果如表丨所示。 312/發明說明書(補件)/03-06/93109393 200533627 實施例7 : 除複合構造接枝共聚物使用乙烯-醋酸乙烯酯共聚物、與 曱基丙烯酸酯-甲基丙烯酸的接枝共聚物（乙烯-醋酸乙烯 酯共聚物/甲基丙烯酸酯/曱基丙烯酸=7 0 / 2 0 / 1 0組成比 率），且相對於聚丙烯1 0 0重量％調配著2重量％之外，其餘 均如同實施例3般的實施。 比較例3〜5 : 取代複合構造接枝共聚物，改為使用界面活性劑的由聚 氧化伸烧基烧基苯驗踏酸酷（H L B = 9 ) 5 0重量份、與聚氧化 伸烷基脂肪酸酯（HLB = 1 2 ) 5 0重量份，相混合而形成的表面 處理劑水溶液，將聚丙烯纖維單紗浸潰於上述界面活性劑 中，經乾燥而形成對總纖維附著0. 2 8重量％之外，其餘均 如同實施例3〜6般的實施。結果如表1所示。 比較例6與7 : 除取代聚丙烯纖維，改為使用鋼纖維或聚乙烯醇纖維（纖 維長度3 0 ηιιη)之外，其餘均如同實施例3般的實施。結果 如表 1所示。 23 31W發明說明書(補件)/93-06/93109393 200533627 (表1) 纖維 纖度 平坦率 纖維重量 彎曲1：刃性 壓縮強度 (-) (dt ) (-) (k g / m") (kg f · cm) (N / ni in2) 實施例3 PP 3 0 0 0 4.2/1 9. 2 380 37.9 實施例4 PP 6 0 0 0 6.4/1 9. 2 390 38.2 實施例5 PP 3 0 0 0 1.8/1 9.2 357 3 7.4 實施例6 PP 500 2. 6/1 9. 2 372 37.7 實施例7 PP 3 0 0 0 4. 2/1 9. 2 412 38. 3 比較例3 PP 3 0 0 0 4.2/1 9. 2 317 37.5 比較例4 PP 6 0 0 0 6. 4/1 9. 2 325 37.8 比較例5 PP 500 2.6/1 9.2 310 37. 3 比較例6 不鑛鋼 Φ 0 . 6 m in 3.0/1 78 330 37. 5 比較例7 PVA 4 0 0 0 1.4/1 13 151 35. 7 24 31W發明說明書(補件)/93-06/93〗09393200533627 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a polypropylene fiber for cement reinforcement, which has excellent adhesion to cementmatri X and has excellent reinforcing effects such as mortar and concrete. And a method for constructing a reinforced cement formed body using the fiber reinforced with polypropylene fibers for cement, a concrete structure using the polypropylene reinforced with fibers for cement, and a spraying concrete method using the polypropylene reinforced with fibers for cement. [Previous technology] In the past, there were cement-formed products using mortar or concrete, or building exterior walls, interior walls, slope faces, etc., if the brittleness of the formed body is too large, and if it is pulled Insufficient physical properties such as tensile strength, Ziqu endurance, bending and traversing edge resistance, and impact resistance may cause the leakage of water due to the splitting of the wall surface, or the risk of accidents such as peeling off the outer wall. Therefore, in terms of reinforcing materials for these cement formed products, in recent years, synthetic resin fibers such as steel fibers, polyvinyl alcohol resins, polyolefin resins, polyacrylonitrile resins, and polyamide resins have been used (for example, refer to Japanese Patent Publication No. Kaisho 6 3-3 0 3 8 7 7; Tokai Kokai Hei 8-2 1 8 2 2 0 number 6). However, the concrete with steel fiber has a specific gravity of 7.8, so it is difficult to handle or mix materials. In sprayed concrete, there will be a stepping back due to the rebound during spraying. Fear of injury caused by falling steel fibers, and even pointed out the shortcomings of rust. The concrete mixed with polyvinyl alcohol fibers has the potential that the fiber itself has 5 312 / Explanation _ Supplement) / 93-06 / 93109393 200533627 has water absorption, and if the fiber reaches a high temperature state in alkali, it will cause Hydrolysis phenomenon, and the slump (s 1 ump) tends to be significantly reduced compared to the case of unblended fibers. To ensure the necessary slump during spraying, the unit water volume must be increased. . In addition, the maintenance of concrete formed products has increased the use of autoclave (aut occ ave) for the purpose of improving dimensional stability and shortening the curing time. When such autoclave maintenance is implemented, In this case, fibers other than the polyolefin-based fibers may be deteriorated due to insufficient alkali resistance, which may cause a problem that the fibers may not be used as reinforcing fibers. In addition, polyolefin resins have very few hydrophilic groups or functional groups that contribute to the adhesion to cement in the molecular structure. Therefore, the adhesion to the cement slurry will be extremely poor. If the cement-formed body reinforced with polyolefin resin fibers is destroyed, the fibers will be easily removed. Even if it is found that the impact strength or bending failure energy can be increased due to the removal resistance of the fibers, the bending strength cannot be significantly improved. In order to improve the affinity between related polyolefin fibers and cement, a method has been proposed to add various inorganic fine particles or hydrophilic polymer materials such as polyvinyl acetate to the fibers. Foreign matter will damage the extensibility, and in addition to failing to obtain sufficient fiber strength, the resin fiber surface portion other than the modifier does not increase the affinity, and cannot be obtained in the proportion of the amount added Fully modified effect. On the other hand, a single yarn or bundled yarn with a fineness of 100 dt or less and a fiber length of 5 mm or less, or a poly yarn 312 / Invention (Supplement) / 93-06 / 93109393 200533627 Hydrocarbon fiber, the shape of these fibers will be fiber balls such as fiber balls, and will form fluffy and difficult to evenly disperse in cement, and if the fineness is coarsened to improve dispersibility In this case, the adhesiveness between the cement and the cement will be deteriorated. Therefore, if a bending stress is applied, the fiber may be pulled out, and the reinforcing effect cannot be sufficiently obtained. On the other hand, although proposals have been made for thick fiber yarns having a single yarn fineness of 2 0 dt or more with a specific average flatness unevenness on the cross section of the fiber, the fibers are cut into polypropylene fibers with a fiber length of 5 mm or more, and polyoxidized fibers are used. Various coating methods, such as a surfactant composed of a fluorenyl phenylene ether phosphate and a polyoxyalkylene fatty acid ester (see Japanese Laid-Open Patent Publication Nos. 1 1 to 1 6 2 9 7), however, Because this surfactant does not have adhesion to polyolefin resin fibers, even if it adheres to cement slurry, sufficient adhesion cannot be obtained between polyolefin resin fibers and cement slurry, and cement molding cannot be improved. Bending toughness of the object. The present invention was conceived to solve the problems of the prior art as described above, and an object thereof is to provide a polyolefin fiber which can impart hydrophilicity, has good dispersibility and physical bonding with cement, and has excellent properties with cement slurry. Cement-reinforced polypropylene fiber with superior adhesion, which can improve the bending strength, impact strength, or bending toughness of cement formed products, and fiber reinforced cement formed body using this cement-reinforced polypropylene fiber, and use this cement-reinforced polymer Construction method of concrete structure using acrylic fiber, and spray concrete method using polypropylene fiber for cement reinforcement. [Summary of the Invention] The present invention basically involves blending a specific amount of a specific compound for a polyolefin resin with a specific compound 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 to construct a surfactant for the graft copolymer to form fibers. That is, a composite structure composed of 50 to 90% by weight of an ethylene-vinyl acetate copolymer segment and 50 to 50% by weight of an ethylene-based polymer segment is contained with respect to 100 parts by weight of propylene. The composition of 1 to 10 parts by weight of the branch copolymer is spun to form polypropylene fibers for cement reinforcement. Thereby, a superior affinity can be imparted to the interface between the polypropylene fiber and the cement, and a cement-molded product manufacturing state having excellent adhesion to the cement slurry and excellent bending strength and impact strength can be formed. In this case, by cutting a single yarn with a single yarn fineness of 2 0 0 dt or more on the surface of the fiber that has been spun as described above, cutting to a fiber length of 5ηυη or more can compensate for the thicker fibers. The disadvantage that the contact area between the cement and the cement decreases is that the physical combination with the cement will be in good condition, and a cement formation with superior bending toughness can be manufactured. Furthermore, the ethylene-based polymer of the present invention is a polymer obtained by polymerizing one or two or more of unsaturated carboxylic acids or unsaturated carboxylic acids S, such as fluorinated acrylic acid, and A polymer obtained by polymerizing methyl methacrylate. Furthermore, the present invention belongs to a fiber-reinforced cement formed body obtained by adding a suitable amount of polypropylene fiber composed as described above to a cement composition containing a cement, fine aggregate, and water in a mortar mixture. In addition, the present invention is a method of constructing a concrete structure by adding a certain amount of polypropylene fibers constituted as described above to a concrete mixture containing cement, fine aggregate, coarse aggregate, and water, and manufacturing the concrete structure. In addition, the present invention is to add an appropriate amount of polypropylene fibers composed as described above, add 8 312 / Instruction of IK Supplement) / 93-06 / 93109393 200533627 to concrete containing cement, fine aggregate, coarse aggregate and water Spraying concrete method of spraying a certain thickness on the surface to be applied in the mixture. [Embodiment] In the present invention, the polypropylene resin used in the fiber raw material may be a polypropylene copolymer such as a propylene monopolymer, an ethylene-propylene block copolymer, or a random copolymer, or a mixture thereof. . Among these, for cement strengthening applications requiring high strength and heat resistance, it is best to use a propylene monopolymer, and in particular, to select an isotactic pentad fraction. · Above 95 is preferred. The so-called "isotactic pentad fraction" here refers to the isotactic pentad unit within a polypropylene molecule as measured by i3C-NMR published by A. Zambel 1 i et al. In Macromolecules 6925 (1973). Isotactic fraction ° The melt flow rate (me 11 f 1 〇wrate) (hereinafter referred to as "MFR") of this polypropylene baking resin is preferably 0.1 to 5.0 g from the viewpoint of continuous and stable productivity. In the range of / 10 points, it is better to choose in the range of 1 to 10 g / 10 points. Polypropylene resin can be added with polyolefin during the spinning process. The "other polyolefins" referred to herein include polyethylene resins such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-alkyl acrylate copolymer. Polybutene-1 and so on. Next, the composite structure graft copolymer will be described. This graft copolymer is composed of an ethylene-vinyl acetate copolymer segment (hereinafter referred to as 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627, which is referred to as "A segment") 5 0 ~ 9 0 weight ° / ◦ And ethylene polymer segment (hereinafter referred to as "B segment") 50 to 10% by weight. Generally, the A segment constitutes the main chain of the graft copolymer, and the B segment constitutes the side chain of the graft copolymer. The content of the ethylene-vinyl acetate copolymer-based vinyl acetate constituting the A segment is 10% by weight or more, preferably in the range of 10 to 80% by weight, and especially in the range of 20 to 5% by weight Better. If the content of vinyl acetate is less than 10% by weight, hydrophilicity will be insufficient, and it is best avoided. The weight-average molecular weight of the ethylene-vinyl acetate copolymer ranges from 100 to 100, 000, and preferably from 500 to 600,000. If the weight-average molecular weight is less than 1,000, heat resistance will be lowered, so it is best to avoid it. On the other hand, if the weight-average molecular weight is more than 1 million, it is not preferable because the moldability is reduced. Next, the ethylenic polymer which forms the B segment of the graft copolymer is obtained by polymerizing one or two or more of these unsaturated carboxylic acid esters. Examples of the unsaturated carboxylic acids include α, /?-Unsaturated carboxylic acids such as acrylic acid, fluoracrylic acid, maleic acid, fumaric acid, and maleic anhydride, and metal salts thereof. In addition, the unsaturated carboxylic acid esters may include, for example, α, / 3 -unsaturated butyl acrylate, n-butyl acrylate, butyl acrylate, fluorenyl acrylate, ethyl methacrylate, butyl methacrylate, and the like. Saturated carboxylic acid esters, etc. Among these, a combination of methacrylic acid and methyl methacrylate is more appropriate. In addition, the weight average molecular weight of the beta-based polymer is 10, 000 to 1,000,000, and preferably 50, 000 to 5,000,000. When the weight-average molecular weight is less than 10 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 1, 0 0 0, since the compatibility with the resin to be modified will decrease, it is best avoided. On the other hand, if it exceeds 1 million, it is better to avoid it for the same reason. In the composite structure graft copolymer, the ratio of the A segment is 50 to 90% by weight, and preferably 60 to 80% by weight. Therefore, in the composite structure graft copolymer, the ratio of the B segment is 50 to 10% by weight, and preferably 40 to 20% by weight. If the ratio of the A segment is less than 50% by weight, the improvement effect of the ethylene-vinyl acetate copolymer is insufficient, and therefore it is not preferable. On the other hand, if the A segment exceeds 90% by weight, it is better to avoid the impact strength and bending strength of the cement formed product because the adhesion between the A segment and the cement slurry will not be improved. The particle size of the dispersed polymer is from 0.01 to 10 μΐϋ, preferably from 0.1 to 5 μm. If the dispersed particle diameter is less than 0.01 μm or more than 10 μm, the dispersibility will be lowered, and the appearance of the obtained molded article will be deteriorated or the mechanical properties will be lowered. The grafting method in the production of the composite structure graft copolymer may be any method such as a generally known chain transfer method or ionizing radiation irradiation method, but the following method is preferably used. In other words, this is because the grafting efficiency is not high, and the secondary condensation is caused by heat, so the performance can be more effectively highlighted, and the manufacturing method is simpler. Next, the manufacturing method of the composite phase structure graft copolymer will be specifically described. First, 100 parts by weight of ethylene-vinyl acetate copolymer is suspended in water, and the following mixed solution is added to the mixed solution. The mixed solution is at least 1 to 400 parts by weight of one type of ethylene-based monomer. 1 to 2 parts by weight of 1 to 2 parts by weight based on 100 parts by weight of the vinyl-based monomer are dissolved in 11 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 由 基The decomposition temperature of a mixture of polymerizable organic peroxides and a total of 100 parts by weight of vinyl monomers and radical polymerizable organic peroxides is 0.5 to 5 parts by weight to obtain a 10-hour half-life. 4 0 ~ 9 0 ° C polymerization initiator. Next, heating is carried out under conditions that do not cause decomposition of the polymerization initiator to substantially cause the vinyl monomer, the radically polymerizable organic peroxide, and the polymerization initiator to be contained in the ethylene-vinyl acetate copolymer. Next, the temperature of this aqueous suspension was raised. Then, a vinyl monomer and a radical polymerizable organic peroxide are copolymerized in an ethylene-vinyl acetate copolymer to obtain a graft precursor. By kneading the graft precursor under melting, a graft copolymer having a composite structure can be obtained. At this time, the graft precursor can be mixed with an ethylene-vinyl acetate copolymer and kneaded under melting to obtain a composite structure graft copolymer. The above radically polymerizable organic peroxide is preferably, for example, third butyl cumene propylene ethoxylate percarbonate, third pentyl cumene propylene ethoxylate percarbonate, Tert-hexylpropenyloxyethyl peroxycarbonate, 1,1,3,3-tetrafluorenyl butylpropenyloxyethyl percarbonate, cumene peroxycarbonate peroxycarbonate, P-Isopropylperoxycarbonate, isopropylbenzylpropenyloxyethyl carbonate, third butylfluorenylpropionyloxyethylperoxide, third pentylisopropylbenzylmethacrylic acid, peroxycarbonate Ethyl ester, tert-hexylfluorenylpropenyloxyethyl carbonate peroxy, tert-butyl allyl carbonate peroxy, tert-butyl peroxycarbonate, etc. 12 312 / Instruction of the Invention (Supplement) / 93-06 / 93109393 200533627 MFR (90 ° C, 2 1 60g load, J IS K 6 9 2 2-1) of the above-mentioned composite structure graft copolymer, tied to 0 Within the range of 1 to 20 g / 10 minutes, preferably in the range of 0.5 to 10 g / 10 minutes. The polypropylene fiber for cement reinforcement of the present invention has a composite structure graft copolymer in an amount of 1 to 10 parts by weight, and preferably in the range of 5 parts by weight, relative to 100 parts by weight of polypropylene. If the compounding ratio of the composite structure graft copolymer is less than 1 part by weight, the effect of imparting hydrophilicity to the polyolefin resin fibers will be reduced, and the effect of improving the adhesiveness with the cement slurry will also be reduced. On the other hand, if it exceeds 10 parts by weight, it is better to avoid it because the mechanical strength to the polyolefin resin fiber is reduced. In the above polypropylene composition, according to the purpose of use, without departing from the scope of the present invention, it can also be formulated such as: antioxidants, lubricants, ultraviolet absorbers, antistatic agents, inorganic fillers, organic fillers, cross-linking Additives, foaming agents, nuclear agents and other additives. The polypropylene fiber to be spun in the present invention constitutes the fiber shape of the main body, and is a short fiber obtained by cutting a single yarn of an arbitrary thickness. The manufacturing method is not particularly limited. Manufacturing technology for single yarns in deformed or chain-shaped dies. For example, a known melt-spinning method may be used, or spinning may be performed using a chain yarn-like mold capable of high-rate stretching. In this case, polypropylene is melt-extruded from the chain-gauze mold, and then the extruded chain-gauze belt is directly subjected to stretching treatment to form fibers. The chain-gauze mold has a shape in which at least two nozzles are connected in series, and generally has a shape in which 5 to 20 nozzles are connected, and preferably 10 to 15 nozzles are connected. 13 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 Furthermore, the single yarn of the present invention may also be a staple fiber that cuts a thick single yarn. In this case, in addition to the single-layer yarn as described above It is also possible to use a multifilament yarn with a polypropylene melting point component as the core layer and a polypropylene low melting point component as the sheath layer. In this manufacturing method, each layer of polypropylene is melt-drilled by an extruder, and a core layer composed of a high melting point component is supplied from a center hole of a mold provided with two layers of discharge holes on a slightly concentric circle. A composite single yarn is obtained by laminating a sheath composed of a low melting point component. In this case, because the actual strength depends on the physical properties of the core layer, the melting point component is preferably used such as: acrylic monomer, isotactic polypropylene, etc., and the point component is preferably used such as: propylene-ethylene block Copolymers and random copolymers, syndiotactic polypropylene, etc. By using the composite single yarn obtained in this way, it is possible to suppress the occurrence of polypropylene fibrillation during heat curing during the formation of concrete. Secondly, the above-mentioned single yarns are subjected to thermal elongation and thermal relaxation treatment, and the rigidity of the yarn is improved by the treatment, and a polypropylene single yarn with better elongation for cement reinforcement can be obtained. The hot elongation is carried out at a temperature below the melting point of polypropylene and above the softness. Generally, the elongation temperature is 90 ~ 150 ° C, and the elongation / rate is usually 5 ~ 12 times, preferably 7 ~ 9 times. , The hot elongation method can adopt a female roller type, a hot plate type, an infrared irradiation type, a hot air oven type, and a hot water type. The tensile strength of the stretched polypropylene yarn is above 5 g / dt and above 6 g / dt. In addition, the tensile elongation is below 20%, preferably below. If the tensile strength and tensile elongation exceed these ranges, the strength of the polypropylene fiber for hydration will be insufficient, and it is best to avoid it. 312 / Explanation of the Invention (Supplement) / 93-06 / 93109393 Dimensions, the mixture will be discharged and melted to the south, and then the heat will be worse than the heat of the comparison point I: the heat is best 15% mud Strong 14 200533627 The single yarn fineness of the polypropylene single yarn formed according to the above method is 5 ~ 1 0,0 0 0 0 decitex (dec it ex) (hereinafter referred to as "dt"), preferably 10 ~ 6, 5 0 0 dt. At this time, the finer single yarn fineness 5 ~ 100 dt is cut into short fibers such as fiber length 3 ~ 30 mm, preferably 5 ~ 15 mm, and the thicker single yarn fineness 2 0 ~ 0 If it is in the range of 1 0, 0 0 0 dt, it will be cut to 5 ~ 1 0 0 _, preferably 20 ~ 70mn. If the fiber length is less than 3mm, it will fall out of the cement. On the other hand, if it exceeds 100 mm, the dispersibility will be poor, so it is best not to. If the single yarn fineness is less than 5 dt, the fiber will be unevenly dispersed in the concrete mixture due to too fine fibers, and fiber balls will be easily formed, which will cause problems in terms of workability or reinforcement. On the contrary, if the single yarn fineness is If it exceeds 200 dt, the contact area between the fiber and the concrete mixture will be reduced, and the bending stress will be easily pulled out, and the reinforcing effect will be deteriorated. Therefore, it is best to avoid it. Therefore, in the present invention, the single yarn fineness The thicker than 2 0 0 dt must give the surface an uneven shape in the subsequent steps of spinning and thermal stretching. This will increase the contact area between the fiber and the concrete, prevent the fiber from being pulled out after the concrete is hardened, and improve the reinforcement effect. This method of imparting an uneven shape to the surface may be, for example, embossing a single yarn. The embossing is performed before or after the single yarn is stretched by passing through an embossing roller, so that unevenness can be continuously formed in the length direction of the single yarn. The shape such as the length and the depth of the embossing may be arbitrary, but it must be set to make the average flatness of the fiber cross-section within the range of 1.5 / 1 to 7/1 by the collapse of the extrusion. This average flatness ratio refers to the fiber wearing surface shaped by various shapes. 15 3 丨 2 / Invention Specification (Supplement) / 93-06 / 93109393 200533627, the value representing the average ratio of width to height. If the average flatness ratio is low, If it is 1.5 / 1, because there are too few irregularities on the surface of the fiber, there will be no difference between the reinforcing effect and the smooth surface fiber. On the contrary, if the average flatness exceeds 7/1, it will cause The strength is significantly deteriorated due to shaping, and the dispersibility of the fibers of the above-mentioned predetermined fineness to the concrete tends to deteriorate, which will constitute a problem. The polypropylene fiber for cement reinforcement of the present invention is mixed in mortar or concrete and can be used in various embodiments. For example, a method of mixing polypropylene fibers in cement or concrete and then using a molding method to manufacture a cement-formed product; or a method of mixing polypropylene fibers and grouting and coating to manufacture a mortar structure or a concrete structure; or A method of mixing acryl fibers into mortar or concrete and manufacturing the mortar structure or concrete structure by spraying. When polypropylene fiber is mixed in mortar, it can be used in cement, fine aggregate, water, and a suitable amount of mixed material. Furthermore, when polypropylene fibers are mixed in concrete, they can be used in cement, fine aggregate, coarse aggregate, water, and an appropriate amount of mixture. Among them, representative examples of cement include: Portland cement (ρ 〇 11 andce in e η t), blast furnace cement, oxidized stone cement, fly ash cement (f 1 yashcement), white brand cement, oxide Hydraulic cement (hydrau 1 iccement) such as cement, or cement such as gypsum, lime and other rigid cement; and fine aggregates can be representative, for example: river sand, sea sand, mountain sand, silica sand, glass sand, Iron sand, lime sand, and other artificial sand. In addition, coarse aggregates can be representative, for example: gravel, gravel, crushed stone, slag, various artificial 16 31W invention specification (Supplement) / 93-06 / 93109393 200533627 light Measure aggregate and so on. When manufacturing cement shaped products, the method of mixing polypropylene fibers in concrete can be, for example, a method in which polypropylene fibers are dispersed in cement powder, or a premix in which polypropylene fibers are dispersed in cement slurry. Method, or a well-known method such as spraying cement, polypropylene fiber, and water simultaneously. 5〜5 重量 ％。 Polypropylene fiber is formulated in the amount of 0. 1 ~ 10% by weight, preferably 0.5 to 5% by weight relative to the cement. If the blending amount is less than 0.1% by weight, the reinforcing effect will be deteriorated. On the other hand, if it is more than 10% by weight, it will be difficult to disperse uniformly, and the bending strength will be reduced, so it is not recommended. The cement slurry thus obtained is formed according to a known molding method such as a papermaking molding method, an extrusion molding method, an injection molding method and the like according to the application, and is a natural curing method that is left in the air or water for a few days at normal temperature. Or, after being left at room temperature for 2 to 3 days, and then performing an autoclave curing method at a temperature of 100 to 200 ° C, a cured and hardened cement formed product can be formed. The use of cement formed articles made of the polypropylene fiber of the present invention spans all cement products, such as building wall materials, floor slab concrete, matte mortar, waterproof concrete, asbestos corrugated roof materials, or civil engineering Components such as the laying of roads and runways, road signs, side trenches and other road components, or the following watercourses, cable pipes and other pipelines; or such as fish reefs, breakwater blocks, diamond blocks, etc., or other various structures such as sleepers, long Chairs, flowerpots, etc. In addition, when the polypropylene fiber of the present invention is used in the construction of mortar structures, cement, fine aggregate, water, and an appropriate amount of mixing agent can be blended into the polypropylene fiber at the same time (or in the state of kneading mortar). After mixing, 17 312 / Invention Specification (Supplement) / 93-06 / 93] 09393 200533627 is used for grouting and coating, and construction and mortar construction are used to manufacture concrete structures. Water and an appropriate amount of mixing agent are mixed together at the same time (or mixed with polypropylene fibers, and after mixing, the concrete structure is manufactured by construction. Moreover, when the polypropylene fibers of the present invention are used in the world, the blending amount is relatively Below 1 m3 of a mixture of cement, fine aggregate, and concrete, it is best to allocate 6 to 14 kg of dispersing poly I, which is an important part. This is because the fiber cannot be evenly divided due to the amount of more than 19 kg. · Bending I: The sharpness has not increased. On the contrary, if the blending amount is increased during spraying, and the hardening method is used to reinforce this case, it is best to use concrete made of coarse aggregate and water. Mix (Basec ο ncrete), and then put the concrete bottom into polypropylene fiber to carry out the kneading method. The amount of mixing time varies, in general, the bottom of the concrete, the kneading after the polypropylene fiber is also set In addition, in the spraying concrete construction method, when using the blending amount described in this report, it is best to drop i Dan within the range. This is because if i Dan is less than 8cm, it is difficult, otherwise, if it exceeds If it is 21 cm, the rebound force will be changed to implement the sprayed concrete method according to this slump range 3 丨 2 / Invention Specification (Supplement) / 93-06 / 93109393. In addition, when used in mud, fine aggregate, coarse bone In the state of good concrete) 4 to 19 kg of diene fibers constructed by grouting, coating, and spraying of concrete with coarse aggregates and water, so that even if the polypropylene fiber is in the concrete, the effect is less than 4 kg. small. After kneading with cement, fine aggregate, and concrete base slurry, the training time is based on the average kneading system of 4 5 ~ 9 ◦ The range of 4 5 ~ 90 seconds is more clear, and the polypropylene fiber is adjusted to 8 ~ 21cin. , The spray operation will become sleepy k, so it is best to avoid. Spray nozzle, the nozzle 18 200533627 is arranged at a right angle with the spray surface, and the distance between the nozzle and the spray surface is set to 0.5 ~ 1.5 η], which will be a more effective state. According to this, when the concrete mixture mixed with the polypropylene fiber of the present invention is used as a shotcrete, it can be used for tunnels (including inclined wells, vertical wells), covering works of large hollow structures, slopes, and slopes. Or prevent wall weathering, peeling / stripping, or repair of tunnels, landslides, bridges, and reinforcement works. Hereinafter, the effectiveness of the polypropylene fiber of the present invention will be described by way of examples. Example 1: (1) Manufacturing of fiber The graft copolymer of a composite structure is an ethylene-vinyl acetate copolymer and a graft copolymer with ethylene-acrylic acid ester-fluorenyl acrylic acid (ethylene-vinyl acetate copolymer / formaldehyde) Copolymer based on acrylic acid ester / fluorenyl acrylic acid = 8 0/1 0/10) and MFR (190 ° C, 21.18N load, JISK6922-1) of 2.0 g / 10 minutes. The content of vinyl acetate in the ethylene-vinyl acetate copolymer was 28% by weight. A mixture of 4 parts by weight of the composite structure graft copolymer with respect to 100 parts by weight of polypropylene (MFR = 1.0 g / 10inin.) Was supplied to an extruder, and at a resin temperature of 230 ° C, Extruded from a chain-gauze nozzle with a hole of 2 mm $ X 1 0, and then according to the hot plate contact extension method, under the conditions of an extension temperature of 130 ° C, an annealing temperature of 1 3 5 ° C, and an extension ratio of 12 times Down to extend. The single yarn fineness of the obtained drawn yarn was 50 d t. The drawn yarn was cut to a length of 10 mm to obtain short fibers. The molding system of the cement molded product is implemented in accordance with J I SR 521. In other words, 19 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 Portland cement 100 parts by weight and 200 parts by weight of standard sand are thoroughly mixed, and 5 parts by weight of the above-mentioned formulation is added, And after adding 65 parts by weight of water, after mixing to make the whole uniform, it flows into a mold frame of 40 mm X 40 0 nm x 16 0 ni in, and left in the atmosphere at room temperature for 48 hours, In an autoclave, it is cured for 20 hours at 16 5 ° C. The obtained molded article had a bending strength of 23.0 MPa, a Charpy impact strength of 8.5 KJ / m2, and good dispersibility. The above evaluation is performed in accordance with the following test method. (1) MFR: based on J ISK 6 9 2 2 -1 (2) flexural strength: based on JISA 1408 (3) Charpy impact strength: based on JISB7 72 2 (4) dispersibility evaluation: polypropylene fiber and cement Knead to make a cement slurry, and visually evaluate the surface condition. Example 2: Graft copolymer in addition to the composite structure uses an ethylene-vinyl acetate copolymer and a graft copolymer with methyl propionate-fluorenyl acrylic acid (ethyl roast-ethyl acetate copolymer / 曱Composition ratio of methacrylic acid ester / methacrylic acid = 7 0/2 0/10), and 2 weight% is blended with 100 weight% of polypropylene, and the rest are implemented as in Example 1. The bending strength of the obtained molded product was 25.0 MPa, the Charpy impact strength was 8.8 K J / n, and the dispersibility was poor. Comparative Example 1: Except that the composite structural graft copolymer was not prepared in polypropylene at all, it was implemented as in Example 1. 20 312 / Invention (Supplement) / 93-06 / 93109393 200533627 The obtained molded article had a bending strength of 16.5 MPa, a Charpy impact strength of 2.8 KJ / m2, and the dispersibility was poor. Comparative Example 2: Ethylene-vinyl acetate copolymer and graft copolymer with acrylic baking nitrile-styrene baking copolymer (ethylene-ethyl acetate baking copolymer / acrylonitrile-benzene) Ethylene copolymer = 7 0/30 composition ratio), and 4 weight% was blended with 100 weight% of polypropylene, and the rest were implemented as in Example 1. The bending strength of the obtained molded product was 17.0 MPa, the Charpy impact strength was 3.5 KJ / m2, and the dispersibility was in a poor state. Example 3: A mixture of 4 parts by weight of the composite structure graft copolymer of Example 1 with respect to 100 parts by weight of polypropylene (MFR = 4.0 g / 10 minutes, Tm = 163 ° C) was put into an extrusion After exiting the machine, spinning is performed from a circular nozzle. After cooling, the hot-air oven-type stretching method is used at a thermal stretching temperature of 11 5 ° C, a thermal relaxation temperature of 120 ° C, and a stretching ratio of 7 to 8 times. It is extended to form a single yarn of several fineness. Next, a diagonal single pattern embossing roller and a hard rubber stick were used to change the embossing pressure (e in b ssnippressure) to obtain a polypropylene monofilament having a concave-convex shape on a surface having a different average flatness, and then cut it. Polypropylene fiber with a fiber length of 30 mm. (2) Evaluation test For the obtained polypropylene fiber, a concrete reinforcement effect test was performed by the following method. The results are shown in Table 1. ①Used material and blending ratio 21 312 / Invention Specification (Supplement) / 93-06 / 93109393 200533627 Cement: Early-strength Portland Cement (highear 1 ystrength P or 11 andcement) (Specific gravity = 3. 1 2) 4 3 0 kg / in3 fine aggregate: mountain sand produced by Kisarazu (specific gravity of dry surface = 2. 6 0) 1 1 2 3kg / in3 coarse aggregate: crushed stone from green plum 1 5 0 5 (specific gravity of dry surface = 2. 6 5 ) 4 9 1 kg / m3 water: tap water 2 1 5 kg / m3 fiber: 1% of volume ② The concrete mixing method uses a forced mortar mixer with a mixing capacity of i 00 liters, and is implemented according to the conditions of batch 60 liters. The temperature when the concrete is kneaded is about 20t. The kneading method ίτ, branch into, ‘field moon wood, cement, water, coarse aggregate, after the 45-second kneading, add a reinforcing fiber while rotating the blender, and then discharge it after kneading for a second. ③ Preparation of test specimens According to the Civil Society's standard "Method for Making Test Specimens for Strength and Toughness of Steel Fiber Reinforced Concrete" (JSCEF552_ 1 983). In addition, the test system was demoulded after 24 hours, and water curing was performed until the age of wood was 7 days. ④ The test method is based on the Civil Society Society Standard Γ steel fiber reinforced concrete compression strength and compression toughness test method "(JSCE G55l — 1 9 8 3), and the Civil Society Society standard" Steel fiber reinforced concrete bending strength and bending toughness test method "(JSCE G552 -1983) ° Examples 4, 5 and 6: Except that the polypropylene fiber fineness and flatness were changed as shown in Table 丨, the rest were implemented as in Example 3. The results are shown in Table 丨. 312 / Invention Specification (Supplement) / 03-06 / 93109393 200533627 Example 7: Except for the composite structure, the graft copolymer uses an ethylene-vinyl acetate copolymer and a graft copolymer with fluorenyl acrylate-methacrylic acid ( Ethylene-vinyl acetate copolymer / methacrylate / fluorenyl acrylic acid = 7 0/2 0/10 composition ratio), and 2% by weight relative to 100% by weight of polypropylene, the rest are the same as Example 3 implementation. Comparative Examples 3 to 5: Instead of the composite structure graft copolymer, a surfactant was used instead of polyoxyalkylene based benzene benzene test acid (HLB = 9) 50 parts by weight and polyoxyalkylene Fatty acid ester (HLB = 1 2) 50 parts by weight, mixed to form a surface treatment agent aqueous solution, the polypropylene fiber single yarn is dipped in the above-mentioned surfactant, and dried to form a total fiber adhesion of 0.2 Except for 8% by weight, the rest were implemented as in Examples 3 to 6. The results are shown in Table 1. Comparative Examples 6 and 7: Except that polypropylene fibers were replaced with steel fibers or polyvinyl alcohol fibers (fiber length of 30 μm), the procedure was carried out as in Example 3. The results are shown in Table 1. 23 31W Invention Specification (Supplement) / 93-06 / 93109393 200533627 (Table 1) Fiber fineness, flatness, fiber weight, bending 1: edge compressive strength (-) (dt) (-) (kg / m ") (kg f Cm) (N / ni in2) Example 3 PP 3 0 0 0 4.2 / 1 9. 2 380 37.9 Example 4 PP 6 0 0 0 6.4 / 1 9. 2 390 38.2 Example 5 PP 3 0 0 0 1.8 / 1 9.2 357 3 7.4 Example 6 PP 500 2. 6/1 9. 2 372 37.7 Example 7 PP 3 0 0 0 4. 2/1 9. 2 412 38. 3 Comparative Example 3 PP 3 0 0 0 4.2 / 1 9. 2 317 37.5 Comparative Example 4 PP 6 0 0 0 6. 4/1 9. 2 325 37.8 Comparative Example 5 PP 500 2.6 / 1 9.2 310 37. 3 Comparative Example 6 Stainless steel Φ 0.6 m in 3.0 / 1 78 330 37. 5 Comparative Example 7 PVA 4 0 0 0 1.4 / 1 13 151 35. 7 24 31W Description of the invention (Supplement) / 93-06 / 93〗 09393