201105783 五、 本案若有化學式時，請揭示最能顯示發日轉_ : 無。 工、 六、 發明說明： ί發明所屬之技術領域】 本發明係關於鎖固螺栓固定材料用組合物及由該組合 物硬化後所形成之鎖固螺栓固定材料。更詳言《，係關於 用於保護隧道構造物之鎖固螺栓施卫法中使用的長期耐久 性優異的鎖固螺栓固定材料用組合物及該組合物硬化後所 形成之鎖固螺栓固定材料。 【先前技術_] 於山岳隧道挖鑿作業中，在以AGF施工法、注入式先 撐管幕施工法、隧道鏡面先撐（face b〇lt)施工法等挖鑿 時，為了提高安全性，採用各種輔助施工法及於挖挖馨後 抑制隧道變形等的鎖固螺栓施工法的2種施工法。 AGF施工法或注入式先撐管幕施工法，係為了防止挖 馨時的端部崩落’將前方上部的土質安定化的施工法，係 確保從挖馨至加襯混凝土置放為止的安全性者。又，隨道 鏡面先撐（face bolt)施工法，係將係挖鑿剖面的鏡面及其 刖方的土質安定化的施工法，確保從一定區間挖鑿完成至 下-人挖鑿開始為止期間的安全性。此等輔助施工法係以 提升挖鑿作業的安全性為目的。 另一方面，鎖固螺栓施工法，係將隧道挖鑿後的周邊 201105783 地基安疋化的施工法’藉由將螺栓以固定材料固定於地 基’保護㈣構造物免於受之後置放之加減凝土及地震 等&成的地盤變動的影響。因此，用於將鎖固螺栓固定在 周邊地基之m定材料’要求需要確保隧道構造物使用時之 安全性的高強度及長期耐久性’與前述挖料使用在各種 輔助施工法的地基固結材料大不相同。 如此㈣固螺栓固定㈣，以往係使用具有高強度的 泥漿等無機系材料。但是，此等無機系材#，需一段長時 間方展現強度’因此作業效率不是很充分，且當發生漏水 或潘水時，會有材料流到水中的問題。 所以，為了解決此等問題，使用由鹼性矽酸鹽水溶液 與異氰酸酯化合物構成之有機—無機複合材料作為固定材 料。 例如，於專利文獻1，揭示：藉由使用含有鹼性矽酸 鹽水溶液、3級胺觸媒及甘油之水玻璃成分，及含二苯基 曱烷一異氰酸酯之異氰酸酯成分作為固定材料用組合物， 能在短時間硬化及展現強度。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2〇〇2—285155號公報 【發明内容】 [發明欲解決之問題] 但是，此等固定材料用組合物由於水玻璃成分與異氰 4 201105783 酸酉曰成；7的互溶性差，$易得到均句的硬化物，故 生裂痕等’於長期耐久性有問題存在。又，由於甘油之配 合量較多’容易在硬化物中殘留未反應的甘油故會有由 於其溶出到水中導致水質污染的顧慮。 本發明係有鑑於上述問題而生’目的在於提供一種鎖 固螺栓固定材料用組合物及該組合物硬化後形成的鎖固螺 栓固定材料’可抑财酸鹽水溶液之分離，切酸鹽水溶 液與異氰酸酯成分之互溶性優異，抑制有機化合物由硬： 物溶$，抑制環境污染（尤其水質污染），且能對於硬化物 賦予高強度’長期耐久性亦優異。 [解決課題之手段] 本發明之鎖固螺栓固定材料用組合物，係置放到隧道 挖鑿後之周邊地基者，其特徵在於：前述固定材料用組合 物由含有矽酸鹽水溶液之（A)成分及含有異氰酸酯化合物 之（B)成分構成，前述（A)成分含有選自（A1)矽酸鈉水溶液 及（A2)選自由三烷醇胺及烷基二烷醇胺基構成之群組的胺 多το醇，且前述（B)成分含有（Bi)異氰酸酯化合物及（B2) 由碳數8〜12之脂肪族醇與多元酸構成之酯化合物。 則述（A2)成分，宜於（A)成分中含有重量％。 前述（B1)成分’宜為使聚異氰酸酯化合物（β11)，與含 有氧乙烯單元5〜50重量％之聚醚多元醇（B12)反應而成的 異氰酸醋基末端胺曱酸乙醋預聚物較佳。 又’本發明之鎖固螺栓固定材料，係使鎖固螺栓固定 材料用組合物硬化而得之鎖固螺栓固定材料。 201105783 鎖固螺栓固定材料用組合 ,.、，、 々 由含有矽酸鹽水溶液夕 (A)成勿及含有異氰酸酯化人 σ物之（B)成分構成，相對於（a) 成为100重量份，配合（Β)成 、 战刀3〇〜120重量份較佳。 [發明效果] 依照本發明之鎖固螺於 螺栓固定材料用組合物及該组合物 硬化後形成之鎖固螺栓固定奸 U疋材料’能抑制矽酸鹽水溶液之 分離，碎酸鹽水溶液與異象酿 呉氰酸酯成分的互溶性優異，抑制 有機化合物由硬化物溶出，灰 4出抑制環境污染（尤其水質污 染）’且能對於硬化物賦予高強译 丁间強度，長期耐久性異優異。 【實施方式】 [實施發明之形態] 本發明之鎖固螺栓固定材料用組合物，係隧道挖鑿後 之周邊地基置放的鎖固螺栓固定材料用組合物，其特徵在 於：前述固定材料用組合物由含有矽酸鹽水溶液之（a)成分 及含有異氰酸酯化合物之（B)成分構成，且前述（A)成分含 有（A1)矽酸鈉水溶液及（A2)由選自三烷醇胺及烷基二烷醇 胺構成之群組的胺多元醇’且前述（B)成分含有（B1)異氰酸 酯化合物及（B2)由碳數8〜12之脂肪族醇與多元酸構成之 酉旨化合物。 前述含有矽酸鹽水溶液之（A)成分，含有（A1)矽酸鈉水 溶液，及（A2)選自由三烷醇胺及烷基二烷醇胺構成之群組 的胺多元醇。 矽酸鈉水溶液（A1)’可使用通常市售的石夕酸納的水溶 6 201105783 液作為主成分。此石夕酸納以通式：Na2〇 . xSi 〇2 . nH2〇表示。 在此’ x表示Si〇2(二氧化矽）與Na2〇(氧化鈉）的莫耳比， 本發明中，為2〜3，較佳為.2. 2〜2. 8。X若小於2，發泡 硬化反應中的無水矽酸凝膠化反應的比例減少，故2成分 混合時的硬化性變差，若超過3，矽酸鈉水溶液的黏度增 高’故與後述（B)成分的混合性及使用時的作業性降低。 *夕酸納水溶液（A1)之固體成分濃度，為35〜50重量 %’較佳為40〜45重量％。矽酸鈉水溶液之固體成分過高 時’可用水稀釋並調整。固體成分濃度小於35重量％時， (A)成分與（B)成分混合時的混合液中，水分含量增多，故 2成分的互溶性有降低的傾向，若超過5 〇重量％，（ A)成分 的黏度增加太多，與（B)成分的混合性及使用時的作業性有 降低的傾向。 規醇胺’例如：三乙醇胺 三丁醇胺、三異丁醇胺等。其中，從泛用性、經濟性的觀 點’三乙醇胺較佳。 烷基二烷醇胺，例如：甲基二乙醇胺、乙基二乙醇胺、 丙基二乙醇胺、異丙基二乙醇胺等烷基二乙醇胺化合物； 甲基二丙醇胺、乙基二丙醇胺、丙基二丙醇胺、異丙基二 丙醇胺等烷基二丙醇胺化合物；甲基二異丙醇胺、乙基二 異丙醇胺、丙基二異丙醇胺，異丙基二異丙醇胺等烷基二 異丙醇胺化合物；甲基二丁醇胺、乙基二丁醇胺、丙基二 丁醇胺、異丙基：丁醇胺等院基二丁醇胺化合物等。其中， 從(A)成分的安定化效果優異的觀點，烷基二乙醇胺化合物 201105783 較佳。 藉由配合（A2)，（A)成分的安定性 異氰酸酯化合物與水反應所產生的二氧化 且抑制（B1) 發泡及龜裂，能賦予硬化物充分強度。 (A2)之配合量，於（A)成分中為〇. 0. 1〜2· 0重量％更佳。若（A2)之配合量 成的硬化物 ~ 5· 0重量％較佳， 於0· 1重量％，（A) 成分的安定化效果不充分’且無法充分抑制由於二氧化碳 造成的硬化物發泡、龜裂’又，即使添加超過5. 〇重量％ 也付不到更1¾的效果。 本發明之鎖固螺栓固定材料中，也可適當配合胺觸媒 (A3)。胺觸媒’例如：三乙二胺、n，N，N，，N’ 一四甲基乙 二胺、N，N，N’ ，N’ 一四甲基丙二胺、N，N，N，，N，一四甲 基六曱二胺、Ν, Ν，Ν’ ，N"，N1，一五甲基二乙三胺， Ν，Ν，Ν’ ，Ν"，Ν"-五甲基二丙三胺、六甲基三乙四胺、六甲 基三丙四胺、Ν，Ν—二甲基環己胺、Ν，Ν—二甲基苄胺、Ν，Ν— 二甲基胺基丙胺、四曱基亞胺基雙丙胺、Ν，Ν，Ν—參（3—二 曱基胺基丙基）胺、Ν—甲基一Ν,Ν—雙（3~二甲基胺基丙基） 胺、Ν —甲基味琳、Ν—乙基味你、Ν，Ν—二曱基胺基乙基 味啉、二味啉二乙醚、Ν，Ν’ 一二甲基哌畊、ν,Ν，，Ν，一 二甲基胺基乙基略哄，Ν —甲基°米吐、1，2 —二甲基咪β坐、 二曱基胺基丙基味唾、1 —異丁基一 2—甲基味唾、雙（二甲 基胺基乙基）醚、三（二甲基胺基甲基）苯酚、Ν,Ν，，Ν，_ 參（3 —二曱基胺基丙基）六氫一 s—三畊等分子内不具羥基 之胺化合物；Ν，Ν—二甲基乙醇胺、Ν，Ν—二甲基胺基乙氧 201105783 基乙醇、N，N—二甲基胺基己醇、N，N，N，一三甲基胺基乙 基乙醇胺、N —曱基一Ν’ 一經基乙基》底哄、三.甲基經基乙 基雙胺基乙醚、三甲基胺基丙基乙醇胺、雙一 3—二甲基胺 基丙基）異丙醇胺、四曱基一2 —羥基乙基二乙三胺等分子 内具有1個羥基之胺化合物。 (A3)之配合量’可視需要的硬化速度適當調整，以（Α) 成分中含有0. 1〜2. 0重量％較佳。 前述（Β)成分’含有（Β1)異氰酸酯化合物及（Β2)由碳數 8〜12之脂肪族醇及多元酸構成之酯化合物。 (Β1)異氰酸酯化合物’例如··二苯基曱烷二異氰酸酯 及其異構物、聚亞甲基聚笨基聚異氰酸酯（p〇lymeric MDI)、碳二醯亞胺變性二笨基甲烷二異氰酸酯、甲苯二異 氛酸西曰、未加工的曱苯二異氰酸醋（crude tolylene diisocyante)、二甲苯二異氰酸酯、異佛爾酮二異氰酸酯、 蔡二異氰酸酯、氩化二苯基甲烷二異氰酸酯、三亞曱基二 甲苯二異氰酸酯等聚異氰酸酯的單獨或混合物。 又’也可使用以公知方法反應得到的異氰酸酯基末端 胺甲酸乙醋預聚物，係使得（B1)異氰酸酯化合物與多元醇 化合物成為NC0基與〇H基之當量比（NC0基/0H基）為1. 5 〜300，較佳為2.〇〜1〇〇之範圍。如此的多元醇化合物， 例如乙—醇、二乙二醇、三乙二醇、丙二醇、二丙二醇、 丁一醇、1,3 — 丁二醇、1，4 — 丁二醇、u —己二醇等二元 醇化合物；甘油、三羥甲基丙烷等三元醇化合物；季戊四 醇山梨糖醇、蔗糖等其他多元醇、單乙醇胺、二乙醇胺、 201105783 三乙醇胺’及對此等加成氧乙烯、氧丙烯、氧丁稀等伸产 基氧化物（alky 1 ene oxide)而成的聚醚多元醇。 听 具中，從 與矽酸鈉（A1)之互溶性優異 战刀混合液在 硬化前接觸到水時的排水污染的觀點，較佳為含有氧乙稀 單元5〜50重量％之聚醚多元醇。 其中’從安全衛生面及經濟性的觀點，^圭為於操作 環境溫度下的揮發性極小’燃點為2 〇 〇 以μ % ^ υ u以上、為液狀且 有經濟性構成的polymeric MDI，及使用此等的異氰酸酯 基末端胺甲酸乙酯預聚物氰酸酯基末端胺甲酸乙酯預 聚物更佳。 (B1)之配合量在（B)成分中為5〇〜95重量％。藉由使在 上述範圍内，（B1)異氰酸酯化合物中之異氰酸酯基與（au 石夕酸納水溶液中的水反應形成腺鍵，藉此能賦予硬化物充 分的強度。 藉由配合（B-2) ’能使（A)成分與（8)成分之互溶性提 =，且能抑制（B1)異氰酸醋化合物與水反應產生的二氧化 碳造成硬化物發泡，能對於硬化物賦予充分強度。 多元酸例如：己二酸、壬二酸、癸二酸、：苯二甲酸 等二元酸、偏苯三酸（trimellitic咖）等三元酸、苯均 四酸（welmic acid)等四元酸。由能使⑻成分為更 低黏度的觀點，以二元酸較佳。x，從環境影響之觀點， 更佳為能使水質污染更減低的己二酸。 藉由使脂肪族醇的碳數為 於水中時之有機化合物溶出量 8〜12 ’能減少硬化物浸泡 碳數8〜12之脂肪族醇， 10 201105783 異癸醇、--醇、十 例如：辛醇 '壬醇、異壬醇、癸醇 二醇等。 1〜5 0重量％，3 能使（B )成分低黏 (B2)之配合量，於（B)成分中較佳為 30重量％更佳。藉由使在上述範圍内， 度化，且能賦予良好的硬化性及強度。 其次，說明本發明之鎖固螺检固定材料。本發明之鎖 固螺栓固定材料’係使前述鎖㈣栓@定材制組合物硬 化得到的鎖固螺栓固定材料。 鎖固螺检固定材料用組合物中，⑴成分與⑻成分之 配合量，相對於（A)成分1〇〇重量份，較佳為（b)成分3〇〜 12。重量份’ 50〜90重量份更佳。若少於上述範圍，容易 發生硬化不良，若多於上述範圍，則硬化時產生的二氧化 碳量變多，故鎖固螺栓固定材料的發泡倍率會增高，容易 於鎖固螺栓固定材料發生龜裂，有不易得到充分強度之虞。 (A )成分與（B)成分開和混合至硬化為止的斯間，當將 (A)成分與（B)成分於液溫2(TC混合時，.以3〇〜18〇秒較 佳。若短於上述範圍，則有無法充分充填到鎖固螺栓前端 之虞’若長於上述範圍，則容易發生作業效率降低。 本發明之鎖固螺栓固定材料，由得到充分強度及耐久 性的觀點，依照JIS K 7220(硬質發泡塑膠之壓縮試驗方 法）測定的50%壓縮強度為20MPa以上較佳，更佳為3〇MPa 以上。 本發明之鎖固螺栓固定材料，由得到充分耐久性的觀 點’依照JIS K7221 (硬質發泡塑膠之彎曲試驗方法）測定 11 201105783 的彎曲強度為5MPa以上較佳，丨〇MPa以上更佳。 1〜3倍’更佳為1〜2倍，又争社故7 Λ 货入更佳為1〜1.5倍，1〜1. 最佳。 由使本發明之鎖固螺栓固定材料的強度更加提升的觀 點’鎖固螺栓固定材料的發泡倍率低者較佳。具體而言， 當將(A)成分與⑻成分於液溫2〇t混合時，發泡倍率宜為 3倍 本發明之鎖固螺栓固定材料，從抑制水質污染之觀 量， 耗量 於液溫2(TC的水中浸泡7曰後於水中含有的有機物 依照JISK〇1〇2(工業排水試驗法）剛定之過猛酸卸消 計算’以1 Omg/L以下較佳。 之氣溶膠組合物 所示配合比例配 以下’以實施例更詳細說明本發明 但本發明不限於此等實施例。 [實施例] 就（A)成分，藉由將下列原料以表 合，製備A— I〜A— IX。 11體成分41重量％ 固體成分40重量％ 固體成分38重量％ 矽酸鈉1 : Si〇2/Na2〇比2·2(莫耳比）、 矽酸鈉2 : Si〇2/Na2〇比2. 5(莫耳比）， 矽酸鈉3 : Si〇2/Na2〇比2. 9(莫耳比）、 胺多元醇：三乙醇胺 胺多元醇2: N —甲基二乙醇胺 多元醇1 :甘油 胺觸媒1 :三乙二胺 胺觸媒2:N，N，N’ 一三甲基胺基乙基乙 12 201105783 [表 1]— Α-Ι Α-ΙΙ A-III A-IV Α—V A—VI A-VII A-VIII A—IX 碎酸納1 98 矽酸鈉2 98 98 98.5 97.5 99 98 89 矽酸鈉3 98 胺多元醇1 1 1 1 0.5 1.5 胺多元醇2 1 多元醇1 1 10 胺觸媒1 0.7 0.75 0.8 0. 75 0. 75 0.75 0.75 0.75 0. 75 胺觸媒2 0.3 0.25 0.2 0.25 0.25 0.25 0. 25 0.25 0.25 黏度(mPa * S/2_i^r、 175 200 325 200 180 ~24〇1 155 200 375 分 ~ 良好 良好 良好 良好 良好 -良好 良好 不良 (黏度測定） 調整液溫為25乞，依照JIS K7301進行測定。結果如 表1所示。 (分散性） 於谷量200mL的聚多杯（polycup)，以表1所示組合， 計量溫度調整為2〇它的（〇成分15〇g，於混合器以 的旋轉速度進行1 0分鐘混合授拌並靜置5分鐘時，以目視 確卜觀f(A)成分為均勻者評為「良好」，觀察到成分 分離：不均句者評為「不良」。結果如表i所示。 :表1所示’當使用多元醇i(甘油)代替胺多元醇！ 、’判斷分散性為不良。 此配置201105783 V. If there is a chemical formula in this case, please reveal the best display of daily turnover _ : None. TECHNICAL FIELD OF THE INVENTION The present invention relates to a composition for locking a bolt fixing material and a locking bolt fixing material formed by hardening the composition. More specifically, it relates to a composition for a bolt-and-bolt material excellent in long-term durability which is used in a bolting method for protecting a tunnel structure, and a bolt fixing material formed by hardening the composition. [Prior Art _] In the excavation work of the mountain tunnel, in order to improve safety, the AGF construction method, the injection type first support curtain construction method, and the tunnel mirror front construction (face b〇lt) construction method are used for excavation. Two kinds of construction methods using various auxiliary construction methods and locking bolt construction methods such as tunnel deformation after digging and digging. The AGF construction method or the injection type first support curtain construction method is a construction method for ensuring the stability of the soil in the front upper portion in order to prevent the end portion from collapsing during the digging of the scent, and to ensure the safety from the digging to the laying of the concrete. By. In addition, the face bolt construction method is a construction method in which the mirror surface of the excavation section and the soil quality of the crucible are stabilized, and the period from the completion of the excavation to the start of the excavation is ensured. Security. These auxiliary construction methods are aimed at improving the safety of the excavation work. On the other hand, the construction method of the locking bolt is a construction method for ampouling the surrounding ground of the 201105783 after the tunnel has been dug. 'By fixing the bolt to the foundation with a fixing material' to protect the (four) structure from being subjected to subsequent addition and subtraction. The influence of site changes such as concrete and earthquakes. Therefore, the m-fixing material used to fix the locking bolt to the surrounding foundation requires the high-strength and long-term durability required to ensure the safety of the tunnel structure, and the above-mentioned excavation is used for foundation consolidation in various auxiliary construction methods. The materials are very different. In this way, (4) fixed bolts (4), in the past, inorganic materials such as mud with high strength were used. However, these inorganic materials # require a long period of time to exhibit strength', so the work efficiency is not sufficient, and when water leakage or pan water occurs, there is a problem that the material flows into the water. Therefore, in order to solve such problems, an organic-inorganic composite material composed of an aqueous alkaline citrate solution and an isocyanate compound is used as a fixing material. For example, Patent Document 1 discloses a composition for a fixing material by using a water glass component containing a basic aqueous solution of citrate, a tertiary amine catalyst, and glycerin, and an isocyanate component containing diphenyl decane monoisocyanate. , can harden and show strength in a short time. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2002-285155 SUMMARY OF INVENTION [Problems to be Solved by the Invention] However, these compositions for fixing materials have a water glass component and Isocyanide 4 201105783 Acid sputum; 7 is poorly miscible, and it is easy to obtain a hardened substance of a uniform sentence, so that cracks and the like have problems in long-term durability. Further, since the amount of glycerin is large, it is easy to leave unreacted glycerin in the cured product, which may cause water pollution due to elution into water. The present invention has been made in view of the above problems. The object of the invention is to provide a composition for locking a bolt fixing material and a locking bolt fixing material formed by hardening the composition, which can separate the aqueous solution of the acid salt, the aqueous solution of the cut acid salt and The isocyanate component is excellent in mutual solubility, and the organic compound is suppressed from being hard: soluble in material, suppressing environmental pollution (especially water pollution), and is excellent in long-term durability with high strength imparted to the cured product. [Means for Solving the Problem] The composition for a bolt-and-bolt fixing material of the present invention is placed in a peripheral foundation after tunneling, wherein the composition for a fixing material is composed of an aqueous solution containing bismuth citrate (A) a component and a component (B) containing an isocyanate compound, wherein the component (A) contains an aqueous solution selected from the group consisting of (A1) sodium citrate and (A2) selected from the group consisting of a trialkanolamine and an alkyldialkylolamine group. The above-mentioned (B) component contains a (Bi) isocyanate compound and (B2) an ester compound composed of an aliphatic alcohol having a carbon number of 8 to 12 and a polybasic acid. The component (A2) is preferably contained in the component (A) in % by weight. The component (B1) is preferably a mixture of a polyisocyanate compound (β11) and a polyether polyol (B12) containing 5 to 50% by weight of an oxyethylene unit. The polymer is preferred. Further, the lock bolt fixing material of the present invention is a lock bolt fixing material obtained by hardening a composition for a bolt fixing material. 201105783 The combination of the locking bolt fixing material, ., , and 々 is composed of a bismuth citrate aqueous solution (A) and a component (B) containing an isocyanated human σ, and is (a) 100 parts by weight. It is preferable to mix (3) to 120 parts by weight. [Effect of the Invention] The locking screw according to the present invention, the composition for the bolt fixing material and the locking bolt formed by the hardening of the composition, can inhibit the separation of the aqueous solution of the citrate, the aqueous solution of the acid salt and the different The bromocyanate component is excellent in mutual solubility, suppresses the elution of the organic compound from the hardened material, and suppresses environmental pollution (especially water pollution), and imparts high strength to the hardened material, and is excellent in long-term durability. [Embodiment] The composition for a bolt-and-bolt fixing material according to the present invention is a composition for a bolt fixing material placed on a peripheral ground after tunnel excavation, and is characterized in that the fixing material is used. The composition is composed of a component (a) containing an aqueous solution of citrate and a component (B) containing an isocyanate compound, and the component (A) contains (A1) an aqueous solution of sodium citrate and (A2) is selected from the group consisting of a trialkanolamine and The amine polyol of the group consisting of alkyl dialkanolamines and the component (B) contains the (B1) isocyanate compound and (B2) a compound composed of an aliphatic alcohol having a carbon number of 8 to 12 and a polybasic acid. The component (A) containing the aqueous citrate solution contains (A1) an aqueous solution of sodium citrate, and (A2) an amine polyol selected from the group consisting of trialkanolamines and alkyldialkylolamines. The sodium citrate aqueous solution (A1)' can be used as a main component using a water-soluble 6 201105783 liquid which is usually commercially available. This sodium sulphate is represented by the formula: Na2〇. xSi 〇2 . nH2〇. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 When X is less than 2, the ratio of the anhydrous citric acid gelation reaction in the foaming and hardening reaction is decreased, so that the hardenability at the time of mixing the two components is deteriorated, and if it exceeds 3, the viscosity of the sodium citrate aqueous solution is increased, so that it will be described later (B). The mixing property of the components and the workability at the time of use are lowered. The solid concentration of the aqueous sodium hydroxide solution (A1) is 35 to 50% by weight, preferably 40 to 45% by weight. When the solid content of the sodium citrate aqueous solution is too high, it can be diluted with water and adjusted. When the solid content concentration is less than 35% by weight, the water content is increased in the mixed liquid when the component (A) and the component (B) are mixed, and the mutual solubility of the two components tends to decrease, and if it exceeds 5 〇 by weight, (A) The viscosity of the component increases too much, and the mixing property with the component (B) and the workability at the time of use tend to decrease. The alcohol amine is, for example, triethanolamine, butanolamine, triisobutanolamine or the like. Among them, triethanolamine is preferred from the viewpoint of generality and economy. An alkyl dialkanolamine, for example, an alkyldiethanolamine compound such as methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine or isopropyldiethanolamine; methyldipropanolamine, ethyldipropanolamine, An alkyldipropanolamine compound such as propyldipropanolamine or isopropyldipropanolamine; methyldiisopropanolamine, ethyldiisopropanolamine, propyldiisopropanolamine, isopropyl An alkyl diisopropanolamine compound such as diisopropanolamine; a dibutylolamine such as methyl dibutanolamine, ethyl dibutanolamine, propyl dibutanolamine, or isopropyl: butanolamine Compounds, etc. Among them, the alkyldiethanolamine compound 201105783 is preferred from the viewpoint of excellent stability of the component (A). By the combination of (A2), the stability of the component (A), the oxidation of the isocyanate compound and water, and the inhibition of (B1) foaming and cracking, the sufficient strength of the cured product can be imparted. The amount of the compound (A2) is 〇. 0. 1~2· 0% by weight is more preferably in the component (A). When the amount of the hardened material (A2) is preferably 5% by weight, the stability of the component (A) is insufficient, and the hardening of the cured product due to carbon dioxide cannot be sufficiently suppressed. , cracks 'again, even if added more than 5. 〇% by weight will not pay more than 13⁄4 effect. In the lock bolt fixing material of the present invention, an amine catalyst (A3) can also be suitably blended. Amine catalysts such as: triethylenediamine, n,N,N,,N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropanediamine, N,N,N ,,N,tetramethyl hexamethylenediamine, hydrazine, hydrazine, hydrazine, N", N1, pentamethyldiethylenetriamine, hydrazine, hydrazine, hydrazine, Ν", Ν"-pentamethyl Dipropylenetriamine, hexamethyltriethylenetetramine, hexamethyltripropylenetetramine, hydrazine, hydrazine-dimethylcyclohexylamine, hydrazine, hydrazine-dimethylbenzylamine, hydrazine, hydrazine-dimethylamine Propylamine, tetradecylidene dipropylamine, hydrazine, hydrazine, hydrazine-tris(3-didecylaminopropyl)amine, hydrazine-methyl hydrazine, hydrazine-bis(3~dimethylamino) Propyl)amine, hydrazine-methyl-methyl, Ν-ethyl-flavored, Ν, Ν-dimercaptoethylamine, di- sulphonic acid diethyl ether, hydrazine, Ν'-dimethyl hydrazine, ν,Ν,,Ν, dimethylaminoethyl oxime, Ν-methyl 米 吐, 1,2-dimethyl ββ sitting, dimethylaminopropyl scent, 1 - different Butyl 2-methyl-salt saliva, bis(dimethylaminoethyl)ether, tris(dimethylaminomethyl)phenol, hydrazine, hydrazine, hydrazine, _ ginseng (3 - two Hydrazine, hydrazine-dimethylethanolamine, hydrazine, hydrazine-dimethylamino ethoxylate 201105783-based ethanol, N, N - dimethylaminohexanol, N, N, N, monotrimethylaminoethylethanolamine, N-fluorenyl-indenyl-monoethylidene, trimethyl-methylethyldiamine Ethyl ether, trimethylaminopropylethanolamine, bis-3-dimethylaminopropyl)isopropanolamine, tetradecyl-2-hydroxyethyldiethylenetriamine, etc. have one hydroxyl group in the molecule Amine compound. 0重量%优选。 Preferably, the amount of (A3) is adjusted as appropriate. The above (Β) component ' contains (Β1) an isocyanate compound and (Β2) an ester compound composed of an aliphatic alcohol having a carbon number of 8 to 12 and a polybasic acid. (Β1) Isocyanate compound 'for example, diphenyldecane diisocyanate and isomer thereof, polymethylene polyphenyl isocyanate (p〇lymeric MDI), carbodiimide denatured dimethane methane diisocyanate , toluene diisoxanthine, crude tolylene diisocyante, xylene diisocyanate, isophorone diisocyanate, cai diisocyanate, diphenylmethane diisocyanate, Separately or as a mixture of polyisocyanates such as tris-methylene xylene diisocyanate. Further, an isocyanate-terminated urethane prepolymer obtained by a known method can be used, whereby the (B1) isocyanate compound and the polyol compound are equivalent to the NC0 group and the hydrazine H group (NC0 group / 0H group). It is a range of 1. 5 to 300, preferably 2. 〇 to 1 。. Such polyol compounds, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butanol, 1,3-butanediol, 1,4-butanediol, u-hexane a glycol compound such as an alcohol; a triol compound such as glycerin or trimethylolpropane; a pentaerythritol sorbitol, other polyols such as sucrose, monoethanolamine, diethanolamine, 201105783 triethanolamine, and addition of oxyethylene to the same, A polyether polyol obtained by stretching an alkali oxide such as oxypropylene or oxybutylene. In the auditory device, from the viewpoint of drainage contamination when the mixed solution of sodium citrate (A1) is excellent in the contact with water before hardening, it is preferably a polyether polyol containing 5 to 50% by weight of the oxyethylene unit. . Among them, 'from the point of view of safety and hygiene and economy, ^gui is a very small volatility at the operating environment temperature'. The ignition point is 2 〇〇 μ % ^ υ u or more, liquid and economical composed of polymeric MDI, It is more preferred to use such an isocyanate-terminated urethane prepolymer cyanate-based terminal urethane prepolymer. The blending amount of (B1) is 5 Å to 95% by weight in the component (B). By allowing the isocyanate group in the (B1) isocyanate compound to react with water in the aqueous solution of the sodium authine to form a gland bond within the above range, sufficient strength can be imparted to the cured product. By blending (B-2 'It is possible to improve the mutual solubility of the component (A) and the component (8), and to suppress the carbon dioxide generated by the reaction of the (B1) isocyanate compound with water to cause the cured product to foam, and to impart sufficient strength to the cured product. The polybasic acid is, for example, a dibasic acid such as adipic acid, azelaic acid, sebacic acid or a dibasic acid such as phthalic acid, or a tribasic acid such as trimellitic coffee or a tetrabasic acid such as welmic acid. From the viewpoint of making the (8) component a lower viscosity, it is preferable to use a dibasic acid. x, from the viewpoint of environmental influence, more preferably adipic acid which can reduce water pollution. By making carbon of an aliphatic alcohol The number of organic compounds dissolved in water is 8~12', which can reduce the hardened alcohol soaked with aliphatic alcohols of 8~12, 10 201105783 isodecyl alcohol, - alcohol, ten, for example: octanol' sterol, isoindole Alcohol, sterol diol, etc. 1~50 0% by weight, 3 can make (B) component low viscosity The amount of the component (B2) is preferably 30% by weight or more, more preferably 30% by weight, and it can be imparted to the above range, and can impart good hardenability and strength. Next, the lock of the present invention will be described. The fixing screw fixing material of the present invention is a locking bolt fixing material obtained by hardening the lock (four) bolt@setting material composition. The composition for locking screw inspection fixing material, (1) component and The amount of the component (8) is preferably from 3 to 12 parts by weight based on 1 part by weight of the component (A). The part by weight is preferably from 50 to 90 parts by weight. If it is less than the above range, it is liable to be hardened. If the amount is more than the above range, the amount of carbon dioxide generated during hardening increases, so that the expansion ratio of the bolt fixing material is increased, and cracking of the bolt fixing material is easy, and it is difficult to obtain sufficient strength. When the component (A) and the component (B) are opened and mixed until the curing is performed, when the component (A) and the component (B) are mixed at a liquid temperature of 2 (TC), it is preferably 3 Torr to 18 sec. If it is shorter than the above range, it may not be fully filled to the front end of the locking bolt. 'If it is longer than the above range, work efficiency is likely to decrease. The locking bolt fixing material of the present invention is 50% measured in accordance with JIS K 7220 (Compression Test Method for Rigid Foamed Plastics) from the viewpoint of obtaining sufficient strength and durability. The compression strength is preferably 20 MPa or more, more preferably 3 MPa MPa or more. The locking bolt fixing material of the present invention is determined from the viewpoint of obtaining sufficient durability in accordance with JIS K7221 (Bending Test Method for Rigid Foamed Plastics) 11 201105783 The bending strength is preferably 5 MPa or more, more preferably 丨〇 MPa or more. 1 to 3 times 'more preferably 1 to 2 times, and the other is 7 Λ. The goods are preferably 1 to 1.5 times, 1 to 1. . The viewpoint of making the strength of the locking bolt fixing material of the present invention more improved is preferable in that the expansion ratio of the locking bolt fixing material is low. Specifically, when the component (A) and the component (8) are mixed at a liquid temperature of 2 〇t, the expansion ratio is preferably three times that of the locking bolt fixing material of the present invention, and the amount of the water is prevented from being contaminated. Temperature 2 (The organic matter contained in the water after soaking 7 times in water in TC is calculated according to JISK〇1〇2 (industrial drainage test method). The aerosol is not more than 1 Omg/L. The aerosol composition is preferred. The present invention is described in more detail by way of the following examples, but the invention is not limited to the examples. [Examples] For the component (A), A-1 to A were prepared by combining the following materials. — IX. 11 Body composition 41% by weight Solid content 40% by weight Solid content 38% by weight Sodium citrate 1 : Si〇2/Na2 〇 ratio 2·2 (Morby ratio), Sodium citrate 2 : Si〇2/Na2 〇 ratio 2.5 (Mo Erbi), sodium citrate 3 : Si〇 2 / Na 2 〇 ratio 2. 9 (mole ratio), amine polyol: triethanolamine amine polyol 2: N - methyl diethanolamine Alcohol 1: Glyceramine Catalyst 1: Triethylenediamine Amine Catalyst 2: N, N, N'-Trimethylaminoethylethyl 12 201105783 [Table 1] - Α-Ι Α-ΙΙ A-III A -IV Α-VA —VI A-VII A-VIII A—IX Sodium Hydrate 1 98 Sodium Citrate 2 98 98 98.5 97.5 99 98 89 Sodium Citrate 3 98 Amine Polyol 1 1 1 1 0.5 1.5 Amine Polyol 2 1 Polyol 1 1 10 Amine catalyst 1 0.7 0.75 0.8 0. 75 0. 75 0.75 0.75 0.75 0. 75 Amine catalyst 2 0.3 0.25 0.2 0.25 0.25 0.25 0. 25 0.25 0.25 Viscosity (mPa * S/2_i^r, 175 200 325 200 180 ~24〇1 155 200 375 minutes~ Good, good, good, good, good, good, good, poor (viscosity measurement) The liquid temperature was adjusted to 25 乞 and measured according to JIS K7301. The results are shown in Table 1. (Dispersibility) 200 mL in the valley Polycup, in the combination shown in Table 1, the metering temperature is adjusted to 2 〇 (the composition of 15 〇g, at the rotation speed of the mixer for 10 minutes mixed mixing and allowed to stand for 5 minutes) It was rated as "good" by visually observing that the component f(A) was uniform, and the separation of the components was observed: the uneven sentence was rated as "bad". The results are shown in Table i: Table 1 shows 'When used Polyol i (glycerol) instead of amine polyol!, 'Determining dispersibility is bad. This configuration
I 〜B— IX 成分，將下列原料以表2所示配合比例配合，藉 13 201105783 [表2] B-I ΡΡ-1*1 90 ΡΡ-2*2 ΡΡ-3<3 酉旨化合物1 10 酯化合物2 酯化合物3 PC DBA 黏度(mPa.S/2^ 200 燃點（°C) 204 B-II 90 10 III 90 10 B-IV B-V B-VI B-VII B-VIII Β-ΙΧ 95 80 90 90 90 90 5 20 10 10 10 10 280 125 180 225 150 165 203 206 204 204 173 185 · Γηη~~,1 ： 203 206 204 204 173 185 重1 量:1106、日本 咖公“)75 預以反應3小時，藉此得到異氰酸醋基末端胺甲酸乙醋 tmrit ： f°amHte NE 500 〇B ' BASF Inoac PolyurethaneI ~ B - IX ingredients, the following raw materials are blended in the proportion shown in Table 2, by 13 201105783 [Table 2] BI ΡΡ-1*1 90 ΡΡ-2*2 ΡΡ-3<3 化合物 化合物 1 1 1 ester compound 2 Ester compound 3 PC DBA Viscosity (mPa.S/2^ 200 Burning point (°C) 204 B-II 90 10 III 90 10 B-IV BV B-VI B-VII B-VIII Β-ΙΧ 95 80 90 90 90 90 5 20 10 10 10 10 280 125 180 225 150 165 203 206 204 204 173 185 · Γηη~~,1 : 203 206 204 204 173 185 Weight 1 Quantity: 1106, Japanese coffee ") 75 Pre-reaction for 3 hours, By this, an isocyanate-terminated urethane formic acid tmrit : f°amHte NE 500 〇B ' BASF Inoac Polyurethane
-3(NC0^* 26tf%)〇 籍制異驗®日基末端胺甲酸乙S旨預聚物PP 酯化合物1:己二酸二異壬酯 酯化合物2:己二酸二辛醋 酯化合物3:己二酸二異癸酯 PC :丙烯碳酸酯 DBA :己二酸二丁酯 (黏度測定） 據JIS K7301進行測定。結果 依 將液溫調整為25°C 如表2。 (燃點） 燃點，係依據Cleveland開放式測定。結果如表2。 燃點為20(TC以上者’係列為消防法危險物第4類第4石 油類’小於跳且7〇t以上者，係列為消防法危險物第 4類第3石油類。如表2所示，Β_νιπ及Β— ιχ中燃點 14 201105783 為2 0 0 °C以下，係低的，判斷可燃性高。 <實施例1〜12及比較例1〜5 > 於容量300mL的聚多杯（p〇lycup)，以表3及表4所示 纽合及配合比（重量比），計量溫度調整為201的（A)成分 及（B)成分，於混合器以50〇rpm的旋轉速度進行1〇秒混合 Π二使硬化’藉此得到鎖固螺栓固定材料。對於此時 的性狀進行以下評價。結果如表3。 15 201105783 A-II B - II 100/110 ㈡ A-II Β-Ιί 100/60 ί三一 10兵二 军 V: A-II B-VII 100/80 ί S " - ^ 2 苳 %: A-II B-VI 100/80 省2 jj[|gtr A-II B-V 100/80 實施例 9 A-II B—IV 100/80 實施例 8 A-II B—III 100/80 ί § 二·-= 實施例 7 A-II B-il 100/80 迄§ — CO写安 實施例 6 A-VI B—I 100/80 i S —卜 e S 實施例 5 A-V B—I 100/80 5 2 3 實施例 4 A—IV B-I 100/80 $二一CO马艺 實施例 3 A-III B-I 100/80 迄 § 二·。Μ 實施例 2 A-II B-I 100/80 迄g — CO爲安 實施例 1 A-I B-I 100/80 (A) 成分 (B) 成分 A/B配合比 (重量比） /—s Ss?lii ifllis 201105783 [表4] 比較例1 比較例2 比較例3 比較例4 比較例5 比較例6 比較例7 (Α)成分 A-VII A-VIII A-IX A-II A-II A-II A-II (Β)成分 B-I B一 I B— I Β—VIII B-IX B-II B-II Α/Β配合比 (重量比） 100/80 100/80 100/80 100/80 100/80 100/20 100/160 混合液之互溶性 不良 不良 不良 良好 良好 不良 良好 硬化時間（秒） 135 130 150 100 110 330 220 發泡倍率（倍） 1.8 1.7 3.5 4 2 1 7 有機物溶出量(mg/L) 3 12 55 35 45 26 2 壓縮強度(MPa) 8 9 2 3 10 0.2 0.5 彎曲強度(MPa) 3 4 1 2 4 0.1 0.3 (混合液之互溶性） 以目視確認將前述A液、B液以前述方法混合得到的 混合液，為均勻者評為「良好」，不均勻者評為「不良」。 (硬化時間） 以馬錶計測以前述方法混合的混合液反應硬化的時 間。 (發泡倍率） 測定以前述方法剛混合後的混合液的液面高度及硬化 後的鎖固螺栓固定材料的高度，並求取發泡倍率。 (有機物溶出量） 將以前述方法混合的混合液快速注入φ5χ1〇ειη的圓 柱狀模框内，於201氣體氛圍下靜置24小時後，從模框 取出，藉此製作受試體。將此受試體浸泡於1〇L的蒸餾水， 於20t靜置7日後，依據JIS κ〇1〇2(工業排水試驗法）， 將試樣水含有的有機物量以過錳酸鉀消耗量計算測定。 (壓縮強度） 依據JIS K 72.20(硬質發泡塑膠之壓縮試驗方法），測 17 201105783 定得到的鎖固螺栓固定材料的壓縮強度。 (彎曲強度） —依據HS K722K硬質發泡塑膠的彎曲試驗方法） 定得到的鎖固螺栓固定材料的彎曲強度。 ^ 如表3及表4所示，於不含胺多元醇的比較例卜（a) 成分與⑻成分的互溶性不佳，判斷無法得到均勾的鎖固螺 检固定材料。又’鎖固螺栓固定材料容易發泡，判斷得不 到充分的強度。使用甘油取代使用胺多元醇的比較例^ 中，（A)成分與（B)成分的互溶性不良，判斷無法得到均勻 的鎖固螺拴固定材料，鎖固螺栓固定材料容易發泡， 判斷無法得到充分的強度’而且判斷有機物溶出量升高。 比起比較例2，更大量使用甘油的比較例3，（A)成分與（b) 成分的互溶性不良，判斷無法得到均勻的鎖固螺栓固定材 料。又，比起比較例丨及2，鎖固螺栓固定材料容易發泡， 判斷無法得到充分的強度。又，判斷比起比較例丨及2， 有機物溶出量增多。使用丙烯碳酸酯取代本發明之酯化合 物1〜3的比較例4，比起比較例丨及2，鎖固螺栓固定材 料變得非常容易發泡，判斷無法得到充分強度。又，比起 比較例1及2，判斷有機物溶出量增多。比起本發明之酯 化合物1〜3 ’使用碳數較少的己二酸二丁酯的比較例5， 比起比較例1及2，鎖固螺栓固定材料更容易發泡，判斷 無法得到充分強度。又，比起比較例丨及2，判斷有機物 溶出量更增多。 18 201105783 【圖式簡單說明】 無。 【主要元件符號說明】-3(NC0^* 26tf%) 异 制 ® ® 日 日 日 日 日 日 日 PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP PP 3: Diisodecyl adipate PC: propylene carbonate DBA: dibutyl adipate (viscosity measurement) It was measured according to JIS K7301. Results The liquid temperature was adjusted to 25 ° C as shown in Table 2. (flame point) The ignition point is determined according to the Cleveland open type. The results are shown in Table 2. The ignition point is 20 (the above series of TC or above is the fourth class of the fire-fighting dangerous goods, the fourth type of petroleum class is less than the jump and 7 〇t or more, and the series is the fire-fighting dangerous goods category 4, the third petroleum class. As shown in Table 2 , Β_νιπ and Β - ιχ中燃点14 201105783 is below 200 °C, low, and high flammability is judged. <Examples 1 to 12 and Comparative Examples 1 to 5 > Polycapsules with a capacity of 300 mL ( P〇lycup), with the combination of the ratios (weight ratio) shown in Table 3 and Table 4, the (A) component and the (B) component whose measurement temperature was adjusted to 201, were carried out at a rotation speed of 50 rpm in the mixer. 1 〇 second mix Π 2 to harden ' thereby obtaining the locking bolt fixing material. The following evaluations were made for the trait at this time. The results are shown in Table 3. 15 201105783 A-II B - II 100/110 (2) A-II Β-Ιί 100/60 ί三一10兵二军V: A-II B-VII 100/80 ί S " - ^ 2 苳%: A-II B-VI 100/80 province 2 jj[|gtr A-II BV 100/80 Example 9 A-II B-IV 100/80 Example 8 A-II B-III 100/80 § II--= Example 7 A-II B-il 100/80 § —— CO writing Embodiment 6 A-VI B-I 100/80 i S —Bu e S Example 5 AV B-I 100/80 5 2 3 Example 4 A-IV BI 100/80 $二一CO马艺例3 A-III BI 100/80 § § II. 实施 Example 2 A- II BI 100/80 up to g — CO is an example 1 AI BI 100/80 (A) Ingredient (B) Component A/B mix ratio (weight ratio) /—s S??lii ifllis 201105783 [Table 4] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 (Α) Component A-VII A-VIII A-IX A-II A-II A-II A-II (Β) Component BI B IB—I Β—VIII B-IX B-II B-II Α/Β mix ratio (weight ratio) 100/80 100/80 100/80 100/80 100/80 100/20 100/160 mixed liquid Poorly soluble, poor, good, good, poor, good hardening time (seconds) 135 130 150 100 110 330 220 Expansion ratio (times) 1.8 1.7 3.5 4 2 1 7 Organic matter dissolution (mg/L) 3 12 55 35 45 26 2 Compressive strength (MPa) 8 9 2 3 10 0.2 0.5 Bending strength (MPa) 3 4 1 2 4 0.1 0.3 (Mixed liquid mutual solubility) The mixed liquid obtained by mixing the above-mentioned liquid A and liquid B by the above method was visually confirmed to be uniform. Ranked as "good" and uneven as " Good. " (Curing time) The time at which the mixed liquid mixed by the above method was reacted and hardened was measured by a horse watch. (Foaming ratio) The liquid level of the mixed liquid immediately after the mixing by the above method and the height of the fixing bolt fixing material after the curing were measured, and the expansion ratio was determined. (Organic substance elution amount) The mixed liquid mixed by the above method was quickly injected into a cylindrical mold frame of φ5χ1〇ειη, and allowed to stand in a gas atmosphere of 201 for 24 hours, and then taken out from the mold frame to prepare a test piece. The test object was immersed in 1 〇L of distilled water, and after standing for 7 days at 20 t, the amount of organic matter contained in the sample water was calculated as potassium permanganate consumption according to JIS κ〇1〇2 (industrial drainage test method). Determination. (Compression Strength) According to JIS K 72.20 (Compression Test Method for Rigid Foamed Plastics), the compressive strength of the locking bolt fixing material determined by 17 201105783 was measured. (Bending strength)—The bending strength of the locking bolt fixing material determined according to the bending test method of HS K722K rigid foamed plastic. ^ As shown in Tables 3 and 4, in the comparative example containing no amine polyol, the mutual solubility of component (a) and component (8) was poor, and it was judged that the hooking screw fixing material was not obtained. Further, the locking bolt fixing material is easily foamed, and it is judged that sufficient strength is not obtained. In the comparative example using glycerin instead of the amine polyol, the miscibility of the component (A) and the component (B) is poor, and it is judged that a uniform locking screw fixing material cannot be obtained, and the locking bolt fixing material is easily foamed, and it is judged that it is impossible to determine A sufficient strength is obtained and the amount of organic matter eluted is judged to increase. In Comparative Example 3 in which glycerin was used in a larger amount than in Comparative Example 2, the mutual solubility of the component (A) and the component (b) was poor, and it was judged that a uniform anchor bolt fixing material could not be obtained. Further, the locking bolt fixing material was easily foamed compared to the comparative examples 2 and 2, and it was judged that sufficient strength could not be obtained. Further, it was judged that the amount of organic matter eluted was larger than that of Comparative Examples 2 and 2. In Comparative Example 4 in which the propylene carbonate was used in place of the ester compounds 1 to 3 of the present invention, the anchor bolt fixing material was very easily foamed compared to Comparative Examples 2 and 2, and it was judged that sufficient strength could not be obtained. Further, compared with Comparative Examples 1 and 2, it was judged that the amount of eluted organic matter increased. Compared with Comparative Example 5 in which the ester compound 1 to 3' of the present invention used a small amount of dibutyl adipate, the locking bolt fixing material was more likely to be foamed than the comparative examples 1 and 2, and the judgment was not sufficiently obtained. strength. Further, it was judged that the amount of organic matter eluted was more increased than in Comparative Examples 2 and 2. 18 201105783 [Simple description of the schema] None. [Main component symbol description]