201236998 六、發明說明 【發明所屬之技術領域】 本發明係有關含有有機纖維，且添加水所施工而得之 不定形耐火物。 【先前技術】 不定形耐火物係用於例如澆桶、餵槽、高爐出鐵槽或 真空脫氣爐等各種熔融金屬容器之內襯。以下，以澆桶內 襯之澆鑄施工爲例說明不定形耐火物的一種施工方式。 首先，於不定形耐火物中添加水予以混合，使其成爲 泥漿。其次，將該泥漿澆鑄於已插入澆桶之模心與澆桶內 壁之間，使其固化至發現定形性爲止。將使經澆鑄之泥漿 固化至發現定形性爲止者稱爲施工體。固化後去除模心， 將殘留之施工體予以乾燥即爲內襯。 施工體之乾燥係藉由以燃燒器或微波加熱進行。加熱 時，自施工體內部產生水蒸氣，有因蒸氣壓而產生施工體 龜裂或爆裂之情形。若將施工體以緩慢的升溫速度長時間 乾燥，可抑制爆裂之產生，但由提高澆桶使用率的觀點來 看則希望縮短乾燥時間。 因此，以往採用使不定形耐火物含有有機纖維之對 策。有機纖維係藉由乾燥中的加熱於施工體內熔融而減少 體積，於施工體中形成水蒸氣的通氣孔。通過由有機纖維 所形成之無數的細微通氣孔群，水蒸氣將由施工體的內部 逸散至外部。藉此，可緩和施工體內部蒸氣壓的上升，抑 -5 " 201236998 制爆裂。 由專利文獻1可知施工體內部的蒸氣壓將自約略200 °C急劇上升，故有機纖維以於蒸氣壓急劇上升前的1 80 °C 以下熔融者爲佳。專利文獻1揭示可作爲低熔點的素材有 維尼綸 '、聚乙烯及聚丙烯等，其中以維尼綸纖維爲最佳。 專利文獻2及3揭示選擇聚乙烯纖維作爲防止爆裂用 的有機纖維之不定形耐火物的具體例（參考專利文獻2的 實施例2及3，與專利文獻3的比較例3)。再者，專利文 獻3揭示聚乙烯纖維的含水率爲0質量％(參考專利文獻3 第2頁右上欄及第2表）。 專利文獻4揭示以密度0.93g/cm 3以下之低密度聚乙 烯作爲防止爆裂用的有機纖維之素材。已知即使於聚乙烯 中低密度聚乙烯的熔點亦屬低，爲100〜13 5°C。 [先前技術文件] [專利文獻] [專利文獻1]特開昭6 1 - 1 0079號公報 [專利文獻2]特開平3 -8 3 8 69號公報 [專利文獻3]特開平3-265572號公報 [專利文獻4]特開2008-1 20669號公報 【發明內容】 [發明欲解決之課題] 以往，單純認爲有機纖維以熔點愈低者爲佳。然而， 不論如何使用低熔點的有機纖維依然有產生爆裂之情形。 -6- 201236998 本發明人進行徹底硏究結果發現，主要原因之一在於有機 纖維含有水分。針對此點，說明如下。 有機纖維並非製造後立即混合於不定形耐火物中，而 是經過搬運至不定形耐火物的製造工廠及保存，至作爲不 定形耐火物的一部份予以混合之期間爲止，於暴露於空氣 中之進料斗內呈待用狀態。上述搬運及保存期間有機纖維 存放於撓性集裝袋中，但當濕氣通過撓性集裝袋時，空氣 中的濕氣等水分可能附著於有機纖維。此外，上述待用狀 態期間空氣中的濕氣等水分亦可能附著於有機纖維。再 者，上述搬運〜待用通常延續數日以上》 另一方面，不定形耐火物中有機纖維以外的剩餘部分 裡含有耐火性粉體及黏合劑。添加水所施工而得之不定形 耐火物，通常使用氧化鋁水泥等水硬性黏合劑作爲黏合 劑。耐火性粉體中含有鎂質原料、氧化鈣質原料、或白雲 石質原料等具有消化性質之原料（以下稱爲消化性原料）， 或二氧化矽粉等超微細粉末。在此，消化係指原料與水反 應生成氫化物之現象。 因此，製造而成之不定形耐火物中，即使於添加施工 時所須要的水之前，已附著水之有機纖維與水硬性黏合 劑'消化性原料及超微細粉末之至少任一者接觸，可成爲 對該等的水分供給源。 此外，製造而成之不定形耐火物並非立即供施工之 用。通常，對不定形耐火物的製造工廠預定訂購，自製造 工廠將不定形耐火物出貨後，以至於施工現場添加水供施 201236998 工之用爲止，係於以撓性集裝袋包裝之狀態，經 略5天〜數月的儲存期間。 此儲存期間中，因有機纖維含有的水分，造 硬性黏合劑、消化性原料或超微細粉末的劣化。 水硬性黏合劑與水分接觸並於施工前完成部分水 施工後的反應性將下降，水硬性黏合劑的強度賦 下降。再者，一旦消化性原料與水分接觸而消化 膨脹成乾燥狀態成爲施工後強度下降的原因。再 超微細粉末與水分接觸時，可能因爲表面氫化， 發生變化，成爲施工後強度下降的原因。 施工體的爆裂係由於施工體內部的蒸氣壓超 的強度而產生。有機纖維的熔點愈低，愈於早期 氣的通氣孔，故內部蒸氣壓不易蓄積，但因爲有 含有的水分造成施工體的強度不足時，施工體便 內部蒸氣壓而產生爆裂。 專利文獻1〜4揭示顯示各自推薦之有機纖維 裂效果之試驗結果，但每一試驗皆於實驗室進行 定形耐火物的樣品後，立即將其與水混合以供驗 法反應實際程序中上述貯存期間等的影響。至今 維所含有的水分成爲阻礙防止爆裂效果的因子一 人知。 專利文獻1所使用的維尼綸纖維含有大量水 綸纖維的公定回潮率爲5質量％。因此，維尼綸 於上述長期儲存的情況時，無法充分發揮防止爆 過例如約 成上述水 即，一旦 解反應， 予效能將 將因體積 者，亦知 隨時間而 過施工體 形成水蒸 機纖維所 無法承受 的防止爆 ，製作不 證，故無 ，有機纖 事尙不爲 分。維尼 纖維尤其 裂效果。 -8- 201236998 一般而言，有機纖維的公定回潮率係指有機纖維組織 內部的含水量。 專利文獻2~4所使用的聚乙烯纖維的公定回潮率爲0 質量％，但如上所述，有於保存中水分附著於纖維表面的 情形。因此，聚乙烯纖維的含水量未必是〇質量％。有因 附著於纖維表面之水分而引發爆裂的情形。 本說明書中有機纖維的含水量係指有機纖維組織內部 的水分量與附著於有機纖維表面的水分量之總合。 本發明的目的係提供乾燥時不易產生龜裂或爆裂之不 定形耐火物。 [解決課題之手段] 根據本發明的一個觀點，可提供含有有機纖維，且添 加水所施工而得之不定形耐火物中，以使用含水量未達3 質量％且使表面附著油分之聚乙烯纖維作爲有機纖維爲特 徵之不定形耐火物。 [發明效果] 爲防止爆裂，必須考慮施工體的強度與施工體內部蒸 氣壓的平衡，使內部蒸氣壓不超過施工體的強度。 本發明中使用之上述有機纖維的含水量未達3質量 %，且藉由使油分附著於其上，水分不易附著於纖維表 面。因此’本發明中使用之上述有機纖維使不定形耐火物 中有機纖維以外的剩餘部份即使於儲存期間亦不易發生劣 -9 - 201236998 化。因此，可防止乾燥程序中施工體的強度下降。 再者，本發明中使用之有機纖維係以聚乙烯爲素材。 聚乙烯即使於公定回潮率可滿足本發明指定的含水量之有 機纖維中熔點亦屬特別低。因此，本發明中使用之有機纖 維於乾燥開始後於早期熔融形成通氣孔，故對於施工體內 部的蒸氣壓之緩和亦具有良好效果。 以上結果可於乾燥時防止施工體內部的蒸氣壓超過施 工體的強度，可防止施工體的龜裂或爆裂。 【實施方式】 本發明的實施方式中，不定形耐火物含有耐火性粉 體，黏合劑及有機纖維。 本發明爲防止因有機纖維所含有的水分造成不定形耐 火物劣化，於不定形耐火物中有機纖維以外的剩餘部份 中，含有因水分而容易劣化之原料時具有尤其重大的意 義。具體而言，本發明於不定形耐火物含有耐火性粉體之 消化性原料、耐火性粉體之超微細粉末及黏合劑之水硬性 黏合劑至少任一者時具有尤其重大的意義。 消化性原料可提及的有，例如選自電融氧化鎂等鎂質 原料、橄欖石等氧化鎂-二氧化矽質原料、氧化鈣熔結塊 等氧化鈣質原料及白雲石熔結塊等白雲石質原料等一種以 上。尤其，消化性原料的摻合量於耐火性粉體中所佔比例 爲5質量％以上時，有因爲有機纖維所含有的水分而劣化 之疑慮。 -10- 201236998 超微細粉末其平均粒徑未達10 μηι者可提及的有，例 如二氧化矽粉等非結晶二氧化矽超微細粉末、煅燒氧化鋁 等氧化鋁超微細粉末、黏土、二氧化鈦超微細粉末等。尤 其二氧化矽粉容易因濕氣而產生劣化。再者，由超微細粉 末的槪念來看，上述消化性原料係被去除者。尤其，超微 細粉末的摻合量於耐火性粉體中所佔比例爲5質量％以上 時，有因爲有機纖維所含有的水分而劣化之疑慮。 本說明書中，平均粒徑係指以雷射繞射散射式粒度分 布測量裝置所測量之粒度分布的中間値之體積平均粒徑。 水硬性黏合劑可提及的有，例如氧化鋁水泥、水硬性 氧化鋁（Ρ-氧化鋁）、波特蘭水泥、輕燒氧化鎂等。尤其， 水硬性黏合劑的摻合量爲對耐火性粉體外加1質量％以上 時，有因爲有機纖維所含有的水分而劣化之疑慮。 有機纖維係使用含水量未達3質量％且使表面附著油 分之聚乙烯纖維。有機纖維的含水量以2質量％以下爲 佳，1.5質量％以下較佳。 本說明書中聚乙烯不僅是乙烯之同元聚合物，而是包 含乙烯與共聚單體之共聚合物之槪念。 含水量的定義如下》 含水量（質量％) = (含有水分之有機纖維的總質量-除去水分 之有機纖維的質量）/除去水分之有機纖維的質量Χ100 聚乙烯纖維因公定回潮率爲0質量％，亦即纖維的組 -11 - 201236998 織內部中不含水分，故其含水量未達3質量％係表示附著 於聚乙烯纖維表面之含水量未達3質量％。 再者，公定回潮率低之有機纖維中除了聚乙烯纖維之 外，亦有聚丙烯纖維、聚氯乙烯纖維及聚酯纖維，但聚乙 烯纖維係其中熔點最低者。因此，可於乾燥開始後於早期 熔融形成通氣孔，具有良好緩和施工體內部蒸氣壓之效 果。再者，例如聚乙烯纖維的熔點爲1 00-1 3 5 °c。 至於油分可提及的有，例如礦物油、蓖麻油以外的植 物油、十八酸異十三酯、POE十八烯醚、POE壬基酚醚、 十二烷基磺酸鈉鹽、POE十二烷基醚磷酸鉀鹽等。此等， 可使1種單獨附著，亦可倂用2種以上使其附著。 油分具有防止空氣中的水分附著於聚乙烯纖維表面上 之效果。因此，經附著油分之聚乙烯纖維於摻合至不定形 耐火物中之前，即使經過暴露於空氣中的儲存時間，亦不 易使不定形耐火物中有機纖維以外的剩餘部份產生劣化。 此結果可防止乾燥時施工體的強度下降。 對聚乙烯纖維之油分附著量無特殊限制，但以1 ~5質 量％爲佳。藉由使油分附著量爲1質量％以上，可進一步 加強防止水分附著於纖維表面之效果；藉由抑制於5質量 %以下，可防止因油分造成纖維的操作性或作業性之惡 化。 油分附著量的定義如下。 油分附著量（質量％)=附著於有機纖維之油分的質量/含有 -12- 201236998 油分之有機纖維的總質量χΙΟΟ 本發明中使用之上述聚乙烯纖維的製造方法無特殊限 制。例如，藉由將聚乙烯熔融紡絲，再將其熱延伸之後， 藉由設置油分附著程序’可連續獲得已附著油分之聚乙烯 纖維。或者’例如依照一般方式製造未附著油分之聚乙烯 纖維後’藉由進行油分之附著亦可獲得本發明之上述聚乙 嫌纖維。此時’於油分附著前，以實施乾燥使纖維的含水 量降低至未達3質量％者爲佳。油分的附著方法可提及的 有’例如塗布、噴塗或浸漬等。 聚乙烯依照密度大致區分爲高密度聚乙烯（11〇1>£)與 低密度聚乙烯（LDPE) ’其任一公定回潮率皆爲〇質量％。 本發明中’以其中的低密度聚乙烯爲佳。根據 JISK6922 ’低密度聚乙烯係指密度爲〇 91〇~〇 929g/cm3之 聚乙烯’但於本說明書中係指密度爲〇.929g/cm3以下之 聚乙稀。再者’高密度聚乙烯係指密度大於低密度聚乙烯 之聚乙烯。 低密度聚乙燒因密度小，故熔點低。因此，於乾燥程 序中可提早形成通氣孔，故具有特別良好緩和施工體內部 的蒸氣壓之效果。再者，低密度聚乙烯的熔點爲90〜135 °C。 再者’與高密度聚乙烯纖維相比，低密度聚乙烯纖維 較柔軟、較不黏’故對不定形耐火物之水的添加量相同 時’較使用高密度聚乙烯纖維時，具有可提高泥漿的流動 -13- 201236998 性之傾向。泥漿的流動性愈高，愈可使其無空隙地塡滿由 模框劃定的空間》 低密度聚乙烯分爲高壓法低密度聚乙烯與直鏈狀低密 度聚乙烯（LLDPE)，本發明中，以其中的直鏈狀低密度聚 乙烯爲佳。直鏈狀的低密度聚乙烯即使於低密度聚乙烯中 亦屬具有良好拉伸強度，故混合時不易碎裂。假若有機纖 維於混合中碎裂時，自然而然於乾燥程序中所形成之數個 通氣孔亦隨之變短，故施工體的通氣性將下降。對此，有 機纖維於混合中不易碎裂時，可防止施工體的通氣性下 降，故可充分發揮有機纖維的防止爆裂效果》 此聚乙烯纖維的摻合量應可依業者的技術常識自行決 定。例如，此聚乙烯纖維的摻合量與以往的有機纖維相 同，可爲對耐火性粉體100質量％外加0.01 ~1質量％。 此聚乙烯纖維的直徑無特別限制。直徑可爲例如 1~100μηι。藉由使直徑爲Ιμηι以上，於施工體中所形成之 數個通氣孔的通氣阻力將變得特別小。藉由使直徑爲 ΙΟΟμιη以下，即使添加量爲〇.〇1〜1質量％亦可充分確保纖 維支數，具有特別良好地降低施工體的通氣性之效果。直 徑以1〜5 0 μ m爲佳。 此聚乙烯纖維的長度亦無特別限制。長度可爲例如 1〜20mm。藉由使長度爲1mm以上，可抑制切割成本的攀 升，且具有良好的通氣孔的連續性。藉由使長度爲20mm 以下，將不易發生將不定形耐火物以水混合而成之泥漿的 流動性的下降。 -14- 201236998 以上針對本發明的一種實施方式進行說明，但本發明 不限於此。 耐火性粉體中自可含有電融氧化鋁或鋁礬土等氧化鋁 質原料、矽石等二氧化矽質原料、藍晶石或紅柱石或燒磨 土等矽鋁質原料、鍩石質原料、碳化矽及碳質原料等不具 消化性質之原料。 黏合劑中自可含有瀝青、焦油、樹脂等有機黏合材 料’矽溶膠、矽酸鹽或磷酸鹽等不具水硬性者。再者，黏 合劑並非必要。本發明之不定形耐火物亦可不含有黏合 劑。 此外，此不定形耐火物自可含有選自例如分散劑、乳 酸鋁、金屬粉末、增黏劑、抗氧化劑、低熔點玻璃及硬化 時間調整劑等一種以上之添加劑。 此不定形耐火物的施工方式若爲添加水施工而得之方 式，無特殊限制。可提及的典型施工方式有澆鑄施工法、 振動鏝塗施工、濕式噴塗施工法及乾式噴塗施工法等。於 澆鑄施工法、振動鏝塗施工及濕式噴塗施工法中，事先將 此不定形耐火物與水共同混合成泥漿。於乾式噴塗施工法 中，將此不定形耐火物對噴嘴以氣流輸送通過輸送管內， 於輸送管內及噴嘴之至少任一者添加水。亦有於輸送管的 數處添加水之情形。不論任一種施工法，只要於不定形耐 火物中添加水施工而成，即須要藉由加熱降低該水分之乾 燥程序。 -15- 201236998 [實施例] 表1揭示不定形耐火物的具體例。表1中以海產氧化 鎂爲消化性原料，以二氧化矽粉及煅燒氧化鋁爲超微細粉 末，以氧化鋁水泥爲水硬性黏合劑。以表1之摻合爲基 礎，變換多種有機纖維。 [表1] 不定形耐火物的組成 摻合量(質量％) 耐 火 性 粉 體 粗粒域(1mm以上） 燒結氧化鋁 46 中粒域(75μηι以上，未達Imm) 燒結氧化銘 25 微粒域(未達75μπι) 電融氧化鋁 10 煅燒氧化鋁 10 海產氧化鎂 7 二氧化矽粉 2 水硬性黏合劑 氧化鋁水泥 (6) 分散劑 六偏磷酸鈉 (0.1) 有機纖維 (0.15) 括弧内的数値係表示對耐火性粉體外加（質量％)。 表2係揭示除了表1的摻合構成中作爲有機纖維使用 者之外’該含水量、含油量及不定形耐火物的評估結果。 -16- 201236998 比較例 I CO 維尼綸 o σ> CO X X m 聚氯乙烯 oq s ◎ X χκπ su tr> ◎ X CO 聚丙烯 p ◎ <1 CM LDPE p < ◎ HDPE OJ CO p <J 〇 實施例 in LLDPE CNJ ◎ ◎◎ 寸 LDPE <1.0 s ◎ ◎ CO LDPE o CO ◎ ◎ CM LDPE 〇 ◎ HDPE CO ◎ 〇 / 素材 含水量 (質量％) 含油量 (質量％) 固化強度 通氣性 is担煺睬 -17- 201236998 表2的任一有機纖維的形狀皆統一爲直徑10~20μηι , 長 3〜5 m m。 含水量係藉由熱風乾燥法’以下述標準式求得。「含 水量（質量％)=(試料的質量-試料的絕對乾燥質量）/試料 的絕對乾燥質量X 1 〇〇」此處，試料的絕對乾燥質量係指將 試料置於105 °c ±2 °c之熱風乾燥機中之恆重的質量。再 者，實驗次數爲2次，該平均値揭示於表2。 含油量係以使用迅速殘脂抽出裝置（東海計器公司 製），將油分以丙醇：己烷=1: 2混合之溶液抽出於托盤 上後，去除溶劑之方法，藉由下述標準式求得。「含油量 (質fl %) = (油分抽出後之托盤的質量-油分抽出前之托盤的 質量）/取樣量XI 〇〇」再者，實驗次數爲2次，該平均値揭 示於表2。 評估係以下述要點進行。首先，將有機纖維置於可使 水分附著於表面之狀況，具體而言，置於溼度75〜85%的 空間中5天。其次，將該有機纖維與表1的剩餘部分的組 成物共同混合獲得不定形耐火物。將所得之不定形耐火物 收納於塑膠袋中放置1星期。接著，對不定形耐火物100 質Μ %另外添加6質量％的水予以混合成泥漿。將所得之 泥漿澆鑄於模框，固化後，以1 50°C進行6小時的高壓釜 處理而成之樣品以其爲測量對象。 固化強度係由上述樣品的抗彎強度以X、△、〇、◎ 4 個階段進行相對評估。抗彎強度愈大，施工體愈能抵抗巨 大的內部蒸氣壓故不易發生爆裂。再者，抗彎強度係以上 18- 201236998 述樣品爲測量對象，依據〗IS-R2553的規定測量。 通氣性係由上述樣品的通氣率以X、△、〇、◎、◎ ◎ 5個階段進行相對評估。通氣率愈大，施工體內部愈不 易蓄積水蒸氣故不易發生爆裂。再者，通氣率M(cm2/ (cmH20· sec))定義爲 n = Qx (L/S^U/PrPJ。此處，Q 爲 於單位時間內通過樣品之氣體的體積（cmVsec)，其係以漏 氣測試器（Air Leak TesterKCOSMO計器股份有限公司製 LS-1821)測量。S爲樣品的剖面面積（cm2)，L爲上述樣品 的厚度（cm)，Ρι爲氣體侵入樣品時的壓力（cmH20)，P2爲 大氣壓力（cmH20)。 實施例1係使用密度爲〇.94g/cm3的高密度聚乙烯纖 維’藉由使油分附著，含水量少，具良好固化強度。再 者’可接受通氣性較實施例2〜5的低密度聚乙烯纖維差。 因此，可稱爲具良好防止爆裂效果。 實施例2係使用低密度聚乙烯作爲聚乙烯纖維，較實 施例1具良好通氣率。再者，與實施例1相比，油分較 少，水分較多，故固化強度較實施例1差。 實施例3及4係較實施例2增加油分，故含水量少， 具良好固化強度。由實施例2〜4的結果來看，可知含水量 依含油量而定。 實施例5係使用直鏈狀的低密度聚乙烯纖維作爲聚乙 烯纖維’通氣性較實施例4提升。理由尙未確定，但推論 直鏈狀的低密度聚乙烯纖維即使於低密度聚乙烯中亦屬具 有良好拉伸強度’故混合時不易碎裂。即，因有機纖維於 -19- 201236998 混合時不易碎裂，故可防止施工體通氣性的下降，可充分 發揮有機纖維的防止爆裂效果。 比較例1係使用不含油分之聚乙烯纖維，熔點低故可 接受其通氣性，但因含水量高故固化強度不足。因此，有 於實施中爆裂的疑慮。藉由比較例1與實施例1的比較， 可知有機纖維的含水量高時施工體的固化強度將下降。可 知爲防止爆裂，必須使聚乙烯纖維的含水量未達3質量 %。 比較例2係使用不含油分之低密度聚乙烯纖維，具良 好通氣性，但含水量高故固化強度不足，有爆裂的疑慮。 .比較例3、4、5係各自使用聚丙烯纖維 '聚酯纖維、 聚氯乙烯纖維，若僅聚焦於含水量雖可滿足本發明的規 定，但因熔點高，故通氣性差，發生爆裂的機率高。 比較例6係使用維尼綸纖維，維尼綸纖維可溶於溫水 中但於施工體表面形成結皮，故通氣性差。再者，維尼綸 纖維的含水量高故固化強度小。 以上沿具體例說明本發明，但本發明不限於此。例如 業者當知可有多種組合及改良。_ -20-201236998 VI. Description of the Invention [Technical Field of the Invention] The present invention relates to an amorphous refractory material which is obtained by adding organic fibers and adding water. [Prior Art] The monolithic refractory is used for the lining of various molten metal containers such as a ladle, a feed tank, a blast furnace tap tank or a vacuum degassing furnace. Hereinafter, a construction method of an amorphous refractory is described by taking a casting construction of a lining of a ladle as an example. First, water is added to the monolithic refractory and mixed to make it a slurry. Next, the slurry is cast between the core of the pouring pour and the inner wall of the ladle, and is solidified until the shape is found. The cast slurry is solidified until it is found to be shaped, and is called a construction body. After curing, the core is removed, and the remaining construction body is dried to form a liner. The drying of the construction body is carried out by heating with a burner or microwave. When heated, water vapor is generated from inside the construction body, and the construction body may be cracked or burst due to vapor pressure. If the construction body is dried for a long time at a slow heating rate, the occurrence of cracking can be suppressed. However, from the viewpoint of improving the use rate of the ladle, it is desirable to shorten the drying time. Therefore, in the past, countermeasures have been made for the amorphous refractory to contain organic fibers. The organic fiber is reduced in volume by heating in the drying body during heating, and forms a vent hole for water vapor in the working body. The water vapor will escape from the inside of the construction body to the outside through a myriad of fine venting groups formed of organic fibers. Thereby, the increase in the vapor pressure inside the construction body can be alleviated, and the burst of the -5 " 201236998 system can be suppressed. According to Patent Document 1, it is understood that the vapor pressure inside the working body rises sharply from about 200 ° C. Therefore, it is preferable that the organic fibers are melted at a temperature of not less than 180 ° C before the vapor pressure rises abruptly. Patent Document 1 discloses that Vinylene, polyethylene, polypropylene, and the like can be used as a material having a low melting point, and vinylon fibers are preferred. Patent Documents 2 and 3 disclose specific examples in which polyethylene fibers are selected as the amorphous refractories for preventing the organic fibers for bursting (refer to Examples 2 and 3 of Patent Document 2, and Comparative Example 3 of Patent Document 3). Further, Patent Document 3 discloses that the water content of the polyethylene fiber is 0% by mass (refer to the upper right column and the second table of the second page of Patent Document 3). Patent Document 4 discloses a low-density polyethylene having a density of 0.93 g/cm 3 or less as a material for preventing organic fibers for bursting. It is known that the low melting point of polyethylene in polyethylene is also low, ranging from 100 to 13 5 °C. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei. No. Hei. [Patent Document 4] JP-A-2008-1 20669 SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] Conventionally, it is considered that the organic fiber has a lower melting point. However, there is still a case of bursting regardless of how the low melting organic fiber is used. -6- 201236998 The inventors found out that the main reason is that the organic fiber contains moisture. For this point, the explanation is as follows. The organic fiber is not mixed in the amorphous refractory immediately after manufacture, but is transported to the manufacturing plant and storage of the amorphous refractory, and is exposed to the air until it is mixed as part of the amorphous refractory. The feed hopper is in a standby state. The organic fibers are stored in the flexible container during the handling and storage, but when moisture passes through the flexible container, moisture such as moisture in the air may adhere to the organic fibers. Further, moisture such as moisture in the air during the above-mentioned standby state may adhere to the organic fibers. Further, the above-mentioned conveyance-to-use is usually continued for several days or more. On the other hand, the remainder of the organic fiber other than the amorphous refractory contains a refractory powder and a binder. A non-shaped refractory material obtained by adding water is usually a hydraulic binder such as alumina cement as a binder. The refractory powder contains a raw material having a digestive property such as a magnesia raw material, a calcium oxide raw material, or a dolomitic raw material (hereinafter referred to as a digestive raw material), or an ultrafine powder such as cerium oxide powder. Here, digestion refers to the phenomenon in which a raw material reacts with water to form a hydride. Therefore, in the manufactured amorphous refractory, even if the water-attached organic fiber is in contact with at least one of the hydraulic binder 'digestive raw material and the ultrafine powder before the water required for the construction is added, It becomes a source of water supply to these. In addition, the manufactured amorphous refractory is not immediately available for construction. Usually, the manufacturing plant for monolithic refractories is ordered, and the unshaped refractory is shipped from the manufacturing plant, so that the water is added to the construction site for use in 201236998, and it is packaged in a flexible container. After a period of 5 days to several months of storage. During this storage period, the moisture contained in the organic fibers deteriorates the hard binder, the digestive material, or the ultrafine powder. The reactivity of the hydraulic binder after contact with moisture and partial water construction before construction will decrease, and the strength of the hydraulic binder will decrease. Further, once the digestive raw material comes into contact with moisture, it is digested and expanded into a dry state, which causes a decrease in strength after the construction. When the ultrafine powder is in contact with moisture, it may change due to surface hydrogenation, which may cause a decrease in strength after construction. The burst of the construction body is caused by the strength of the vapor pressure inside the construction body. The lower the melting point of the organic fiber, the higher the vent hole of the early gas, so that the internal vapor pressure is less likely to accumulate. However, if the strength of the working body is insufficient due to the contained moisture, the internal vapor pressure of the working body may cause a burst. Patent Documents 1 to 4 disclose test results showing the cracking effect of the respective recommended organic fibers, but each test is carried out in the laboratory immediately after the sample of the shaped refractory is mixed with water for the above-mentioned storage in the actual procedure of the test reaction. The impact of the period, etc. The moisture contained in the U.S. has become a factor that hinders the effect of preventing the bursting. The vinylon fiber used in Patent Document 1 contains a large amount of urethane fiber and has a predetermined moisture regain of 5% by mass. Therefore, in the case of the above-mentioned long-term storage, Vinylon cannot fully exert the prevention of bursting, for example, into the above-mentioned water. Once the reaction is resolved, the effect will be due to the volume, and it is also known that the water is formed by the construction body over time. Unbearable to prevent explosion, production does not prove, so no, organic fiber is not a part. Pooh fibers are especially cracking. -8- 201236998 In general, the nominal moisture regain of organic fibers refers to the water content inside the organic fiber structure. The polyethylene ray used in Patent Documents 2 to 4 has a specific moisture regain of 0% by mass, but as described above, moisture adheres to the surface of the fiber during storage. Therefore, the water content of the polyethylene fiber is not necessarily 〇% by mass. There is a case where a crack occurs due to moisture attached to the surface of the fiber. The water content of the organic fiber in the present specification means the sum of the amount of water inside the organic fiber structure and the amount of moisture attached to the surface of the organic fiber. SUMMARY OF THE INVENTION It is an object of the present invention to provide an amorphous refractory which is less prone to cracking or bursting when dried. [Means for Solving the Problem] According to one aspect of the present invention, it is possible to provide an amorphous refractory material containing organic fibers and added with water, and to use a polyethylene having a water content of less than 3% by mass and having an oil adhered to the surface. Fibers are unshaped refractories characterized by organic fibers. [Effect of the Invention] In order to prevent bursting, it is necessary to consider the balance between the strength of the working body and the vapor pressure inside the working body so that the internal vapor pressure does not exceed the strength of the working body. The organic fiber used in the present invention has a water content of less than 3% by mass, and moisture is less likely to adhere to the surface of the fiber by adhering the oil to it. Therefore, the above-mentioned organic fibers used in the present invention make the remaining portion other than the organic fibers in the monolithic refractory hard to be inferior even during storage. Therefore, the strength of the working body in the drying process can be prevented from being lowered. Further, the organic fiber used in the present invention is made of polyethylene. The polyethylene has a particularly low melting point even in an organic fiber which has a predetermined moisture regain and which satisfies the water content specified in the present invention. Therefore, the organic fiber used in the present invention melts to form a vent hole at an early stage after the start of drying, and therefore has a good effect on the relaxation of the vapor pressure in the inside of the construction. The above results prevent the vapor pressure inside the construction body from exceeding the strength of the working body during drying, and can prevent cracking or bursting of the construction body. [Embodiment] In an embodiment of the present invention, the monolithic refractory contains a refractory powder, a binder, and an organic fiber. In the present invention, in order to prevent the deterioration of the amorphous fire-resistant material due to the moisture contained in the organic fiber, it is particularly important to contain a raw material which is easily deteriorated by moisture in the remaining portion other than the organic fiber in the amorphous refractory. Specifically, the present invention is particularly significant in the case where the monolithic refractory contains at least one of a digestive raw material of a refractory powder, an ultrafine powder of a refractory powder, and a hydraulic binder of a binder. Examples of the digestive raw material include, for example, a magnesium raw material selected from the group consisting of a magnesia raw material such as electromagnetized magnesia, a magnesia-cerium oxide raw material such as olivine, a calcium oxide raw material such as a calcium oxide frit, and a dolomite sintered agglomerate. More than one type of dolomitic raw materials. In particular, when the blending amount of the digestive raw material is 5% by mass or more in the amount of the refractory powder, there is a fear that the moisture contained in the organic fiber is deteriorated. -10- 201236998 Ultrafine powders with an average particle size of less than 10 μηι include, for example, non-crystalline cerium oxide ultrafine powder such as cerium oxide powder, alumina ultrafine powder such as calcined alumina, clay, and titanium dioxide. Ultrafine powder, etc. In particular, the cerium oxide powder is easily deteriorated by moisture. Further, from the viewpoint of the ultrafine powder, the above-mentioned digestive raw material is removed. In particular, when the blending amount of the ultrafine powder is 5% by mass or more in the amount of the refractory powder, there is a fear that the moisture contained in the organic fiber is deteriorated. In the present specification, the average particle diameter refers to the volume average particle diameter of the intermediate crucible of the particle size distribution measured by the laser diffraction scattering type particle size distribution measuring device. As the hydraulic binder, there may be mentioned, for example, alumina cement, hydraulic alumina (yttrium-alumina), Portland cement, light burned magnesia, and the like. In particular, when the amount of the hydraulic binder to be added is 1% by mass or more to the refractory powder, the water contained in the organic fiber may be deteriorated. The organic fiber is a polyethylene fiber having a water content of less than 3% by mass and having an oil adhered to the surface. The water content of the organic fiber is preferably 2% by mass or less, and more preferably 1.5% by mass or less. The polyethylene in this specification is not only a homopolymer of ethylene but a complication of a copolymer of ethylene and a comonomer. The water content is defined as follows: Water content (% by mass) = (total mass of organic fiber containing moisture - mass of organic fiber from which moisture is removed) / mass of organic fiber to be removed by water Χ 100 polyethylene fiber has a specific moisture regain of 0 mass %, that is, the group of fibers -11 - 201236998 The inside of the woven fabric does not contain water, so that the water content is less than 3% by mass, indicating that the water content attached to the surface of the polyethylene fiber is less than 3% by mass. Further, in addition to the polyethylene fiber, the organic fiber having a low moisture regaining rate also has a polypropylene fiber, a polyvinyl chloride fiber, and a polyester fiber, but the polyethylene fiber is the one having the lowest melting point. Therefore, the vent holes can be melted at an early stage after the start of drying, and the effect of the vapor pressure inside the working body can be well relaxed. Further, for example, the polyethylene fiber has a melting point of 1 00-1 3 5 °c. As the oil component, there may be mentioned, for example, mineral oil, vegetable oil other than castor oil, isotridecyl octadecylate, POE octadecyl ether, POE nonylphenol ether, sodium dodecyl sulfate, POE twelve. Alkyl ether phosphate potassium salt and the like. In this case, one type may be attached alone or two or more types may be used for adhesion. The oil component has an effect of preventing moisture in the air from adhering to the surface of the polyethylene fiber. Therefore, the polyethylene fiber to which the oil is attached is not easily deteriorated in the amorphous refractory except for the storage time in the air before being mixed into the amorphous refractory. This result prevents the strength of the construction body from decreasing when it is dried. The amount of oil adhering to the polyethylene fiber is not particularly limited, but is preferably 1-5 mass%. When the amount of the oil to be adhered is 1% by mass or more, the effect of preventing moisture from adhering to the surface of the fiber can be further enhanced. When the amount of the oil is less than 5% by mass, the handling property of the fiber or the deterioration of workability due to oil can be prevented. The amount of oil adhering is defined as follows. The amount of the oil component (% by mass) = the mass of the oil component attached to the organic fiber / the total mass of the organic fiber containing -12 - 201236998 oil component χΙΟΟ The method for producing the above-mentioned polyethylene fiber used in the present invention is not particularly limited. For example, after the polyethylene is melt-spun and then thermally extended, the polyethylene fiber to which the oil is adhered can be continuously obtained by providing the oil adhering procedure. Alternatively, the above-mentioned polyethylene fibers of the present invention can be obtained by, for example, producing a polyethylene fiber having no oil component in a general manner. At this time, it is preferred to carry out drying to reduce the water content of the fiber to less than 3% by mass before the oil component is attached. The method of attaching the oil may be mentioned, for example, coating, spraying or dipping. Polyethylene is roughly classified into high-density polyethylene (11〇1>£) and low-density polyethylene (LDPE) according to density, and any of the specified moisture regain ratios is 〇% by mass. In the present invention, the low density polyethylene is preferred. According to JIS K6922, 'low-density polyethylene refers to polyethylene having a density of 〇91〇~〇 929g/cm3', but in the present specification, it refers to polyethylene having a density of 929.929g/cm3 or less. Further, 'high density polyethylene means a polyethylene having a density higher than that of low density polyethylene. Low-density polyethylene has a low melting point due to its low density. Therefore, the vent hole can be formed early in the drying process, so that it has an effect of particularly relaxing the vapor pressure inside the working body. Further, the low density polyethylene has a melting point of 90 to 135 °C. Furthermore, 'lower density polyethylene fiber is softer and less sticky than high density polyethylene fiber', so when the amount of water added to the amorphous refractory is the same, it can be improved when using high density polyethylene fiber. The flow of mud-13- 201236998 Sexual tendency. The higher the fluidity of the mud, the more it can fill the space defined by the mold frame without voids. Low-density polyethylene is divided into high-pressure process low-density polyethylene and linear low-density polyethylene (LLDPE), the present invention Among them, a linear low-density polyethylene is preferred. Linear low-density polyethylene has good tensile strength even in low-density polyethylene, so it is not easily broken when mixed. If the organic fibers are broken during mixing, the number of vent holes naturally formed in the drying process is also shortened, so that the air permeability of the construction body is lowered. In this case, when the organic fiber is not easily broken during mixing, the air permeability of the construction body can be prevented from being lowered, so that the effect of preventing the bursting of the organic fiber can be sufficiently exerted. The blending amount of the polyethylene fiber should be determined by the technical know-how of the manufacturer. . For example, the blending amount of the polyethylene fibers is the same as that of the conventional organic fibers, and may be 0.01 to 1% by mass based on 100% by mass of the refractory powder. The diameter of this polyethylene fiber is not particularly limited. The diameter may be, for example, 1 to 100 μm. By making the diameter Ιμηι or more, the ventilation resistance of the plurality of vent holes formed in the construction body becomes extremely small. When the diameter is ΙΟΟμηη or less, the fiber count can be sufficiently ensured even when the amount is 〇.〇1 to 1% by mass, and the effect of particularly reducing the air permeability of the construction body is obtained. The diameter is preferably 1 to 50 μm. The length of the polyethylene fiber is also not particularly limited. The length can be, for example, 1 to 20 mm. By making the length 1 mm or more, the cutting cost can be suppressed and the continuity of the vent hole can be improved. When the length is 20 mm or less, the fluidity of the slurry obtained by mixing the amorphous refractory with water is less likely to occur. -14-201236998 An embodiment of the present invention has been described above, but the present invention is not limited thereto. The refractory powder may contain alumina raw materials such as fused alumina or bauxite, cerium oxide raw materials such as vermiculite, yttrium aluminum raw materials such as kyanite or andalusite or burnt earth, and strontium. Raw materials, such as raw materials, tantalum carbide and carbonaceous raw materials, which are not digestible. The binder may contain organic binders such as pitch, tar, and resin, such as sol, citrate or phosphate, which are not hydraulic. Furthermore, adhesives are not necessary. The monolithic refractory of the present invention may also contain no binder. Further, the monolithic refractory may contain one or more additives selected from, for example, a dispersant, aluminum lactate, metal powder, a tackifier, an antioxidant, a low-melting glass, and a hardening time adjuster. The construction method of the monolithic refractory is not limited unless it is a method of adding water. Typical construction methods that can be mentioned include casting construction method, vibration coating construction, wet spraying construction method and dry spraying construction method. In the casting construction method, the vibration coating application, and the wet spraying construction method, the amorphous refractory is mixed with water in advance to form a slurry. In the dry spray application method, the amorphous refractory is conveyed through the transfer pipe to the nozzle by air flow, and water is added to at least one of the transfer pipe and the nozzle. There are also cases where water is added to several places in the duct. Regardless of any construction method, as long as water is added to the amorphous fire resistant material, it is necessary to reduce the drying process by heating. -15-201236998 [Examples] Table 1 discloses specific examples of the amorphous refractories. In Table 1, sea-based magnesium oxide is used as a digestive raw material, cerium oxide powder and calcined alumina are ultrafine powders, and alumina cement is used as a hydraulic binder. A variety of organic fibers were converted based on the blending of Table 1. [Table 1] Composition blending amount of unshaped refractory (% by mass) Refractory powder coarse grain domain (1 mm or more) Sintered alumina 46 in grain domain (75 μηι or more, less than 1 mm) Sintered oxide Ming 25 particle domain ( Less than 75μπι) fused alumina 10 calcined alumina 10 marine magnesia 7 cerium oxide powder 2 hydraulic binder alumina cement (6) dispersant sodium hexametaphosphate (0.1) organic fiber (0.15) This indicates that the refractory powder is added in vitro (% by mass). Table 2 shows the evaluation results of the water content, the oil content and the amorphous refractory except for the use of the organic fiber in the blending composition of Table 1. -16- 201236998 Comparative Example I CO Vinylon o σ> CO XX m Polyvinyl chloride oq s ◎ X χκπ su tr> ◎ X CO Polypropylene p ◎ <1 CM LDPE p < ◎ HDPE OJ CO p <J 〇Example in LLDPE CNJ ◎ ◎◎ inch LDPE <1.0 s ◎ ◎ CO LDPE o CO ◎ ◎ CM LDPE 〇 ◎ HDPE CO ◎ 〇 / Material moisture content (% by mass) Oil content (% by mass) Curing strength ventilation is煺睬-17- 201236998 The shape of any of the organic fibers in Table 2 is uniform to a diameter of 10 to 20 μm and a length of 3 to 5 mm. The water content was determined by a hot air drying method by the following standard formula. "Water content (% by mass) = (mass of sample - absolute dry mass of sample) / absolute dry mass of sample X 1 〇〇" Here, the absolute dry mass of the sample means that the sample is placed at 105 °c ± 2 ° The mass of the constant weight in the hot air dryer of c. Furthermore, the number of experiments was 2, and the average 値 is shown in Table 2. The oil content is obtained by using a rapid residual fat extraction device (manufactured by Tokai Keiki Co., Ltd.), and extracting the oil into a tray with a solution of a mixture of propanol:hexane = 1:2, and removing the solvent by the following standard formula. Got it. "Oil content (quality fl %) = (the quality of the tray after the oil is extracted - the mass of the tray before the oil is extracted) / the sampling amount XI 〇〇" Again, the number of experiments is 2, and the average 値 is shown in Table 2. The evaluation is carried out with the following points. First, the organic fibers are placed in a state where moisture can adhere to the surface, specifically, in a space of 75 to 85% humidity for 5 days. Next, the organic fiber was mixed with the composition of the remaining portion of Table 1 to obtain an amorphous refractory. The obtained monolithic refractory was placed in a plastic bag and left for 1 week. Next, 5% by mass of water was added to the monolithic refractory 100, and the mixture was mixed into a slurry. The obtained slurry was cast in a mold frame, and after solidification, a sample obtained by autoclaving at 1500 ° C for 6 hours was used as a measurement object. The curing strength was relatively evaluated by the bending strength of the above samples in four stages of X, Δ, 〇, and ◎. The greater the flexural strength, the more the construction body resists the large internal vapor pressure and is less prone to bursting. Furthermore, the flexural strength is above 18- 201236998 The sample is the measurement object and is measured according to the provisions of IS-R2553. The air permeability was evaluated by the air permeability of the above samples in five stages of X, Δ, 〇, ◎, ◎ ◎. The higher the ventilation rate, the less likely it is to accumulate water vapor inside the construction body, so that it is less prone to bursting. Furthermore, the ventilation rate M (cm2/(cmH20·sec)) is defined as n = Qx (L/S^U/PrPJ. Here, Q is the volume of gas passing through the sample per unit time (cmVsec), which is It was measured by a leak tester (LS-1821 manufactured by Air Leak Tester KCOSMO Co., Ltd.). S is the cross-sectional area (cm2) of the sample, L is the thickness (cm) of the above sample, and Ρ is the pressure at which the gas invades the sample (cmH20). P2 is atmospheric pressure (cmH20). Example 1 uses a high-density polyethylene fiber having a density of 94.94g/cm3. By adhering the oil, the water content is small, and the curing strength is good. The properties are inferior to those of the low-density polyethylene fibers of Examples 2 to 5. Therefore, it can be said to have a good effect of preventing bursting. Example 2 uses low-density polyethylene as the polyethylene fiber, which has a better aeration rate than Example 1. Compared with Example 1, the oil content was less and the water content was higher, so the curing strength was inferior to that of Example 1. Examples 3 and 4 were more oil-rich than Example 2, so the water content was small and the curing strength was good. From the results of Examples 2 to 4, it is understood that the water content depends on the oil content. Example 5 uses a linear low-density polyethylene fiber as the polyethylene fiber. The air permeability is improved compared to Example 4. The reason is not determined, but the linear low-density polyethylene fiber is inferred even in low-density polyethylene. It also has good tensile strength, so it is not easy to be broken when mixed. That is, since the organic fiber is not easily broken when mixed in -19-201236998, it can prevent the decrease of the air permeability of the construction body, and the organic fiber can be fully prevented from bursting. In the first comparative example, a polyethylene fiber containing no oil is used, and the melting point is low, so that the air permeability is acceptable. However, since the water content is high, the curing strength is insufficient. Therefore, there is a concern that bursting in practice. By comparison example 1 and In the comparison of Example 1, it is understood that the solidification strength of the organic fiber is lowered when the water content of the organic fiber is high. It is understood that the water content of the polyethylene fiber is less than 3% by mass in order to prevent the burst. Comparative Example 2 uses no oil. Low-density polyethylene fiber, which has good air permeability, but has high water content, so the curing strength is insufficient, and there is doubt about bursting. Comparative Examples 3, 4, and 5 are each using polypropylene fiber. Fibers and polyvinyl chloride fibers can satisfy the requirements of the present invention only when they are focused on the water content. However, since the melting point is high, the air permeability is poor, and the probability of occurrence of cracking is high. Comparative Example 6 uses vinylon fiber, and the vinylon fiber is soluble. In the warm water, the skin is formed on the surface of the construction body, so that the air permeability is poor. Further, the vinylon fiber has a high water content, so the curing strength is small. The present invention is described above by way of specific examples, but the present invention is not limited thereto. There are many combinations and improvements. _ -20-