200415170 (1) 玖、發明說明 【發明所屬之技術領域】 本發明有關聚酯多醇。詳言之，有關聚胺基甲酸乙酯 ，特別是，使用爲硬質聚胺基甲酸乙酯泡體時，能呈現與 發泡劑優異的相溶性，且黏度低而操作處理容易@ _自乡 醇0 【先前技術】 由於硬質聚胺基甲酸乙酯泡體具有優異的絕熱特性之 故，廣泛用爲一般建造物之絕熱材料等。硬莺聚胺基甲酸 乙酯泡體一般係依製備聚異氰酸酯成分液（以下，簡稱爲 A液）、及混合有聚醚多醇及/或聚酯多醇、發泡劑、以 及需要時之觸媒或整泡劑等的混合液（以下，簡稱爲B液 )，並將A液與B液混合以使在短時間進行發泡、固化 的方法所製造者。因此，聚酯多醇亦必須具備與發泡劑的 相溶性佳之同時，黏度低且操作處理容易的性質。 發泡劑而言，一般使用低沸點無極性有機溶劑，亦即 具體上除HCFC系發泡劑之外，尙可使用戊烷、環戊烷等 飽和烴系溶劑。又，視用途或硬質聚胺基甲酸乙酯泡體之 製造條件，如使用引火點低，具有曝發性的飽和烴系溶劑 時則有實用上之問題，故多採用HCFC (氫氯氟代烴）系 發泡劑。 另一方面，臭氧層之破壞成爲問題以來’從以往普遍 所採用的CFC (氯氟代烴）系發泡劑，特別是CFC-1 1E等 -5- (2) (2)200415170 ’改用爲臭氧破壞係數小的hcfc發泡劑，特別是目前之 HCFC]41b。然而，此種HCFC-141b亦並非臭氧破壞係數 零者’故預定在2003年末以後將被限制使用。HCFC-14 1b之替代品而言，可能選定HFC (氫氟代烴）系發泡 劑，特別是 HFC-245fa、HFC-365mfc。 使用目前以及將來可能選定的發泡劑所存在的共通問 題而言’可例舉：作爲B液之主成分之由聚醚多醇及/或 聚酯多醇而成的多醇成分與此等發泡劑的相溶性不佳的事 實。特別是，與可能被選定爲HCFC系發泡劑之替代品的 HFC-245fa、HFC-365 fc等之HFC系發泡劑的相溶性不佳 ，將成爲今後多大問題。 又，爲謀求B液之均一安定化起見，一般作爲整泡劑 而廣泛採用添加表面活性劑之方式，特別是添加非離子系 表面活性劑的作法，惟其效果不能謂足夠。又，近年來逐 漸有種種關於具有能改善相溶性的某種表面活性效果的相 溶化劑的提案。然而，此等相溶化劑通常幾乎全部爲不具 有羥基的化合物。因而，即使作爲B液之補助成分而對與 上述之發泡劑的相溶性改善有助益，由於不參與胺基甲酸 乙酯反應之故，照原來形態存在於硬質聚胺基甲酸乙酯泡 體中，以致可能顯著惡化其物性，特別是強度或耐熱性等 〇 因而，爲解決發泡劑與B液的相溶性不佳的問題時， 必須爲能提升相溶性之同時，亦能作爲在分子的具有羥基 的多元醇發揮功能的化合物，在實用上可能係很重要的條 -6 - (3) (3)200415170 件。 聚酯多醇，特別是芳香族聚酯多醇，常以提升所得硬 質聚胺基甲酸乙酯泡體之耐熱性等爲目的，而與聚醚多醇 倂用。然而，芳香族聚酯多醇，一般由於黏度高之故，引 起操作處理困難，或與發泡劑的相溶性不佳，以致難於在 滿足發泡劑與B液的相溶性的範圍內對B液中調配所需 量，而存在有種種實用上的問題。 另一方面，爲提升包括相溶性在內之聚酯多醇之物性 起見’選擇二元醇、三元醇等原料之醇亦屬有效，特別是 ’爲提升相溶性時，如將醇之全量或一部分作成1,2-丁二 醇（以下，簡稱爲1，2-BG)。然而，即使使用1,2-BG時 ，所得聚酯多醇之低黏度化方面有其限度，而在通常普遍 所用的羥基値在250 ( mgKOH/g )附近之聚酯多醇而言， 則難於合成2萬mPa*S(25°C)以下之黏度者。此乃表 示對B液之調整時並不符合需求。 因而，如存在有能與發泡劑的相溶性良好，且黏度低 的新穎的聚酯多醇，則作爲多元醇成分之一部分而適當量 使用時即可得均勻安定性良好的B液，進一步能提升B 液之各成分之調配比例之自由度，結果可製得具有優異的 物性的硬質聚胺基甲酸乙酯泡體。 【發明內容】 發明揭示 本發明人等，爲解決此種課題而專心硏究之結果發現 -7- (4) (4)200415170 ’如作爲聚酯多醇之製造原料的醇，使用特定量含有選自 卜經基-2-乙醯氧丁烷（以下，簡稱，ι，2-ΗΑΒ)及乙醯 氧基-2-羥基丁烷（以下，簡稱i，2-Ahb)及1,2-二乙醯氧 丁院（以下’簡稱1，2-DAB )而成的群中之至少1種的混 合物即可製得與發泡體的相溶性良好，且低黏度之聚酯多 醇之事實，而完成本發明。所得聚酯多醇，由於與在來普 遍所使用的聚酯多醇同樣，作爲聚胺基甲酸乙酯之一構成 成分而被吸收於聚胺基甲酸乙酯之分子內之故，不致影響 聚胺基甲酸乙酯之物性之下，可發揮如上述之特性。 亦即，本發明，係具有如下述特徵之要旨者。 (1) 一種聚酯多醇，係使多元羧酸及醇進行酯化反 應而得的聚酯多醇，其特徵爲：作爲醇而使用含有選自1-羥基-2-乙醯氧丁烷、1-乙醯氧基-2-羥基丁烷以及1，2·二 乙醯氧丁烷而成的群中之至少1種2至40重量％者。 (2 ) —種聚酯多醇，係醇爲含有1，2-丁二醇，與選 自1-羥基-2·乙醯氧丁烷、1-乙醯氧基-2-羥基丁烷以及 1，2-二乙醯氧丁烷而成的群中之至少1種的混合物，其特 徵爲：該混合物之1,2-丁二醇之含量爲60至98重量％。 (3 )如上述（2 )所記載之聚酯多醇，其中混合物係 在分子狀氧氣及鈀系觸媒之存在下使1，3-丁二烯與乙酸進 行乙醯氧反應，將所得二乙醯氧丁烯類及一乙醯氧丁烯等 之反應生成物在貴金屬存在下進行如氫，接著將所得二乙 醯氧丁烷類及一乙醯氧丁烷類等之反應生成物在固態酸觸 媒之存在下進行加水分解，餾除乙酸及水後依蒸餾加以分 -8- (5) (5)200415170 離而製得者。 (4) 一種聚胺基甲酸乙酯，其特徵爲：使含有上述 (1 )至（3 )中之任一項所記載之聚酯多醇的多元醇與異 氰酸酯化合物進行反應而成者。 (5) —種硬質聚胺基甲酸乙酯泡體，係使用上述（4 )所記載之聚胺基甲酸乙酯而成者。 (6) 如上述（5)所記載之硬質聚胺基甲酸乙酯泡體 ’其中再含有臭氧破壞係數爲0.8以下之發泡劑而成者。 (7) 如上述（6)所記載之硬質聚胺基甲酸乙酯泡體 ，其中發泡劑係HFC-245fa及/或HFC-365mfc。 發明之效果 如採用本發明，則可提供聚胺基甲酸乙酯，特別是， 作爲硬質聚胺基甲酸乙酯之原料多元醇，低黏度且操作處 理容易之同時，與發泡劑，特別是HFC-245fa及/或HFC-3 65 mfc等之HFC發泡劑的相溶性良好的聚酯多醇。 實施本發明之最佳形態 就本發明，加以詳細說明如下。 本發明之聚酯多醇，較佳爲聚胺基甲酸乙酯，特別是 爲硬質聚胺基甲酸乙酯泡體所使用的聚酯多醇，而係由多 元羧酸與醇所製得的·聚酯多醇。 (多元羧酸） -9- (6) (6)200415170 本發明之多元羧酸而言，可例舉：二或三羧酸。較佳 爲可舉：鄰苯二甲酸、異苯二甲酸、對苯二甲酸、偏苯三 甲酸等之芳香族二或三羧酸以及此等之酸酐。此等之中， 特佳爲可舉：苯二甲酸、苯二甲酸酐或對苯二甲酸。 又，此等芳香族羧酸類亦可使用甲醇、乙醇、2 -乙基 己醇等碳數1至8之單醇而被酯化者，例如二甲基對苯二 甲酸等。 再者，亦可將琥珀酸、馬來酸、己二酸等之脂肪族二 羧酸混合於芳香族羧酸類，或視情況，亦可單獨使用。 (醇） 含有選自1，2·ΗΑΒ、1，2-AHB以及1，2-DAB而成的群 中之至少1種的醇 本發明中作爲起始原料而使用的醇係含有選自1，2-HAB、1，2-AHB以及1，2-DAB而成的群中之至少1種2至 40重量％者。 選自1,2-ΗΑΒ、1，2·ΑΗΒ以及1，2-D ΑΒ而成的群中之 至少1種之含量較佳爲5重量％以上、更佳爲10重量％以 上而較佳爲35重量以下、更佳爲30重量％以下。如此量 過少時，則幾乎不能呈現降低聚酯多醇之黏度的效果。另 一方面，如此量過多時，則在合成聚酯多醇時，所生成的 聚酯多醇中之羥基將顯著減少，有時視與所用的多元羧酸 的使用比例，會生成完全不存在羥基的化合物，亦即，僅 能製得非多醇者。如使用有此種傾向的範圍之比例所製得 •10- (7) (7)200415170 的聚酯多醇，則對後續之與聚異氰酸酯進行胺基甲酸乙酯 化反應所得硬質聚胺基甲酸乙酯泡體之強度或耐熱性等性 能有顯著的不良影響的可能。 又，1,2-HAB、1，2-AHB 以及 1，2 - D A B 之中，1，2 - D A B 之量係對此3種合計量’係通常爲1重量％以上、較佳爲 5重量％以上、更佳爲1〇重量以上而通常爲50重量以下 、較佳爲33重量％以下、更佳爲25重量％以下。 作爲此種醇，更具體而言，使用含有1，2-BG、與選自 1,2-HAB、1,2-AHB以及1，2 - D A B而成的群中之至少丨種 的混合物，而該混合物中之1，2-BG之含量，而該混合物 中之1，2-BG之含量通常較佳爲60至98重量％的混合物。 此混合物，係在分子狀氧氣及鈀系觸媒之存在下主要使 1，3-丁二烯與乙酸進乙醯氧反應，將所得二乙醯氧丁烯類 及一乙醯氧丁烯等之反應生成物在貴金屬觸媒之存在下進 fr加氫’接者將所得一乙醯氧丁院類及一乙醯氧丁院類等 之反應生成物在固態酸觸媒之存在下進行加水分解，館除 乙酸及水後依蒸餾加以分離而製得者。亦即，在使丨，3_丁 二烯與乙酸進行反應以製造1,4 -丁二醇時可作爲同時生成 的副生成物而製得。 本發明所使用的鈀系觸媒而言，可將鈀金屬或其鹽以 單獨或者作爲助觸媒而與鉍、硒、銻、締、銅等之金屬或 其鹽組合使用。觸媒較佳爲使氧化砂、氧化銘、活性碳等 之載體載持而使用。 含有 1，2-BG、與選自 1，2-ΑΗΒ、1，2·ΑΗΒ 以及 1，2· -11 - (8) (8)200415170 DAB而成的群中之至少1種的混合物中，通常較佳爲含有 1,2-BG 60重量％以上、98重量％以下。如HBG之含量 過少，則在合成聚酯多醇時，所得聚酯多醇中之羥基將顯 著減少’甚至視與所使用的多元殘酸的使用比例，有完全 不存在羥基的化合物，亦即僅能製得非多醇者的情形。如 使用有此種傾向的範圍所製得的聚酯多醇，則可能對由此 再與聚異氰酸酯進行胺基甲酸乙酯化反應所製得的硬質聚 胺基甲酸乙酯泡體之強度或耐熱性等之性能有非常不良影 響。另一方面，如過多時，則幾乎不能獲得降低聚酯多醇 之黏度的效果。 因而，1,2-BG之含量，係對混合物之總重量較佳爲 65重量％以上、更佳爲70重量％以上，而較佳爲95重量 %以下、更佳爲90重量％以下之範圍。 混合物中，除1，2-BG、與選自1，2-HAB、1，2-AHB以 及1，2-DAB而成的群中之至少1種以外，尙可微量含有乙 酸、水、1，4-丁二醇、1,4-丁二醇之乙酸酯等。 通常，混合物中較佳爲含有選自1,2-HAB、1，2-AHB 以及1，2-DAB而成的群中之至少1種2重量％以上、40重 量％以下。如選自1，2-HAB、1，2-AHB以及1,2-DAB而成 的群中之至少1種之含量過多時，則合成聚酯多醇時，所 得聚酯多醇中之羥基將顯著減少，甚至視與所使用的多元 羧酸的使用比例，有完全不存在羥基的化合物’亦即僅能 製得非多醇者的情形。如使用有此種傾向的範圍所製得的 聚酯多醇，則可能對由此再與聚異氰酸酯進行聚胺基甲酸 -12- (9) 200415170 乙酯化反應所製得的硬質聚胺基甲酸乙酯泡體之強 熱性等之性能有非常不良影響。另一方面，如過少 幾乎不能獲得降低聚酯多醇之黏度的效果。 因而，選自 1，2-HAB、1，2-AHB 以及 1，2-DAB 群中之至少1種之含量，係對混合物之總重量較佳 量％以上、更佳爲10重量％以上，而較佳爲35重量 、更佳爲30重量％以下之範圍。 (其他醇） 本發明之醇而言，除上述混合物以外，亦尙可 他醇。通常，可倂用的其他醇而言，可例舉：乙二 乙醇、三乙二醇、丙二醇、二丙二醇、三丙二醇、 二醇、1，3-丁 二醇、1,4-丁 二醇、1,5-戊二醇、1,6-、新戊二醇、環己二醇、環己二甲醇等之二元醇以 •，三羥甲基丙烷等之三元醇等。 再者，亦可使用聚乙二醇、聚丙二醇、聚氧^ 丙烯共聚合甘醇以及聚四伸甲基醚二醇等之長鏈聚 〇 倂用此種醇時，如上述混合物之使用量係對原 全量過少時，則不能獲得對發泡劑的相溶性之提昇 度化之顯著效果。亦即，上述混合物之使用量係對 醇全量通常爲40重量％以上、較佳爲50重量％以 ’視聚酯多醇所要求的低黏度化及/或相溶性之特 之黏度，亦可爲前述範圍以下。 度或耐 時，則 而成的 爲5重 %以下 倂用其 醇、二 1，2 - 丁 己二醇 及甘油 V烯/氧 醚多醇 料之醇 及低黏 原料之 上。但 性平衡 •13- (10) (10)200415170 又，降低聚酯多醇之黏度的方法而言，亦可使用甲醇 、乙醇、異丙醇、2-乙基己醇等之一元醇，惟有時在聚酯 多醇之合成時餾出反應系外而使收率惡化，或對聚胺基甲 酸乙酯之強度或耐熱性有不良影響。 (酯化觸媒） 本發明之酯化反應中，通常使用酯化觸媒。觸媒而言 ，通常使用酸觸媒。路易斯酸（Lewis acid )而言，例如 可使用四異丙基鈦酸酯、四正丁基鈦酸酯等之鄰鈦酸酯、 或二乙基錫氧化物、二丁基錫氧化物等之錫系化合物，或 氧化鋅等之金屬化合物。 又，路易斯酸之外，尙可使用對甲苯磺酸等之布朗斯 台德酸（Brensted acid)。 另一方面，所得聚酯多醇將與聚異氰酸酯進行胺基甲 酸乙酯化反應而成爲聚胺基甲酸乙酯，惟此時聚酯多醇之 合成所使用的觸媒，不會影響胺基甲酸乙酯化反應之反應 動態上無不良影響較合適。上述之酯化觸媒之中，較佳爲 原鈦酸酯，使用量亦對原料所使用的多元羧酸與醇之合計 ，通常爲1.0重量％以下，較佳爲0.2重量％以下，而通常 爲0.01重量％以上、較佳爲0.03重量％以上。 視聚胺基甲酸乙酯之用途，亦可不使用此等酯化觸媒 之下進行反應。 (反應條件） 14- (11) (11)200415170 本發明之聚酯多醇，可由多元羧酸與醇中通常添加上 述酯化觸媒，並進行酯化反應而製得。 多元羧酸與醇所使用的比例而言，雖然視作爲目標的 聚酯多醇之羥基値或黏度等而異，惟對多元羧酸之羧基i 當量的醇之羥基之當量計，通常爲1·1當量以上、較佳爲 1.3當量以上，更佳爲1.5當量以上，而通常爲4.0當量以 下、較佳爲3.0當量以下、更佳爲2.7當量以下。特別是 ，對醇使用本發明之混合物4 0重量％以上時，如此値過 小時，則所得聚酯多醇中之羥基將顯著減少，視混合物中 之1，2·ΗΑΒ、1,2·ΑΗΒ以及1，2-DAB之含量，有完全不存 在羥基的化合物，亦即僅能製得非多醇者的情形。如使用 有此種傾向的範圍所製得的聚酯多醇，則可能對由此再與 聚異氰酸酯進行胺基甲酸乙酯反應所製得的硬質聚胺基甲 酸乙酯泡體之強度或耐熱性等之性能有非常不良影響。另 一方面，如此値過大時，則在聚酯多醇中未能供與酯化反 應之游離之醇會多量殘留。如使用如此所得聚酯多醇時， 則可能對由此再與聚異氰酸酯進行胺基甲酸乙酯化反應所 製得的硬質聚胺基甲酸乙酯泡體之強度或耐熱性等之性能 ，亦有非常不良影響。在此，如作爲醇而使用本發明之混 合物時，1，2-HAB等之一元酯類係各換算爲以羥基計爲1 當量、1，2-DAB係以羥基計爲〇當量，以推算混合物之羥 基當量。 反應溫度在通常爲15(TC以上、較佳爲180°C以上， 而通常爲250 °C以下、較佳爲230°C以下之範圍進行。例 -15- (12) (12)200415170 如，如係於18(TC開始反應，隨著反應之進行而徐徐升溫 至20(TC的條件，則容易控制反應。 反應壓力可爲常壓，惟爲所副生的水及微量之乙酸去 除系外，以儘速完成反應起見，較佳爲隨著反應之進行而 徐徐加以減壓。惟如反應時之減壓度不足時，則酯化反應 之完成度不足，以致生成酸値高的聚酯多醇。另一方面， 如反應時過度減壓時，則不僅1，2-BG、1，2-HAB、1，2-AHB 等之醇成份將被餾除於系外而損及收率，甚至在極端的情 形，供於酯化反應的1,2-HAB或1,2_AHB等的乙醯基將再 因酯交換反應而引起脫乙酸，結果會形成高分子量之聚酯 多醇。此等現象不僅會顯著上升所得聚酯多醇之黏度，尙 會顯現降低對發泡劑的相溶性的傾向的情形。因而，雖然 適當的到達反應壓力，係視反應溫度而異，惟反應溫度在 200°C時，壓力通常爲20kPa以上，較佳爲30kPa以上， 而通常爲60kPa以下，較佳爲50kPa以下。但，視作爲目 標的聚酯多醇之黏度或羥基値、所用的混合物之使用量、 混合物中之選自1，2-HAB、1，2-AHB以及l，2-DAB而成的 群中之至少1種之含量，亦可依上述之壓力範圍以外之條 件進行反應。 又，亦可不加以減壓，而少量倂用甲苯、二甲苯等之 有機溶劑’並使所副生的水及微量之乙酸共沸以去除於系 外。 反應之終點，在聚酯多醇之情形，通常係按所用的多 元羧之未反應之羧基之量加以決定。另一方面，在聚胺基 -16- (13) 200415170 甲酸乙酯之用途上，對與聚異氰酸酯的胺基甲酸乙酯 應，酸之存在係會降低反應性等不合適情況較多。因 就聚酯多醇而言，亦較佳爲未反應之羧酸之量，亦即 儘量低者。在硬質聚胺基甲酸乙酯泡體之用途上，酸 常爲10mgK〇H/g以下、較佳爲5 mgK〇H/g以下、更 3 mg ΚΟΗ/g以下。又，在更嚴格的胺基甲酸乙酯化反 件下，有時需要爲1 mgK〇H/g以下。 如上述方式所得聚酯多醇，通常係由具有由所用 元羧酸與醇而成的構造的酯化合物及未反應之醇而成 發明中所得聚酯多醇中，上述酯化合物之平均官能基 在僅以含有1，2-BG、與選自1，2-ΗΑΒ、1，2·ΑΗΒ以及 DAB而成的群中的至少1種和2元之多元羧酸所合成 形，通常爲0 · 8以上、較佳爲1 · 1以上、更佳爲i. 5 。如酯化合物之平均官能基數過低時，則將使由此再 異氰酸酯進行胺基甲酸乙酯化反應所得的聚胺基甲酸 之聚合度降低，例如，在硬質聚胺基甲酸乙酯泡體之 ，有特別使強度或耐熱性顯著惡化的情形。 又，爲將酯化合物之平均官能基數保持爲一定之 値及/或將平均分子量保持爲一定以下時，需要儘量 在酯化反應中隨著酯交換反應而成爲平衡狀態的1，2 、1，2-AHB以及1，2-DAB之乙酸酯之乙酸餾出反應系 如乙酸之餾出過多時，則酯化合物之平均官能基數將 初之製品設計成爲不相同者，或平均分子量增大而其 所得聚酯多醇之黏度變成非常大之故不合適。因而， 化反 而， 酸値 値通 佳爲 應條 的多 。本 數， 1,2- 的情 以上 與聚 乙酯 情形 目標 不使 -HAB 外。 對當 結果 在酯 -17- (14) (14)200415170 化反應中餾出系外的乙酸之量，係對1,2-HAB、i,2-AHB 以及1，2-DAB所結合的乙酸之量，通常爲30%以下、較佳 爲20%以下、更佳爲10%以下。但，視作爲目標的聚酯多 醇之黏度或羥基値，所用混合物之使用量、混合物中之 1，2-HAB、1，2-AHB以及1，2·DAB之含量，亦可超出上述 範圍而餾出乙酸。 另外，在反應開始時，較佳爲防止所生成的聚酯多醇 之著色而將反應容器之容間部加以氮氣取代，並進一步去 除反應液中之溶存氧氣。 又，反應終了之後，亦可在適當的減壓條件下，使未 反應之游離之醇餾出系外，以調節聚酯多醇之物性或性能 (反應形式） 本發明中之聚酯多醇之反應形式，可適用通常之批式 設備或連續式設備，惟由於反應時間需要長時間、以及所 得聚酯多醇之黏度較用爲原料的醇之黏度爲高很多等之故 ，較佳爲採用批式反應者。 (用途） 由本發明所得聚酯多醇，係很適合用爲使多醇與異氰 酸酯化合物進行反應所得聚胺基甲酸乙酯，特別是硬質聚 胺基甲酸乙酯泡體，除低黏度且操作處理容易以外，尙可 作爲臭氧破壞係數在〇· 8以下之發泡劑，特別是與今後將 -18- (15) (15)200415170 採用的HFC-245fa及/或HFC- 3 6 5 mfc等之發泡劑的相溶性 高的聚酯多醇有用者。 硬質聚胺基甲酸乙酯泡體，係可依將由聚異氰酸酯成 分而成的 A液，與混合由聚醚多醇及/或聚酯多醇等而成 的多醇成分、發泡劑、觸媒以及整泡劑，再視需要的其他 添加劑、助劑而成的B液，在短時間的進行混合、發泡、 固化的方法製造。 聚異氰酸酯成分而言，衹要是在1分子中具有2個異 氰酸酯基的有機化合物，則並不特別限定。可例舉：脂肪 族系、脂環族系以及芳香族系聚異氰酸酯或此等之改性物 。具體的脂肪族系及脂環族系聚異氰酸酯而言，可例舉： 六伸甲嫌二異氰酸酯、異佛爾酮（isophorone)二異氰酸 酯等。芳香族系聚異氰酸酯而言，可例舉：甲伸苯基二異 氰酸酯、二苯基甲烷二異氰酸酯以及聚伸苯基聚伸甲基聚 異氰酸酯等，再可包含此等之碳化二亞胺改性物或預聚合 物等之改性物。 本發明之較佳聚異氰酸酯，係芳香族聚異氰酸酯或其 改性物，特佳爲二苯基甲烷二異氰酸酯、聚伸苯基聚伸甲 基聚異氰酸酯、甲伸苯基二異氰酸酯以及此等之改性物， 而可以單獨或混合此等使用。 聚伸苯基聚伸甲基聚異氰酸酯而言，可使用NCO基 含有率通常爲29至32重量％、黏度通常爲250mPa· S( 2 5 °C )以下者。 又，此等改性物之中，羧醯二亞胺改性物，係使用周 -19- (16) (16)200415170 知之磷系觸媒以導入羧醯二亞胺鍵者。預聚合物，係使上 述之聚異氰酸酯與多醇進行反應，在末端殘留異氰酸酯基 者。此時所用的多醇，通常可使用製造聚胺基甲酸乙酯所 使用的多醇。 又’除此等聚異氰酸酯之外，有時視需要將添加劑、 助劑混合於聚異氰酸酯成分中使用。 例如，以改善與B液的混合性爲目的，有時將B液 中亦可用的整泡劑作爲相溶化劑倂用。此時，通常較佳爲 非離子系表面活性劑，特別是矽酮系表面活性劑較常用。 又，以改善難燃性及黏度之調整爲目的，有時倂用難 燃劑。在硬質聚胺基甲酸乙酯泡體之用途而言，通常，氯 烷基磷酸酯類，例如，參（α-氯代乙基）磷酸酯或參（ 氯代丙基）磷酸酯等較常用。 上述以外之添加劑、助劑而言，並不特別限定，衹要 是在通常之樹脂中以改善物性或改善操作性等之目的所使 用，而對胺基甲酸乙酯化反應無顯著惡影響者，則可使用 任一種。 多醇成分而言，可使用羥基値通常爲200至800、官 能基數通常爲2至8之聚醚多醇或聚酯多醇等，亦可將此 等混合2種以上使用。聚醚多醇而言，可例舉：環氧乙烷 、環氧丙烷、1，2-環氧丁烷以及四氫呋喃等之單獨或倂用 所得的烯化氧（alkylene oxide)之聚合物、蔗糖或山梨 糖醇及甘油等之3官能以上之多元醇類與上述烯化氧之附 加物、脂肪族胺及芳香族胺與上述烯化氧之附加物等。 -20- (17) (17)200415170 聚酯多醇而言，可使用將前述之本發明之多元羧酸與 醇進行酯化反應所得者，而較佳爲全多醇成分中在通常爲 2重量％以上、較佳爲5重量％以上、更佳爲1 〇重量％以 上，通常爲50重量％以下、較佳爲30重量％以下、更佳 爲20重量％以下之範圍使用。 又，除本發明之聚酯多醇以外，常用的聚酯多醇而言 ，可例舉：將作爲多元羧酸的鄰苯二甲酸酐、以及對苯二 甲酸及偏苯三甲酸等之芳香族二或三羧酸、與乙二醇、二 乙二醇、丙二醇、二丙二醇等及甘油、三羥甲基丙烷等之 2至3元之甘醇單獨或混合並進行酯化反應所得之羥基値 在通常爲200至400、平均官能基數在通常爲2至3程度 之聚酯多醇。 又，此外，乙二醇、二乙二醇、丙二醇以及甘油等之 醇或二乙醇胺、三乙醇胺等之烷醇胺等，在1分子中具有 活性氫2個以上的化合物亦可倂用。 發泡劑而言，除臭氧破壞係數在通常爲〇 . 8以下之發 泡劑，例如，HCFC-141b、環戊烷及正戊烷等之外，由於 特別是與今後將採用的 HFC-245 fa、HFC- 3 6 5 mfc等之發 泡劑的相溶性已經改善之故，很適合使用。此等發泡劑可 以單獨使用或混合使用。 觸媒而言，通常之胺基甲酸乙酯泡體之製造所使用的 周知之觸媒均可使用。除三乙胺、Ν，Ν·二甲基己胺等之胺 系觸媒之外，尙可例舉：二丁基錫二月桂酸酯、辛酸錫等 之錫系及辛酸鉛等之鉛系等之金屬系觸媒等。 -21 - (18) 200415170 整泡劑而言，雖然可使用非離子系 子系表面活性劑，惟較佳爲非離子系表 矽酮系表面活性劑較常用。 其他，視用途，有時種種化合物可 而倂用。 代表性的添加劑而言，可例舉：難 基甲酸乙酯泡體之用途上，通常氯代烷 ，參（α-氯代乙基）磷酸酯或參（α-等較常用。 上述以外之添加劑、助劑而言，並 是通常之樹脂中以改善物性或改善操作 ，而對胺基甲酸乙酯化反應無顯著惡影 一種0 【實施方式】 實施例 以下，依實施例更詳細說明本發明 本發明衹要是不超越本發明之要旨，則 所限定。 (含有選自 1，2-ΗΑΒ、1，2-ΑΗΒ 以 群中之至少1種混合物） 含有選自1,2-ΗΑΒ、1，2-ΑΗΒ以及 中之至少1種的混合物，係使用具有下 、陰離子系、陽離 面活性劑、特別是 作爲添加劑 '助劑 燃劑。在硬質聚胺 基磷酸酯類，例如 氯代丙基）磷酸酯 不特別限定，衹要 性等之目的所使用 響者，則可使用任 之具體性狀態，惟 並不因此等實施例 泛1,2-DAB而成的 1，2-DAB而成的群 述組成的3種原液 -22- (19)200415170 (crude )之1，2-丁二醇（三菱化學（股）製，以下簡稱 原液 1，2-BG)。 3種原液1，2-BG之含有成分爲如下所示。 原液1，2-BG① 1，2-BG 1，2HAB 及 1，2-AHB 1,2-DAB 其他 9 1 . 0重量％ 2.4重量％ 0.3重量％ 6.3重量％ 原液1，2-BG② 1，2-BG 1，2-HAB 及 1，2·ΑΗΒ 1,2-DAB 其他 7 5.0重量％ 1 9.8重量％ 4.5重量％ 0.7重量％ 原液1，2-BG③ 1.2- BG 1，2-HAB 及 1，2-AHB 1.2- DAB 其他 7 6.0重量％ 1 8.7重量％ 3.9重量％ 1.4重量％ (1 ,2-BG ) 使用和光純藥工業（股）製、試藥特級1，2-BG。試藥 -23- (20) (20)200415170 標籤所記載的純度爲98%以上者，惟由本公司依氣體層析 儀法所分析的純度爲99.5 %以上。 (評估方法） (1 )酸値 準照JIS K 1 5 5 719 7。所測定者。 (2 )羥基値 準照JIS K 1 5 5 719 7 〇所測定者。 (3)黏度 準照JIS K 1 5 5 7197。並使用旋轉黏度計（B型黏度計） ，在25t下所測定者。 (4 )對聚酯多醇的發泡劑之溶解度 於3 00ml之燒杯中採取聚酯多醇100g，在室溫•大氣 壓力下之開放系中，使用30 0之三方後掠翼（在實施例 1至4及比較例1至3則爲30 0之平漿翼）按400rpm之 速度攪拌下徐徐添加發泡劑，並將以目視測定能在30 # 鐘以內形成透明的均勻相的最大添加量所求出的溶解度’ 作爲聚酯多醇與發泡劑之相溶性之指標。 在此，實施例1至4及比較例1至3中，由於使用直 徑3 0mm之平漿翼之故攪拌效率差，因而難於區別氣泡與 白濁’以致HFC-365mfc之相溶性之判定困難。於是，在 -24- (21) (21)200415170 實施例5至14及比較例4及5，則使用攪拌效率良好的 直徑30mm之三方後掠翼以求正確。 實施例1 於裝備有攪拌機、回流冷卻器、溫度計、壓力計、加 熱裝置等之容量1公升之玻璃製反應器中，飼裝鄰苯二甲 酸酐222g、原液1,2-BG②299g (飼裝當量比：羥基/羧基 = 1.81 )，將反應器之空間部加以氮氣取代後，開始反應 器內容物之加熱。當反應器內溫到達18(TC時，作爲觸媒 於反應器內添加四異丙基鈦酸酯0.3g，開始反應。然後， 耗費3小時將內溫升溫爲200 °C，並維持此溫度至反應完 成止。另一方面，反應器內之壓力在內溫從180 °C時至 200 °C止當中則維持在97.3 kPa。然後，耗費2小時徐徐減 壓爲37· 3 kPa，並維持此壓力至反應完成止。反應進行中 ，從反應器抽出反應混合物之一部分，並就所抽出的試料 測定酸値作爲確認反應進行狀況的指標。反應之完成係以 酸値成爲3以下爲終點，並將對反應容器內添加觸媒時起 算至反應終了止的所用時間作爲反應時間（於下述實施例 及比較例中均同）。此時之反應時間爲7.5小時。反應終 了後停止加熱並冷卻至1 〇〇 °C附近，抽出反應生成物，並 就所抽出試料測定黏度 '酸値以及羥基値。又，測定對所 得聚酯多醇的發泡劑（HFC-245fa、HFC-365mfc )之溶解 度。 •25- (22) (22)200415170 實施例2 除不用實施例1所記載之側中的飼裝成分之原液1，2-BG②299g，而使用原液1，2-BG①275g以外，其餘則按 該例中同樣步驟進行反應（飼裝當量比：羥基/羧基=1.87 )。反應進行中從反應益抽出反應混合物之一部分，並就 所抽出的試料測定酸値以確認反應完結，藉以終止反應。 此時之反應時間爲7.5小時。分別於表1中表示就反應生 成物的黏度、酸値、羥基値以及發泡劑（HFC-24 5 fa、 HFC-3 65 mfc)溶解度之測定結果。 比較例1 除不用實施例1所記載之例中的飼裝成分之原液1，2-BG②299g，而使用試藥1，2-BG 270g以外，其餘則按該 例中同樣步驟進行反應（飼裝當量比：羥基/羧基=2.00 ) 。反應進行中從反應器抽出反應混合物之一部分，並就所 抽出的試料測定酸値以確認反應完結，藉以終止反應。此 時之反應時間爲7 · 5小時。分別於表1中表示就反應生成 物的黏度、酸値、羥基値以及發泡劑（HFC-245fc、HFC-3 65mfc)溶解度之測定結果。 實施例3 於裝備有攪拌機、回流冷卻器、溫度計、壓力計、加 熱裝置等之容量1公升之玻璃製反應器中，飼裝鄰苯二甲 酸酐222g、原液1，2-BG②150g以及二乙二醇150g (飼 -26- (23) (23)200415170 裝當量比：羥基/羧基=1 · 9 1 )，將反應器之空間加以氮氣 取代後，開始反應器內容物之加熱。當反器內溫到達1 8 0 °C時，作爲觸媒於反應應內添加四異丙基鈦酸酯〇. 3 g，開 始反應。然後，耗費3小時將內溫升溫爲20(TC，並維持 此溫度至反應完成止。另一方面，反應器內之壓力在內溫 從1 8 0 °C時至2 0 0 °C止當中則維持在9 7 · 3 kP a。然後，耗費 3小時徐徐減壓爲25.3 kPa，並維持此壓力至反應完成止 。此時之反應時間爲7.5小時。分別於表1中表示就反應 生成物的黏度、酸値、羥基値以及發泡劑（HFC-2 45 fa、 HFC-3 65mfc)溶解度之測定結果。 比較例2 除不用實施例3所記載之例中的飼裝成分之原液1，2 -BG②150g，而使用試藥1，2-BG 135g以外，其餘則按該 例中同樣步驟進行反應（飼裝當量比：羥基/羧基=2.00 ) 。反應進行中從反應器抽出反應混合物之一部分，並就所 抽出的試料測定酸値以確認反應完結，藉以終止反應。此 時之反應時間爲7.5小時。分別於表1中表示就反應生成 物的黏度、酸値、羥基値以及發泡劑（HFC-24 5 fa、HFC-3 6 5 mfc )溶解度之測定結果。 實施例4 於裝備有攪拌機、回流冷卻器、溫度計、壓力計、加 熱裝置等之容量1公升之玻璃製反應器中，飼裝對苯二甲 -27- (24) (24)200415170 酸249g、原液1，2-BG②299(飼裝當量比：羥基/殘基 = 1.81)，將反應器之空間部加以氮氣取代後，開始反應 器內容物之加熱。當反應器內溫到達180X：時，作爲觸媒 於反應器內添加四異丙基鈦酸酯0.3 g，開始反應。然後， 耗費8小時將內溫升溫爲200 °C，並維持上溫度至反應完 成止。另一方面，反應器內之壓力在內溫從180°C時至 2 00 °C止當中則維持在97.3 kPa。然後，耗費2小時徐徐減 壓爲1 7 · 5小時。分別於表1中表示就反應生成物的黏度 、酸値、羧基値以及發泡劑（H F C - 2 4 5 f a、H F C - 3 6 5 m f c ) 溶解度之測定結果。 比較例3 除不用實施例4所記載之例中的飼裝成分之原液1，2-BG②299g，而使用試藥1,2-BG 270g以外，其餘則按該 例中同樣步驟進行反應（飼裝當量比：羥基/羧基=2.00 ) 。反應進行中從反應器抽出反應混合物之一部分，並就所 抽出的試料測定酸値以確認反應完結，藉以終止反應。此 時之反應時間爲7.5小時。分別於表1中表示就反應生成 物的黏度、酸値、羥基値以及發泡劑（HFC-245 fa、HFC-3 65 mfc)溶解度之測定結果。 -28- (25) 200415170 表 當量比 1，2-BG 純度 乙醯氧 物含量 黏度 (25°〇 酸値 羥基値 發泡齊! 溶解度 HFC· 245fa HFC- 365mfc (重量％) (重量 %) (mPa · s) (mgKOH/g) (mgKOH/g) (g/l〇〇gi 聚酯多醇 實施例 1 1.82 75 24 7,500 0.84 203 100 以上 30 實施例 2 1.87 91 3 16,500 0.70 250 70 13 比較例 1 2.00 99.5 0.5 以下 20,000 0.65 341 50 8 實施例 3 1.91 75 15 4,200 0.48 279 80 14 比較例 2 75 0.5 以下 7,500 0.65 332 30 5 實施例 4 1.82 75 H 24 7,500 0.89 209 100 以上 45 比較例 3 2.00 99.5 0.5 以下 22,000 1.14 342 65 9 表-i中，「當量比」，係指飼裝成分中之羥基與羧基的 當量比（羥基/羧基）之意，而「乙醯氧化含量」，係指 總和醇中之1，2-AHB以及1，2_DAB的含量之意。 實施例5 於裝備有攪拌機、回流冷卻機、溫度計、壓力計、加 熱裝置等之容量2公升之玻璃製反應器中，飼裝鄰苯二甲 酸酐45 8g、原液1，2-BG③5 98g (飼裝當量比：羥基/羧 基=1 . 7 7 )，將反應器之空間部加以氮氣取代後，開始反 應器內容物之加熱。當反應器內溫到達1 8 0 °C時，作爲觸 媒於反應器內添加四異丙基鈦酸酯〇. 5 g，開始反應。然後 ，耗費3小時將內溫升溫爲200°C，並維持此溫度至反應 完成止。另一方面，反應器內之之壓力在內溫從180 °C至 2 00 °C止當中則維持在93.3kPa。然後，耗費2.5小時徐徐 -29- (26) (26)200415170 減壓爲33.3kPa，並維持壓力至反應完成止。反應完成後 之判定及反應完成後之操作，係按實施例1同樣進行，此 時之反應時間爲8小時。分別於表2表示就反應生成物的 黏度、酸値、羥基値以及發泡劑（1^(：-24 5。、：^(：-3 65 mfc、HCFC14 1b以及環戊院）溶解度之測定結果。 又，確認至反應完成止當中餾出系外的乙酸之量之結 果，餾出液中存在有合計0.5 4g之乙酸。此量係相當於源 液1，2-BG中所含有的一元酯物及二元酯物之乙醯氧基所 相對的乙酸之量之約0.8%。在此，爲更正確實施例測定 起見，於減壓裝置與反應器之間設置有以乾冰與丙酮所冷 卻的真空阱（vac cum trap )，惟其中並未有乙酸之存在。 實施例6 除於實施例5所記載之例中，將飼裝成分改變爲鄰苯 二甲酸酐429g、原液1，2-BG③623g以及最終到達壓力 改變爲44. OkPa以外，其餘則按該例中同樣步驟進行反應 (飼裝當量比：羥基/羧基=1.97 )。反應進行中從反應器 抽出抽出反應混合物之一部分，並就所抽出的試料測定酸 値以確認反應完結’藉以終止反應。此時之反應時間爲8 小時。分別於表2中表示就反應生成物的黏度、酸値、羥 基値以及發泡劑（HFC_245 fa、HFC-365mfc、HCFC141b 以及環戊烷）溶解度之測定結果。 實施例7 -30- (27) 200415170 除於實施例5所記載之例中，將飼裝成分改變 二甲酸酐439g、原液1，2-BG①164g、原液1,2 4 5 0g以及最終到達壓力改變爲38.7kPa以外，其餘 例中同樣步驟進行反應（飼裝當量比：羥基/羧基= 。反應進行中從反應器抽出反應混合物之一部分， 抽出的試料測定酸値以確認反應完結，藉以終止反 時之反應時間爲8小時。分別於表2表示就反應生 黏度、酸値、羥基値以及發泡劑（HFC-245 fa 3 6 5 mfc、HCFC.141b以及環戊烷）溶解度之測定結| 實施例8 除於實施例5所記載之例中，將飼裝成分改變 二甲酸酐45 9g、原液1，2-BG①3 5 8 g、原液1，2 2 3 9g以及最終到達壓力改變爲42.7kPa以外，其餘 例中同樣步驟進行反應（飼裝當量比：羥基/羧基= 。反應進行中從反應器抽出反應混合物之一部份， 抽出的試料測定酸値以確認反應完結，藉以終止反 時之反應時間爲8小時。分別於表2表示就反應生 黏度、酸値、羥基値以及發泡劑（HFC-245 fa 365mfc以及HCFC141b)溶解度之測定結果。 實施例9 除於實施例5所記載之例中，將飼裝成分改變 二甲酸酐428g、原液1，2-BG①375g、原液1，2 爲鄰苯 -BG③ 則按該 :1.95) 並就所 應。此 成物的 、HFC- 爲鄰苯 _BG③ 則按該 1.88) 並就所 應。此 成物的 、HFC- 爲鄰苯 •BG③ -31 - (28) 200415170 2 5 Og以及最終到達壓力改變爲44. OkPa以外，其餘 例中同樣步驟進行反應（飼裝當量比：羥基/羧基= 。反應進行中從反應器抽出反應混合物之一部份， 抽出的試料測定酸値以確認反應完結，藉以終止反 時之反應時間爲8小時。分別於表2表示就反應生 黏度、酸値、羥基値以及發泡劑（HFC-24 5 fa 3 65 mfc以及HCFC 141b及環戊烷）溶解度之測定結 實施例1 0 除於實施例5所記載之例中，將飼裝成分改變 二甲酸酐3 97g、原液1，2-BG①391g、原液1,2 261g以及最終到達壓力改變爲48.0kPa以外，其餘 例中同樣步驟進行反應（飼裝當量比：羥基/羧基= 。反應進行中從反應器抽出反應混合物之一部份， 抽出的試料測定酸値以確認反應完結，藉以終止反 時之反應時間爲8小時。分別於表2表示就反應生 黏度、酸値、羥基値以及發泡劑（HFC-245fa 3 65mfc以及HCFC141b以及環戊烷）溶解度之測 實施例1 1 除於實施例5所記載之例中，將飼裝成分改變 二甲酸酐482g、原液1，2-BG①5 7 7g以及最終到 改變爲34.7kPa以外，其餘則按該例中同樣步驟進 則按該 2AI ) 並就所 應。此 成物的 、HFC- 果。 爲鄰苯 BG③ 則按該 :2.3 8) 並就所 應。此 成物的 、HFC- 疋結果 爲鄰苯 達壓力 行反應 -32- (29) (29)200415170 (飼裝當量比：羥基/羧基=1 . 8 1 )。反應進行中從反應器 抽出反應混合物之一部份，並就所抽出的試料測定酸値以 確認反應完結，藉以終止反應。此時之反應時間爲8小時 。分別於表2表示就反應生成物的黏度、酸値、羥基値以 及發泡劑（HFC-245 fa、HFC-365mfc 以及 HCFC141b)溶 解度之測定結果。 實施例1 2 除於實施例5所記載之例中，將飼裝成分改變爲鄰苯 二甲酸酐423 g、原液1，2-BG①628g以及最終到達壓力 改變爲44· 9kPa以外，其餘則按該例中同樣步驟進行反應 (飼裝當量比：羥基/羧基=2.24 )。反應進行中從反應器 抽出反應混合物之一部份，並就所抽出的試料測定酸値以 確認反應完結，藉以終止反應。此時之反應時間爲8小時 。分別於表2表示就反應生成物的黏度、酸値、羥基値以 及發泡劑（HFC-245fa、HFC-3 65mfc 以及 HCFC141b 以及 環戊烷）溶解度之測定結果。 實施例13 除於實施例5所記載之例中，將飼裝成分改變爲鄰苯 二甲酸酐489g、原液1,2-BG①3 42g、原液1，2-BG③ 2 2 8 g及最終到達壓力改變爲3 3 · 3 kPa以外，其餘則按該例 中同樣步驟進行反應（飼裝當量比··羥基/羧基=1 . 6 9 )。 反應進行中從反應器抽出反應混合物之一部份，並就所抽 -33- (30) (30)200415170 出的試料測定酸値以確認反應完結’藉以終止反應。此時 之反應時間爲8小時。分別於表2表示就反應生成物的黏 度、酸値、羥基値以及發泡劑（HFC-24 5 fa、HFC-3 6 5 mfc 以及H C F C 1 4 1 b以及環戊烷）溶解度之測定結果。 比較例4 除於實施例5所記載之例中，將飼裝成分改變爲鄰苯 二甲酸酐5 5 9 g、試藥1，2 - B G 5 0 9 g以外，其餘則按該例中 同樣步驟進行反應（飼裝當量比：羥基/羧基=1 . 5 0 )。反 應進行中從反應器抽出反應混合物之一部份，並就所抽出 的試料測定酸値以確認反應完結，藉以終止反應。此時之 反應時間爲8小時。分別於表2表示就反應生成物的黏度 、酸値、羥基値以及發泡劑（HFC-245 fa、HFC-3 65mfc以 及H C F C 1 4 1 b以及環戊烷）溶解度之測定結果。 比較例5 除於實施例5所記載之例中，將飼裝成分改變爲鄰苯 二甲酸酐5 2 8g、試藥1，2-BG 5 3 23 g以及最終到達壓力改 變爲3 7 · 3 k g以外，其餘則按該例中同樣步驟進行反應（ 飼裝當量比：羥基/羧基=1.63 )。反應進行中從反應器抽 出反應混合物之一部份，並就所抽出的試料測定酸値以確 認反應完結，藉以終止反應。此時之反應時間爲8小時。 分別於表2表示就反應生成物的黏度、酸値、羥基値以及 發泡劑（HFC-245fa、HFC-365mfc、HCFC141b 以及環戊 -34 - (31) (31)200415170 烷）溶解度之測定結果。 實施例1 4 於裝備有攪拌機、回流冷卻機、溫度計、壓力計、加 熱裝置等之容量2公升之玻璃製反應器中’飼裝琥拍酸 201g、對苯二甲酸281g以及原液1，2-BG③641g (飼裝 當量比：羥基/羧基=1 . 7 3 )，將反應器之空間部加以氮氣 取代後，開始反應器內容物之加熱。當反應器內溫到達 1 5 0 °C時，作爲觸媒於反應器內添加四異丙基鈦酸酯0.5 g ，開始反應。然後，耗費8小時將內溫升溫爲2 1 0 °C ’並 維持此溫度至反應完成止。另一方面，反應器內之壓力在 內溫從180°C時至210°C止當中則維持在80.0kPa。然後， 耗費4小時徐徐減壓爲40.OkPa，並維持此壓力至反應完 成止。反應完結之判定及反應完結後之操作則與實施例1 同樣實施，而此時之反應時間爲1 4小時。分別於表2中 表示就反應生成物的黏度、酸値、羥基値以及發泡劑（ HFC-245fa、HFC-3 65mfc 以及 H C F C 1 4 1 b )溶解度之測定 結果。 200415170 一 0 發泡劑溶解度 〇戊院 (gAOOg聚酯多醇） VO 卜 I 〇> I 卜 寸 因高黏度之故不能測定 1 HCFC- 141b 100以上 100以上 100以上 100以上 100以上 100以上 100以上 100以上 100以上 泛 〇 ψ *" ^ HFC- 365mfc 100以上 100以上 I_ 100以上 1_ in ^Τ) οο in ^Τ) Ό in CN o ψ '< HFC- 245fa 100以上 100以上 100以上 100以上 100以上 100以上 v〇 o 羥基値 j 1 E Ο bO On 等j_ Η VO (Ν ΓΜ S m ο m (N m VO 〇 (Ν <ys m (Ν 酸値 (mgKOH/g) ο 〇 ο VO 〇 〇 rn 〇 吞 Ο 〇 卜 m ο 〇 s· (Ν 黏度 (25°〇 (mPa · s) Ο (Ν ΟΝ 3,3〇〇 4,900 〇 〇〇 3,200 ο § -Η 〇 〇 3,100 Ο m 20萬 以上 160,000 2,430 祕Εΐ_ 廳郗 NO i- (重量％) m (Ν <N ▼—i m m ▼Η 0.5以下 0.5以下 m (N 1,2-BG 純度 (重量％) ν〇 VO § 00 00 00 00 〇； On cK ON v〇 _ $s τ—^ as ψ < 00 00 1*-^ r_ _ (Ν 00 m (Ν So Ά (Ν ν〇 τ—^ ΠΊ vq r—4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例10 實施例11 實施例12 實施例13 比較例4 比較例5 實施例14 。舾*Nig2a·迦：^T「腦芒ύ」 但.«^«<fflso%_ svaCNuF^KIPQHV-r 一 , βνΗ-(Ν二忉發·迦康了「_·^祕 ishoJ 但，個忉(稍您/稍觀)±5__s糊愁感稍勧忉 -36- (33) (33)200415170 從表1及表2可知下述事實。 (1 )實施例與比較例之比較結果 如醇中之1，2-HAB、1，2-AHB以及1，2-DAB總和的含 量在2至24重量％的實施例的情形’較比較例之〇 · 5重量 %以下之情形，可製得黏度爲低’且發泡劑之溶解度爲高 的聚酯多醇。 (2 )實施例1、2及5至13與比較例1、4以及5之 比較結果 如以飼裝當量比（羥基/羧基）或羥基値在同水準者 比較時，則如原液1，2-BG中所含1，2-BG之含量（純度） 在70重量％以上、95重量％以下之情形，較以純度99.5 重量％以上之試藥特級之1，2-BG爲原料的情形，可製得黏 度爲低，且發泡劑之溶解度爲高的聚酯多醇。 (3 )實施例3與比較例2之比較結果 即使爲原料醇之一部分而使用原液1，2_Β(}以外之醇 (此時爲二乙二醇），仍可製得黏度低、且發泡劑之溶解 度高的聚酯多醇。 (4 )實施例4與比較例3之比較結果及實施例14 即使作爲原料芳香族羧酸，使用對苯二甲酸而非鄰苯 二甲酸或鄰苯二甲酸酐時，則同樣可製得黏度低，且發泡 -37- (34) (34)200415170 劑之溶解度高的聚酯多醇。 又，即使將原料芳香族羧酸之一部分取代爲脂肪酸羧 酸（此時爲琥珀酸），仍可製得黏度更低、且發泡劑之溶 解度高的聚酯多醇。 產業上利用之可能性 本發明之聚酯多醇，係由於低黏度且操作處理容易之 外，尙與發泡劑，特別是與HFC-245fa及/或HFC-3 65mfc 等之HFC系發泡劑的相溶性高之故，可作爲聚胺基甲酸 乙酯，特別是，硬質聚胺基甲酸乙酯泡體之原料多醇有用 者。 另外，本發明之說明書之指示，係引用並包含有成爲 本申請案之優先權主張之基礎的日本專利申請案2002-313420號（2 00 2年10月28日提出申請）之說明書全部 內容者。 -38-200415170 (1) (i) Description of the invention [Technical field to which the invention belongs] The present invention relates to polyester polyols. Specifically, regarding polyurethane, in particular, when it is used as a rigid polyurethane foam, it can exhibit excellent compatibility with the foaming agent, and has low viscosity and easy handling. @ _ 自 乡Alcohol 0 [Prior art] Because rigid polyurethane foams have excellent thermal insulation properties, they are widely used as thermal insulation materials for general buildings. Polyurethane foams are generally prepared according to the preparation of polyisocyanate component liquid (hereinafter referred to as liquid A), mixed with polyether polyol and / or polyester polyol, foaming agent, and if necessary Produced by a method of mixing a liquid such as a catalyst or a foam stabilizer (hereinafter referred to as liquid B), and mixing liquid A and liquid B to cause foaming and curing in a short time. Therefore, polyester polyols must have good compatibility with the blowing agent, low viscosity, and easy handling. As the blowing agent, a low-boiling non-polar organic solvent is generally used, that is, specifically, in addition to the HCFC-based blowing agent, saturated hydrocarbon-based solvents such as pentane and cyclopentane can be used. In addition, depending on the application or the manufacturing conditions of the rigid polyurethane foam, there are practical problems when using saturated hydrocarbon-based solvents with low ignition points and exposing properties. Therefore, HCFC (hydrochlorofluoro Hydrocarbon) -based blowing agent. On the other hand, since the destruction of the ozone layer has become a problem, 'from the CFC (chlorofluorocarbon) -based blowing agents commonly used in the past, especially CFC-1 1E, etc.-5- (2) (2) 200415170' has been changed to HCFC blowing agent with small ozone destruction coefficient, especially the current HCFC] 41b. However, this HCFC-141b is not a zero ozone depletion factor, so it is scheduled to be restricted from the end of 2003. As an alternative to HCFC-14 1b, HFC (hydrofluorocarbon) blowing agents may be selected, especially HFC-245fa and HFC-365mfc. Common problems in using foaming agents currently and in the future can be exemplified: a polyol component made of polyether polyol and / or polyester polyol, which is the main component of liquid B, and the like The fact that the compatibility of the blowing agent is not good. In particular, poor compatibility with HFC-based blowing agents such as HFC-245fa and HFC-365 fc, which may be selected as alternatives to HCFC-based blowing agents, will be a major problem in the future. In addition, in order to achieve uniform stabilization of the B liquid, a method of adding a surfactant is generally widely used as a foam stabilizer, especially a method of adding a nonionic surfactant, but the effect cannot be said to be sufficient. In addition, in recent years, various proposals have been made for a solubilizing agent having a certain surface-active effect capable of improving compatibility. However, these compatibilizing agents are usually almost all compounds without a hydroxyl group. Therefore, even as a supplementary component of liquid B, it is helpful to improve the compatibility with the above-mentioned blowing agent. Since it does not participate in the urethane reaction, it exists in the rigid polyurethane foam in its original form. In order to solve the problem of poor compatibility between the foaming agent and the B liquid, it is necessary to improve the compatibility and also be used as Compounds that have a function of a hydroxyl-containing polyhydric alcohol may be practically important Articles 6-(3) (3) 200415170. Polyester polyols, especially aromatic polyester polyols, are often used with polyether polyols for the purpose of improving the heat resistance of the obtained rigid polyurethane foam. However, aromatic polyester polyols generally have difficulty in handling due to their high viscosity, or poor compatibility with the blowing agent, making it difficult for B to meet the compatibility between the blowing agent and the B liquid. The required amount is formulated in the liquid, and there are various practical problems. On the other hand, in order to improve the physical properties of polyester polyols including compatibility, it is effective to select alcohols of raw materials such as glycols and triols. In particular, in order to improve the compatibility, 1,2-butanediol (hereinafter, abbreviated as 1,2-BG) is produced in whole or in part. However, even when 1,2-BG is used, there is a limit to the reduction in viscosity of the obtained polyester polyol, and for polyester polyols in which the hydroxyl group is generally used around 250 (mgKOH / g), then It is difficult to synthesize a viscosity below 20,000 mPa * S (25 ° C). This indicates that the adjustment of the B liquid did not meet the requirements. Therefore, if there is a novel polyester polyol that has good compatibility with the foaming agent and low viscosity, it can be obtained as a part of the polyol component in an appropriate amount to obtain a liquid B with good stability. The degree of freedom of the mixing ratio of each component of the liquid B can be improved, and as a result, a rigid polyurethane foam having excellent physical properties can be obtained. [Summary of the Invention] The invention revealed that the present inventors and others have intensively researched in order to solve such a problem and found that -7- (4) (4) 200415170 'As an alcohol used as a raw material for the production of polyester polyols, it is contained in a specific amount. It is selected from the group consisting of dioxin-2-ethoxybutane (hereinafter, abbreviated as ι, 2-ΗΑΒ) and ethoxy-2-hydroxybutane (hereinafter, abbreviated as i, 2-Ahb) and 1,2-diethyl The fact that a mixture of at least one of the group consisting of oxobutane (hereinafter referred to as 1,2-DAB) can produce a polyester polyol with good compatibility with the foam and low viscosity, and The present invention has been completed. The obtained polyester polyol is absorbed in the molecule of polyurethane as one of the constituent components of polyurethane, as is the polyester polyol commonly used in the past, and does not affect the polymerization. Under the physical properties of urethane, the above characteristics can be exhibited. That is, the present invention has the following features. (1) A polyester polyol is a polyester polyol obtained by subjecting a polycarboxylic acid and an alcohol to an esterification reaction, and is characterized in that an alcohol containing 1-hydroxy-2-ethoxybutane is used as the alcohol. 2 to 40% by weight of at least one of the group consisting of 1-ethoxy-2-hydroxybutane and 1,2 · diethoxybutane. (2) a polyester polyol containing 1,2-butanediol, and selected from 1-hydroxy-2 · ethoxybutane, 1-ethoxy-2-hydroxybutane, and A mixture of at least one of the group consisting of 1,2-diacetoxybutane, characterized in that the content of 1,2-butanediol in the mixture is 60 to 98% by weight. (3) The polyester polyol according to the above (2), wherein the mixture is made by reacting 1,3-butadiene with acetic acid in the presence of molecular oxygen and a palladium catalyst, and the obtained two The reaction products of acetoxybutenes and monoacetoxybutene are carried out in the presence of a noble metal such as hydrogen, and then the reaction products of diacetoxybutane and monoacetoxybutane are It is prepared by hydrolyzing in the presence of a solid acid catalyst, distilling off acetic acid and water, and then separating it by distillation. (5) (5) 200415170 (4) A polyurethane obtained by reacting a polyol containing the polyester polyol according to any one of (1) to (3) above with an isocyanate compound. (5) A kind of rigid polyurethane foam, which is obtained by using the polyurethane described in (4) above. (6) The rigid polyurethane foam as described in the above (5), which further contains an ozone destruction coefficient of 0. Made of a foaming agent below 8. (7) The rigid polyurethane foam as described in (6) above, wherein the foaming agent is HFC-245fa and / or HFC-365mfc. Effects of the Invention According to the present invention, polyurethane can be provided. In particular, as a raw material for rigid polyurethane, the polyol has low viscosity and is easy to handle. At the same time, it is compatible with foaming agents, especially Polyester polyols with good compatibility with HFC blowing agents such as HFC-245fa and / or HFC-3 65 mfc. Best Mode for Carrying Out the Invention The present invention will be described in detail below. The polyester polyol of the present invention is preferably a polyurethane, especially a polyester polyol used for a rigid polyurethane foam, and is made of a polycarboxylic acid and an alcohol. Polyester polyols. (Polycarboxylic acid) -9- (6) (6) 200415170 As the polycarboxylic acid of the present invention, dicarboxylic acid or tricarboxylic acid can be exemplified. Preferred are: aromatic di- or tricarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and the like and anhydrides thereof. Among these, particularly preferred are phthalic acid, phthalic anhydride or terephthalic acid. In addition, these aromatic carboxylic acids may be esterified using a monoalcohol having 1 to 8 carbons such as methanol, ethanol, and 2-ethylhexanol, such as dimethyl terephthalic acid. Further, aliphatic dicarboxylic acids such as succinic acid, maleic acid, and adipic acid may be mixed with the aromatic carboxylic acids, or they may be used alone as the case may be. (Alcohol) Contains at least one alcohol selected from the group consisting of 1,2 · ΗΑΒ, 1,2-AHB, and 1,2-DAB. The alcohol system used as a starting material in the present invention contains 1 2 to 40% by weight of at least one of the groups consisting of 2-HAB, 1,2-AHB, and 1,2-DAB. The content of at least one member selected from the group consisting of 1,2-ΗΑΒ, 1,2 · ΑΗΒ, and 1,2-D ΑB is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 35 weight% or less, more preferably 30 weight% or less. When the amount is too small, the effect of reducing the viscosity of the polyester polyol is hardly exhibited. On the other hand, when the amount is too large, when synthesizing the polyester polyol, the hydroxyl group in the produced polyester polyol will be significantly reduced, and depending on the use ratio of the polycarboxylic acid used, it may be completely absent. Hydroxyl compounds, that is, only non-polyols can be made. If a polyester polyol of • 10- (7) (7) 200415170 is produced using a ratio in a range that has this tendency, the rigid polyurethane is obtained by subsequent urethane reaction with polyisocyanate Ethyl acetate foam may have significant adverse effects on properties such as strength and heat resistance. In addition, among 1,2-HAB, 1,2-AHB, and 1,2-DAB, the amount of 1,2-DAB is the total of the three kinds. The amount is usually 1% by weight or more, and preferably 5% by weight. It is 10% by weight or more, more preferably 10% by weight or more, and usually 50% by weight or less, preferably 33% by weight or less, and more preferably 25% by weight or less. As such an alcohol, more specifically, a mixture containing 1,2-BG and at least one selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB, The content of 1,2-BG in the mixture, and the content of 1,2-BG in the mixture is usually preferably a mixture of 60 to 98% by weight. This mixture is mainly made by reacting 1,3-butadiene with acetic acid in the presence of molecular oxygen and palladium-based catalysts, and the obtained diethyloxobutenes and ethylacetoxybutene etc. The reaction product is subjected to hydrogenation in the presence of a precious metal catalyst, and then the reaction products such as acetoxetine and acetoxetine are added to water in the presence of a solid acid catalyst. Decomposed, after removing acetic acid and water, it is obtained by distillation and separation. That is, it can be produced as a by-product that is produced simultaneously when 1,3-butadiene is reacted with acetic acid to produce 1,4-butanediol. For the palladium-based catalyst used in the present invention, palladium metal or a salt thereof can be used alone or as a promoter in combination with a metal such as bismuth, selenium, antimony, copper, copper, or a salt thereof. The catalyst is preferably used by supporting a carrier such as oxidized sand, oxidized oxide, or activated carbon. A mixture containing 1,2-BG and at least one member selected from the group consisting of 1,2-ΑΗΒ, 1,2 · ΑΗΒ, and 1,2 · -11-(8) (8) 200415170 DAB, Usually, it is preferred to contain 1,2-BG at 60% by weight or more and 98% by weight or less. If the content of HBG is too small, when synthesizing polyester polyols, the hydroxyl groups in the obtained polyester polyols will be significantly reduced. 'Even depending on the proportion of the polybasic residual acid used, there are compounds without hydroxyl groups at all, that is, In the case where only non-polyols can be made. If a polyester polyol prepared in a range having such a tendency is used, the strength or the rigid polyurethane foam obtained by further urethane reaction with polyisocyanate may be Properties such as heat resistance have a very bad effect. On the other hand, if it is too much, the effect of reducing the viscosity of the polyester polyol is hardly obtained. Therefore, the content of 1,2-BG is preferably in the range of 65% by weight or more, more preferably 70% by weight or more, and more preferably 95% by weight or less, and more preferably 90% by weight or less based on the total weight of the mixture. . In the mixture, in addition to 1,2-BG and at least one member selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB, 尙 may contain acetic acid, water, and 1 in trace amounts. , 4-butanediol, acetate of 1,4-butanediol and the like. In general, the mixture preferably contains at least one species selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB in an amount of 2% by weight or more and 40% by weight or less. If there is too much content of at least one selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB, when a polyester polyol is synthesized, the hydroxyl group in the obtained polyester polyol It will be significantly reduced, even depending on the proportion of the polycarboxylic acid used, there are no compounds with hydroxyl groups at all, that is, those that can only be made of non-polyols. If a polyester polyol prepared in a range having such a tendency is used, it is possible to perform rigid polyamines prepared by further performing polyurethane-12- (9) 200415170 ethylation reaction with polyisocyanate. The strong thermal properties of ethyl formate foam have a very bad effect. On the other hand, if it is too small, the effect of reducing the viscosity of the polyester polyol is hardly obtained. Therefore, the content of at least one selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB is preferably at least% by weight, more preferably at least 10% by weight based on the total weight of the mixture, It is more preferably in a range of 35 weight%, more preferably 30 weight% or less. (Other alcohols) In addition to the above-mentioned mixtures, the alcohols of the present invention are also metabolites. In general, other alcohols that can be used include ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycol, 1,3-butanediol, and 1,4-butanediol , 1,5-pentanediol, 1,6-, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, and other triols, trimethylol and other triols. Furthermore, long-chain polyoxyethylene such as polyethylene glycol, polypropylene glycol, polyoxypropylene copolymerized glycol, and polytetramethylene ether glycol can also be used. When using this alcohol, the amount of the above-mentioned mixture is used. When the total amount is too small, a significant effect of improving the compatibility of the foaming agent cannot be obtained. That is, the amount of the above-mentioned mixture is usually a specific viscosity for the total alcohol amount of 40% by weight or more, preferably 50% by weight, depending on the viscosity reduction and / or compatibility required by the polyester polyol It is below the aforementioned range. It is less than 5% by weight. Use alcohol, di-1,2-butanediol, glycerol Vene / oxyether polyol, and low viscosity raw materials. But sex balance • 13- (10) (10) 200415170 Also, as a method for reducing the viscosity of polyester polyols, monohydric alcohols such as methanol, ethanol, isopropanol, and 2-ethylhexanol can also be used. At the time of synthesis of polyester polyols, the reaction system is distilled off and the yield is deteriorated, or the strength or heat resistance of polyurethane is adversely affected. (Esterification catalyst) In the esterification reaction of the present invention, an esterification catalyst is usually used. For catalysts, acid catalysts are usually used. For Lewis acid, for example, o-titanates such as tetraisopropyl titanate and tetra-n-butyl titanate, or tin-based compounds such as diethyltin oxide and dibutyltin oxide can be used. Compounds, or metal compounds such as zinc oxide. In addition to the Lewis acid, Brensted acid such as p-toluenesulfonic acid can be used. On the other hand, the obtained polyester polyol will undergo urethane reaction with polyisocyanate to become polyurethane, but the catalyst used in the synthesis of polyester polyol at this time will not affect the amine group. Ethyl formate reaction is more suitable without adverse effects on the reaction dynamics. Among the above-mentioned esterification catalysts, ortho titanate is preferred, and the amount used is also the total of the polycarboxylic acid and alcohol used in the raw material, usually 1. 0% by weight or less, preferably 0. 2% by weight or less, and usually 0. 01% by weight or more, preferably 0. 03% by weight or more. Depending on the use of polyurethane, the reaction can also be performed without using these esterification catalysts. (Reaction conditions) 14- (11) (11) 200415170 The polyester polyol of the present invention can be obtained by adding the above-mentioned esterification catalyst to a polycarboxylic acid and an alcohol, and performing an esterification reaction. The ratio of the polycarboxylic acid to the alcohol varies depending on the hydroxyl group, viscosity, etc. of the target polyester polyol, but it is usually 1 for the hydroxyl equivalent of the alcohol of the carboxyl equivalent of the polycarboxylic acid. 1 equivalent or more, preferably 1. Above 3 equivalents, more preferably 1. 5 equivalents or more, but usually 4. Below 0 equivalent, preferably 3. Below 0 equivalent, more preferably 2. 7 equivalents or less. In particular, when the mixture of the present invention is used in an amount of 40% by weight or more, the hydroxyl group in the obtained polyester polyol will be significantly reduced when it is so small, depending on 1,2 · ΗΑΒ, 1,2 · ΑΗΒ in the mixture. And the content of 1,2-DAB, there are compounds without hydroxyl groups at all, that is, the case where only non-polyols can be obtained. If a polyester polyol obtained in a range having such a tendency is used, the strength or heat resistance of the rigid polyurethane foam obtained by further urethane reaction with the polyisocyanate may be possible. Sexual performance has a very bad effect. On the other hand, when it is too large, the free alcohol that is not available for esterification reaction in the polyester polyol will remain in a large amount. If the polyester polyol obtained in this way is used, the properties such as the strength or heat resistance of the rigid polyurethane foam obtained by further urethane reaction with the polyisocyanate may also be affected. Has very bad effects. Here, if the mixture of the present invention is used as an alcohol, monovalent esters such as 1,2-HAB are each converted to 1 equivalent in terms of hydroxyl groups, and 1,2-DAB is 0 equivalent in terms of hydroxyl groups, to be calculated. The hydroxyl equivalent of the mixture. The reaction temperature is usually in the range of 15 ° C or higher, preferably 180 ° C or higher, and usually 250 ° C or lower, preferably 230 ° C or lower. Example-15- (12) (12) 200415170 For example, If the reaction is started at 18 ° C, and the temperature is gradually raised to 20 ° C as the reaction progresses, it is easy to control the reaction. The reaction pressure can be normal pressure, except for the by-product water and a small amount of acetic acid removal. In order to complete the reaction as soon as possible, it is preferable to gradually reduce the pressure as the reaction proceeds. However, if the degree of decompression during the reaction is insufficient, the degree of completion of the esterification reaction is insufficient, so that a polymer with a high acid content is formed. Ester polyols. On the other hand, if excessive decompression occurs during the reaction, not only alcohol components such as 1,2-BG, 1,2-HAB, 1,2-AHB will be distilled out of the system and damage will be lost. Rate, even in extreme cases, ethyl acetate such as 1,2-HAB or 1,2-AHB for the esterification reaction will cause deacetic acid due to the transesterification reaction, resulting in the formation of high molecular weight polyester polyols. These phenomena not only significantly increase the viscosity of the obtained polyester polyol, but also tend to decrease the compatibility with the blowing agent. However, although the appropriate reaction pressure varies depending on the reaction temperature, when the reaction temperature is 200 ° C, the pressure is usually 20 kPa or more, preferably 30 kPa or more, and usually 60 kPa or less, and preferably 50 kPa or less. Based on the target polyester polyol viscosity or hydroxyl group, the amount of the mixture used, the mixture selected from the group consisting of 1,2-HAB, 1,2-AHB, and 1,2-DAB The content of at least one kind can also be reacted under conditions outside the above-mentioned pressure range. Alternatively, a small amount of organic solvent such as toluene and xylene can be used without reducing the pressure, and the by-product water and a small amount of Acetic acid is azeotropically removed to remove it from the system. The end point of the reaction, in the case of polyester polyols, is usually determined by the amount of unreacted carboxyl groups of the polycarboxylic acid used. On the other hand, in polyamine-16- ( 13) 200415170 For the use of ethyl formate, it is not suitable for polyisocyanate urethane. The presence of acid will reduce the reactivity. It is not suitable for polyester polyols. The amount of unreacted carboxylic acid, that is, as low as possible For the use of rigid polyurethane foam, the acid is usually 10 mgKOH / g or less, preferably 5 mgKOH / g or less, more than 3 mg KOH / g. Also, in the more stringent In the case of urethane reaction, it may be required to be 1 mgKOH / g or less. The polyester polyol obtained as described above is usually an ester compound having a structure composed of a carboxylic acid and an alcohol to be used, and In the polyester polyol obtained in the invention from an unreacted alcohol, the average functional group of the above-mentioned ester compound is obtained by containing only 1,2-BG, and selected from 1,2-ΗΑΒ, 1,2 · ΑΗΒ, and DAB. The group of at least one and two-membered polycarboxylic acid is usually synthesized in a form of 0. 8 or more, preferably 1.1 or more, and more preferably i. 5. If the average number of functional groups of the ester compound is too low, the degree of polymerization of the polyurethane obtained from the urethanization reaction of the isocyanate will be reduced, for example, in a rigid polyurethane foam. In some cases, the strength or heat resistance is significantly deteriorated. In addition, in order to keep the average number of functional groups of the ester compound constant and / or keep the average molecular weight below a certain value, it is necessary to achieve an equilibrium state of 1,2, 1, in the esterification reaction as much as possible with the transesterification reaction. When the acetic acid distillation reaction system of 2-AHB and 1,2-DAB acetic acid ester is too much, such as acetic acid, the average number of functional groups of the ester compound will be different from the original product design, or the average molecular weight will increase. It is not suitable that the viscosity of the obtained polyester polyol becomes very large. Therefore, instead, the acid content is better. In the case of 1,2- the above case is not the same as that in the case of polyethylene. The goal is not to make -HAB out. For the result, the amount of acetic acid that was distilled out of the system in the esterification reaction of ester-17- (14) (14) 200415170 was calculated based on the combined acetic acid of 1,2-HAB, i, 2-AHB and 1,2-DAB. The amount is usually 30% or less, preferably 20% or less, and more preferably 10% or less. However, depending on the viscosity or hydroxyamidine of the target polyester polyol, the amount of the mixture used, the content of 1,2-HAB, 1,2-AHB, and 1,2 · DAB in the mixture may also exceed the above range. The acetic acid was distilled off. In addition, at the start of the reaction, it is preferable to replace the intervening portion of the reaction vessel with nitrogen in order to prevent the colored polyester polyol from being colored, and to further remove the dissolved oxygen in the reaction solution. In addition, after the reaction is completed, the unreacted free alcohol can be distilled out of the system under appropriate reduced pressure conditions to adjust the physical properties or properties of the polyester polyol (reaction form). The polyester polyol in the present invention The reaction form can be applied to ordinary batch equipment or continuous equipment. However, since the reaction time requires a long time and the viscosity of the obtained polyester polyol is much higher than the viscosity of the alcohol used as the raw material, it is preferably Use batch responders. (Usage) The polyester polyol obtained by the present invention is very suitable for the polyurethane, especially the rigid polyurethane foam obtained by reacting the polyol with an isocyanate compound, except for low viscosity and handling. In addition to being easy to use, plutonium can be used as a blowing agent with an ozone destruction coefficient below 0.8, especially with HFC-245fa and / or HFC-3 6 5 mfc which will be used in the future -18- (15) (15) 200415170. A polyester polyol having a high compatibility with the blowing agent is useful. Rigid polyurethane foam can be obtained by mixing liquid A made of polyisocyanate with polyol component, foaming agent, and polyether polyol and / or polyester polyol. Liquid B, which is made of a vehicle, a foam stabilizer, and other additives and auxiliaries as required, is produced by a method of mixing, foaming, and curing in a short time. The polyisocyanate component is not particularly limited as long as it is an organic compound having two isocyanate groups in one molecule. Examples include: aliphatic, cycloaliphatic, and aromatic polyisocyanates or modified products thereof. Specific examples of the aliphatic-based and alicyclic-based polyisocyanate include hexamethylene diisocyanate, isophorone diisocyanate, and the like. As the aromatic polyisocyanate, for example, methylenediphenyl diisocyanate, diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, and the like, and these carbodiimide modifications may be included. Modified products such as polymers or prepolymers. The preferred polyisocyanate of the present invention is an aromatic polyisocyanate or a modification thereof. Particularly preferred are diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, methylenephenyl diisocyanate, and the like. Modified products can be used alone or in combination. As the polyphenylene polymethylene polyisocyanate, those having a NCO group content of usually 29 to 32% by weight and a viscosity of usually 250 mPa · S (25 ° C) or lower can be used. In addition, among these modifications, the carboxyamidodiimide modified product is one that introduces a carboxyamidodiimide bond using a phosphorus-based catalyst known from Zhou -19- (16) (16) 200415170. The prepolymer is one in which the above-mentioned polyisocyanate is reacted with a polyol, and an isocyanate group is left at the terminal. As the polyol to be used at this time, a polyol used in the production of polyurethane is usually used. In addition to these polyisocyanates, if necessary, additives and auxiliaries are mixed with the polyisocyanate component and used. For example, for the purpose of improving the miscibility with liquid B, a foam stabilizer that can be used in liquid B may be used as a compatibilizer. In this case, a nonionic surfactant is generally preferred, and a silicone surfactant is more commonly used. For the purpose of improving flame retardancy and viscosity adjustment, a flame retarder may be used. For the use of rigid polyurethane foam, generally, chloroalkyl phosphates, such as ginseng (α-chloroethyl) phosphate or ginsyl (chloropropyl) phosphate are more commonly used. . Additives and auxiliaries other than the above are not particularly limited, as long as they are used in ordinary resins for the purpose of improving physical properties or improving workability, and have no significant adverse effect on the urethane reaction, Either can be used. As the polyol component, polyether polyols or polyester polyols having a hydroxyl group of usually 200 to 800 and a functional base number of 2 to 8 can be used, or two or more of them can be used in combination. Examples of the polyether polyol include polymers of alkylene oxide, sucrose, alone or by using ethylene oxide, propylene oxide, 1,2-butylene oxide, and tetrahydrofuran. Or trifunctional or higher polyhydric alcohols such as sorbitol and glycerol, and the above-mentioned alkylene oxides, and aliphatic amines and aromatic amines, and the above-mentioned alkylene oxides. -20- (17) (17) 200415170 For polyester polyols, those obtained by esterifying the polyvalent carboxylic acid of the present invention with an alcohol may be used, and the total polyol component is usually 2 in general. It is used in an amount of not less than 5 wt%, preferably not less than 5 wt%, more preferably not less than 10 wt%, usually not more than 50 wt%, preferably not more than 30 wt%, and more preferably not more than 20 wt%. In addition to the polyester polyols of the present invention, commonly used polyester polyols include phthalic anhydride, which is a polycarboxylic acid, and aromatics such as terephthalic acid and trimellitic acid. Di- or tricarboxylic acids, hydroxy groups obtained by esterification reaction with ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, etc., and glycerol, trimethylolpropane, etc. of 2- to 3-membered glycols alone or in mixture Polyester polyols are generally 200 to 400, and the average number of functional groups is usually about 2 to 3. In addition, alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerol, or alkanolamines such as diethanolamine and triethanolamine, and the like can also be used as compounds having two or more active hydrogens in one molecule. For foaming agents, the ozone removal factor is usually 0. Foaming agents below 8, such as HCFC-141b, cyclopentane, and n-pentane, etc., are especially compatible with the blowing agents such as HFC-245 fa and HFC-3 6 5 mfc to be used in the future. Because the solubility has been improved, it is suitable for use. These foaming agents can be used alone or in combination. As the catalyst, any of the well-known catalysts used in the production of ordinary urethane foams can be used. In addition to amine-based catalysts such as triethylamine, Ν, Ν · dimethylhexylamine, etc., examples include tin-based dibutyltin dilaurate, tin octoate, and lead-based octanoate. Metal catalysts. -21-(18) 200415170 Regarding foam stabilizers, although nonionic surfactants can be used, nonionic surfactants are more commonly used. In addition, depending on the application, various compounds may be used. As a representative additive, for example, for the use of ethyl ethyl formate foam, chloroalkane, ginseng (α-chloroethyl) phosphate or ginseng (α-, etc.) are more commonly used. In terms of additives and auxiliaries, it is a common resin to improve physical properties or improve operation without significant negative effects on the urethane reaction. [Embodiment] The following is a detailed description of the present invention in accordance with the following examples. The present invention is limited as long as it does not exceed the gist of the present invention. (Contains at least one mixture selected from the group consisting of 1,2-ΗΑΒ, 1,2-ΑΗΒ) Contains at least one selected from 1,2-ΗΑΒ, 1 , 2-AΗΒ and a mixture of at least one of the two, is used with lower, anionic, cation-off surfactant, especially as an additive 'combustion agent. In the rigid polyamidophosphates, such as chloropropyl The phosphoric acid ester is not particularly limited, and any specific state can be used as long as it is used for the purpose of sex and the like, but it is not limited to the 1,2-DAB in which the examples are generalized by 1,2-DAB. 3 kinds of stock solutions composed of group -22-22 (19) 200415170 (crude) 1,2-butanediol (manufactured by Mitsubishi Chemical (shares), hereinafter referred to as liquid 1,2-BG). The constituents of three kinds of stock solutions 1,2-BG are as follows. Stock solution 1,2-BG①1,2-BG 1,2HAB and 1,2-AHB 1,2-DAB Others 9 1. 0% by weight 2. 4% by weight 3% by weight 6. 3% by weight stock solution 1,2-BG②1,2-BG1,2-HAB and 1,2 · ΑΗΒ 1,2-DAB Others 7 5. 0% by weight 1 9. 8% by weight 4. 5% by weight 7 wt% stock solution 1,2-BG③ 1. 2- BG 1,2-HAB and 1,2-AHB 1. 2- DAB other 7 6. 0% by weight 1 8. 7% by weight 3. 9% by weight 1. 4% by weight (1,2-BG) It is manufactured by Wako Pure Chemical Industries, Ltd. and has a special test grade of 1,2-BG. Reagent -23- (20) (20) 200415170 The purity listed in the label is 98% or more, but the purity analyzed by our company according to the gas chromatography method is 99. 5% or more. (Evaluation method) (1) Acid acid Standard according to JIS K 1 5 5 719 7. Measured by. (2) Hydroxyl hydrazone is measured according to JIS K 1 5 5 719 7 0. (3) Viscosity According to JIS K 1 5 5 7197. And use a rotational viscometer (B-type viscometer), measured at 25t. (4) Solubility of foaming agent for polyester polyol 100 g of polyester polyol was taken in a beaker of 3,000 ml. In an open system at room temperature and atmospheric pressure, three-thirds rear swept wings (in the implementation) Examples 1 to 4 and Comparative Examples 1 to 3 are flat wing blades of 300.) The foaming agent is slowly added under stirring at 400 rpm, and the maximum addition that can form a transparent homogeneous phase within 30 # minutes is visually determined. The solubility calculated by the amount is used as an index of the compatibility between the polyester polyol and the blowing agent. Here, in Examples 1 to 4 and Comparative Examples 1 to 3, since a flat blade wing having a diameter of 30 mm was used, the stirring efficiency was poor, and it was difficult to distinguish between bubbles and white turbidity ', making determination of the compatibility of HFC-365mfc difficult. Therefore, in -24- (21) (21) 200415170 in Examples 5 to 14 and Comparative Examples 4 and 5, a three-way rear swept wing with a diameter of 30 mm with good stirring efficiency was used for correctness. Example 1 A glass reactor having a capacity of 1 liter equipped with a stirrer, a reflux cooler, a thermometer, a pressure gauge, and a heating device was fed with 222 g of phthalic anhydride and 1,2-BG stock solution of 299 g (feed equivalent Ratio: hydroxyl / carboxyl = 1. 81). After replacing the space portion of the reactor with nitrogen, heating of the reactor contents was started. When the internal temperature of the reactor reached 18 ° C, tetraisopropyl titanate was added to the reactor as a catalyst. 3g, start reaction. Then, it took 3 hours to raise the internal temperature to 200 ° C, and maintained the temperature until the reaction was completed. On the other hand, the pressure in the reactor was maintained at 97 from 180 ° C to 200 ° C. 3 kPa. Then, it took 2 hours to gradually reduce the pressure to 37.3 kPa, and maintained this pressure until the reaction was completed. During the reaction, a part of the reaction mixture was withdrawn from the reactor, and acid tritium was measured on the extracted sample as an index for confirming the progress of the reaction. The completion of the reaction is based on the acidic acid being 3 or less as the end point, and the time taken from the time the catalyst is added to the reaction vessel to the end of the reaction is taken as the reaction time (the same applies to the following examples and comparative examples). The response time at this time is 7. 5 hours. After the reaction was completed, the heating was stopped and the temperature was cooled to about 100 ° C. The reaction product was extracted, and the viscosity 'acid' and hydroxy 'of the sample were measured. The solubility of the blowing agent (HFC-245fa, HFC-365mfc) to the obtained polyester polyol was measured. • 25- (22) (22) 200415170 Example 2 Except that the stock solution of the feeding ingredients in the side described in Example 1 was not used as the stock solution 1,2-BG②299g, and the stock solution 1,2-BG①275g was used. The reaction was carried out in the same steps (feeding equivalent ratio: hydroxyl / carboxyl = 1. 87). During the reaction, a portion of the reaction mixture was extracted from the reaction mixture, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The response time at this time is 7. 5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agent (HFC-24 5 fa, HFC-3 65 mfc). Comparative Example 1 The reaction was carried out in the same manner as in this example except that 270 g of the stock solution 1,2-BG② of the feeding ingredient in the example described in Example 1 was used instead of 270 g of the test reagent 1,2-BG. Equivalent ratio: hydroxyl / carboxyl = 2. 00). A part of the reaction mixture was taken out from the reactor while the reaction was in progress, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 7.5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agent (HFC-245fc, HFC-3 65mfc). Example 3 A glass reactor having a capacity of 1 liter equipped with a stirrer, a reflux cooler, a thermometer, a pressure gauge, and a heating device was charged with 222 g of phthalic anhydride, 150 g of stock solution 1, 2-BG②, and diethylene glycol. 150 g of alcohol (Feed-26- (23) (23) 200415170 equivalence ratio: hydroxyl / carboxyl = 1.91), the reactor space was replaced with nitrogen, and the reactor contents were heated. When the internal temperature of the reactor reached 180 ° C, tetraisopropyl titanate was added as a catalyst to the reaction. 3 g, start the reaction. Then, it took 3 hours to raise the internal temperature to 20 ° C, and maintained the temperature until the reaction was completed. On the other hand, the pressure in the reactor was from 180 ° C to 200 ° C. Then maintained at 9 7 · 3 kP a. Then, it took 3 hours to slowly decompress to 25. 3 kPa, and maintain this pressure until the reaction is completed. The response time at this time is 7. 5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agent (HFC-2 45 fa, HFC-3 65mfc). Comparative Example 2 The reaction was carried out according to the same procedure in this example (except for feeding 135 g of the stock solution of the feeding ingredients in the example described in Example 3, 1,2 -BG②, and using 135 g of the reagent 1,2-BG). Equivalent ratio: hydroxyl / carboxyl = 2. 00). A part of the reaction mixture was taken out from the reactor while the reaction was in progress, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The response time at this time is 7. 5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the blowing agent (HFC-24 5 fa, HFC-3 6 5 mfc). Example 4 In a 1-liter glass reactor equipped with a stirrer, a reflux cooler, a thermometer, a pressure gauge, and a heating device, terephthalic acid-27- (24) (24) 200415170 was fed with 249 g of acid, Stock solution 1,2-BG②299 (feeding equivalent ratio: hydroxyl / residue = 1. 81). After replacing the space portion of the reactor with nitrogen, heating of the reactor contents was started. When the internal temperature of the reactor reached 180X: as a catalyst, tetraisopropyl titanate was added to the reactor as a catalyst. 3 g, start to react. Then, it took 8 hours to raise the internal temperature to 200 ° C, and maintained the upper temperature until the reaction was completed. On the other hand, the pressure in the reactor was maintained at 97 from 180 ° C to 200 ° C. 3 kPa. Then, it took 2 hours to depressurize slowly to 17 · 5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the carboxyfluorene, and the solubility of the blowing agent (H F C-2 4 5 f a, H F C-3 6 5 m f c). Comparative Example 3 A reaction was carried out in the same manner as in this example except that 1,270-g of stock solution of the feeding ingredients in the example described in Example 4 was used instead of 299 g of 1,2-BG ②, and 270 g of the test reagent was used. Equivalent ratio: hydroxyl / carboxyl = 2. 00). A part of the reaction mixture was taken out from the reactor while the reaction was in progress, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The response time at this time is 7. 5 hours. Table 1 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agent (HFC-245 fa, HFC-3 65 mfc). -28- (25) 200415170 Table-equivalent ratio 1,2-BG purity Acetyloxy content Viscosity (25 ° 〇Acid hydroxy hydroxyl foaming uniform! Solubility HFC · 245fa HFC- 365mfc (wt%) (wt%) ( mPa · s) (mgKOH / g) (mgKOH / g) (g / 100g) Polyester polyol Example 11 1. 82 75 24 7,500 0. 84 203 100 or more 30 Example 2 1. 87 91 3 16,500 0. 70 250 70 13 Comparative example 1 2. 00 99. 5 0. 5 or less 20,000 0. 65 341 50 8 Example 31. 91 75 15 4,200 0. 48 279 80 14 Comparative Example 2 75 0. 5 or less 7,500 0. 65 332 30 5 Example 41. 82 75 H 24 7,500 0. 89 209 100 or more 45 Comparative Example 3 2. 00 99. 5 0. 5 or less 22,000 1. 14 342 65 9 In Table-i, "equivalent ratio" refers to the equivalent ratio of hydroxyl to carboxyl groups (hydroxy / carboxyl) in the feeding ingredients, and "acetic acid oxidation content" refers to 1 in the total alcohol The meaning of the content of 2-AHB and 1,2 DAB. Example 5 A glass reactor having a capacity of 2 liters equipped with a stirrer, a reflux cooler, a thermometer, a pressure gauge, and a heating device was fed with 45 8 g of phthalic anhydride and 1, 2-BG ③ 5 98 g of stock solution (feed Equivalent ratio: hydroxyl / carboxyl = 1. 7 7), after replacing the space portion of the reactor with nitrogen, heating of the reactor contents was started. When the internal temperature of the reactor reached 180 ° C, tetraisopropyl titanate was added to the reactor as a catalyst. 5 g, start to react. Then, it took 3 hours to raise the internal temperature to 200 ° C, and maintained this temperature until the reaction was completed. On the other hand, the pressure in the reactor was maintained at 93 ° C from 180 ° C to 200 ° C. 3kPa. Then, it costs 2. 5 hours slowly -29- (26) (26) 200415170 reduced to 33. 3kPa, and maintain the pressure until the reaction is completed. The determination after the completion of the reaction and the operation after the completion of the reaction were performed in the same manner as in Example 1. The reaction time at this time was 8 hours. Table 2 shows the measurement of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the foaming agents (1 ^ (: -24 5 ..,: ^ (: -3 65 mfc, HCFC14 1b, and cyclopentane)). As a result, it was confirmed that the amount of acetic acid outside the distilling system was distillate until the completion of the reaction, and there was a total of 0.1 in the distillate. 5 4 g of acetic acid. This amount is equivalent to the amount of acetic acid relative to the acetoxy group of the mono- and di-esters contained in the source liquid 1,2-BG. 8%. Here, for a more accurate measurement of the example, a vacuum trap (vac cum trap) cooled with dry ice and acetone was provided between the decompression device and the reactor, but no acetic acid was present therein. Example 6 Except for the example described in Example 5, the feeding ingredients were changed to 429 g of phthalic anhydride, 1,2-BG ③ 623 g of the stock solution, and the final arrival pressure was changed to 44. Except for OkPa, the rest are reacted in the same way as in this example (feeding equivalent ratio: hydroxyl / carboxyl = 1. 97). A portion of the reaction mixture was drawn out from the reactor while the reaction was in progress, and the acid 値 was measured on the extracted sample to confirm the completion of the reaction ', thereby terminating the reaction. The response time at this time was 8 hours. Table 2 shows the results of measuring the viscosity of the reaction product, the solubility of the acid hydrazone, the hydroxyl hydrazone, and the foaming agents (HFC_245 fa, HFC-365mfc, HCFC141b, and cyclopentane). Example 7 -30- (27) 200415170 In addition to the example described in Example 5, the feed composition was changed to 439 g of dicarboxylic anhydride, 1, 2-BG ① 164 g, 1,2, 450 g of the undiluted liquid, and finally the pressure reached. For 38. In addition to 7kPa, the reaction was performed in the same steps in the other examples (feeding equivalent ratio: hydroxyl / carboxyl =. A portion of the reaction mixture was extracted from the reactor during the reaction, and the extracted sample was measured for acid tritium to confirm the completion of the reaction, thereby terminating the anti-time reaction The time is 8 hours. Table 2 shows the reaction viscosity, acid hydrazone, hydroxyl hydrazone, and foaming agent (HFC-245 fa 3 6 5 mfc, HCFC. 141b and cyclopentane) solubility measurement results | Example 8 Except for the example described in Example 5, the feeding ingredients were changed to 45 9 g of dicarboxylic anhydride, stock solution 1, 2-BG① 3 5 8 g, stock solution 1,2 2 3 9g and the final arrival pressure changed to 42. In addition to 7kPa, the reaction was performed in the same steps in the other examples (feeding equivalent ratio: hydroxyl / carboxyl =. A portion of the reaction mixture was drawn from the reactor during the reaction, and the extracted sample was measured for acid tritium to confirm the completion of the reaction, thereby stopping the reaction time. The reaction time was 8 hours. Table 2 shows the measurement results of the reaction viscosity, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agent (HFC-245 fa 365mfc and HCFC141b). Example 9 Except that described in Example 5 In the example, the feed composition is changed to 428g of dicarboxylic anhydride, stock solution 1,2-BG①375g, stock solution 1,2 to o-benzene-BG③, then this: 1. 95) And respond. The HFC- of this product is o-benzene_BG. 88) And respond. The HFC- of this product is o-benzeneBG③ -31-(28) 200415170 2 5 Og and the final arrival pressure changes to 44. Except for OkPa, the reaction was performed in the same steps in the other examples (feeding equivalent ratio: hydroxyl / carboxyl =. A portion of the reaction mixture was withdrawn from the reactor during the reaction, and the extracted sample was measured for acid tritium to confirm the completion of the reaction, thereby stopping the reaction time. The reaction time is 8 hours. Table 2 shows the reaction viscosity, acid hydrazone, hydroxyl hydrazone, and the solubility of the blowing agent (HFC-24 5 fa 3 65 mfc, HCFC 141b, and cyclopentane). 0 Except for the example described in Example 5, the feeding ingredients were changed to 97 g of dicarboxylic anhydride, 1, 2-BG ① 391 g, 1,2 261 g of the stock solution, and the final pressure reached 48. Other than 0kPa, the reaction was performed in the same steps in the other examples (feeding equivalent ratio: hydroxy / carboxyl =. A part of the reaction mixture was withdrawn from the reactor during the reaction, and the extracted sample was measured for acid tritium to confirm the completion of the reaction, thereby stopping the reaction time. The reaction time is 8 hours. Table 2 shows the reaction viscosity, acid hydrazone, hydroxyl hydrazone, and the solubility of the foaming agent (HFC-245fa 3 65mfc, HCFC141b, and cyclopentane). Example 1 1 Except for the examples In the example described in 5, the feeding ingredients were changed to 482 g of dicarboxylic anhydride, stock solution 1,2-BG① 5 7 7 g, and finally changed to 34. Other than 7kPa, the rest follow the same steps in this example and follow the 2AI) and respond as appropriate. The HFC-result of this product. For o-benzene BG ③ then press this: 2. 3 8) And respond. The HFC-- result of this product was o-phenylene pressure. Reaction -32- (29) (29) 200415170 (feeding equivalent ratio: hydroxyl / carboxyl = 1. 8 1). A portion of the reaction mixture was withdrawn from the reactor while the reaction was in progress, and acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 8 hours. Table 2 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agents (HFC-245 fa, HFC-365mfc, and HCFC141b). Example 1 2 Except that in the example described in Example 5, the feeding ingredients were changed to 423 g of phthalic anhydride, 1,2-BG ①, 628 g of the stock solution, and the final arrival pressure was changed to 44.9 kPa. In the example, the reaction was performed in the same steps (feeding equivalent ratio: hydroxyl / carboxyl = 2. twenty four ). A portion of the reaction mixture was withdrawn from the reactor while the reaction was in progress, and acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 8 hours. Table 2 shows the results of the measurement of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the foaming agents (HFC-245fa, HFC-3 65mfc, HCFC141b, and cyclopentane). Example 13 Except for the example described in Example 5, the feeding ingredients were changed to 489 g of phthalic anhydride, stock solution 1,2-BG①3 42 g, stock solution 1,2-BG③ 2 2 8 g, and the final arrival pressure was changed. Other than 3 3 · 3 kPa, the rest are reacted according to the same steps in this example (feeding equivalent ratio · hydroxyl / carboxyl = 1. 6 9). A portion of the reaction mixture was withdrawn from the reactor while the reaction was in progress, and the acid was measured for the sample withdrawn -33- (30) (30) 200415170 to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 8 hours. Table 2 shows the results of measuring the viscosity of the reaction product, the solubility of the acid hydrazone, the hydroxyl hydrazone, and the foaming agents (HFC-24 5 fa, HFC-3 6 5 mfc, H C F C 1 4 1 b, and cyclopentane). Comparative Example 4 Except that in the example described in Example 5, the feeding ingredients were changed to phthalic anhydride 5 5 9 g and reagent 1, 2-BG 5 0 9 g. The rest were the same as in this example. Step reaction (feeding equivalent ratio: hydroxyl / carboxyl = 1. 5 0). A portion of the reaction mixture was withdrawn from the reactor while the reaction was in progress, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 8 hours. Table 2 shows the results of measurement of the viscosity of the reaction product, the solubility of the acid hydrazone, the hydroxyl hydrazone, and the foaming agents (HFC-245 fa, HFC-3 65mfc, and H C F C 1 4 1 b and cyclopentane). Comparative Example 5 Except for the example described in Example 5, the feeding ingredients were changed to phthalic anhydride 5 2 8g, reagent 1,2-BG 5 3 23 g, and the final arrival pressure was changed to 3 7 · 3 Other than kg, the rest are reacted according to the same steps in this example (feeding equivalent ratio: hydroxyl / carboxyl = 1. 63). A portion of the reaction mixture was withdrawn from the reactor while the reaction was in progress, and the acid hydrazone was measured on the extracted sample to confirm the completion of the reaction, thereby terminating the reaction. The reaction time at this time was 8 hours. Table 2 shows the results of measuring the viscosity of the reaction product, the acid hydrazone, the hydroxyamidine, and the foaming agents (HFC-245fa, HFC-365mfc, HCFC141b, and the solubility of cyclopentane-34-(31) (31) 200415170 alkane). . Example 14 4 In a glass reactor with a capacity of 2 liters equipped with a stirrer, a reflux cooler, a thermometer, a pressure gauge, and a heating device, 201 g of succinic acid, 281 g of terephthalic acid, and 1, 2-dichloromethane were fed. BG③641g (feeding equivalent ratio: hydroxyl / carboxyl = 1. 7 3), after replacing the space portion of the reactor with nitrogen, heating of the reactor contents was started. When the internal temperature of the reactor reached 150 ° C, tetraisopropyl titanate was added as a catalyst in the reactor 0. 5 g, start to react. Then, it took 8 hours to raise the internal temperature to 210 ° C 'and maintained this temperature until the reaction was completed. On the other hand, the pressure in the reactor was maintained at 80 ° C from 180 ° C to 210 ° C. 0kPa. Then, it took 4 hours to slowly decompress to 40. OkPa, and maintain this pressure until the reaction is complete. The determination of the completion of the reaction and the operation after the completion of the reaction were performed in the same manner as in Example 1, and the reaction time at this time was 14 hours. Table 2 shows the measurement results of the viscosity of the reaction product, the acid hydrazone, the hydroxyl hydrazone, and the solubility of the blowing agent (HFC-245fa, HFC-3 65mfc, and H C F C 1 4 1 b). 200415170-0 Solubility of blowing agent 〇 Wuyuan (gAOOg polyester polyol) VO BU I 〇> I cannot measure 1 HCFC- 141b 100 or more 100 or more 100 or more 100 or more 100 or more 100 Above 100 or more and 100 or more 0 ψ * " ^ HFC- 365mfc 100 or more and 100 or more I_ 100 or more 1_ in ^ Τ) οο in ^ Τ) Ό in CN o ψ ' < HFC- 245fa 100 or more 100 or more 100 or more 100 or more 100 or more 100 or more v0 o Hydroxyl 値 j 1 E 〇 bO On etc. j_ Η VO (N ΓΜ S m ο m (N m VO 〇 (Ν < ys m (N acid acid (mgKOH / g) ο 〇ο VO 〇〇rn 〇 swallow 0 〇 〇 〇 s) 〇4,900 〇〇〇〇3,200 ο § -Η 〇〇3,100 〇m 200,000 or more 160,000 2,430 Secret ΐ NO i- (wt%) m (N < N ▼ -i m m ▼ Η 0.5 or less 0.5 or less m (N 1,2-BG purity (% by weight) ν〇 VO § 00 00 00 00 〇; On cK ON v〇 _ $ s τ— ^ as ψ < 00 00 1 *-^ r_ _ (N 00 m (N So Ά (N ν〇τ- ^ ΠΊ vq r-4) Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Comparative Example 4 Comparative Example 5 Example 14 舾 * Nig2a · Ga: ^ T 「脑 芒 ύ」 but. ^^ « < fflso% _ svaCNuF ^ KIPQHV-r I, βνΗ- (Ν 二 忉 发 · 康康 了 "_ · ^ 秘 ishoJ But, a 忉 (slightly you / a little look) ± 5__s sorrow slightly 勧 忉 -36 -(33) (33) 200415170 The following facts are known from Tables 1 and 2. (1) The results of comparison between the examples and the comparative examples are 1,2-HAB, 1,2-AHB, and 1,2- in alcohol In the case of the examples in which the total content of DAB is 2 to 24% by weight, compared with the case of 0.5% by weight or less in the comparative example, a polyester polyol having a low viscosity and a high solubility of the foaming agent can be obtained. (2) If the comparison results of Examples 1, 2 and 5 to 13 and Comparative Examples 1, 4 and 5 are compared at the same level by using the feed equivalent ratio (hydroxyl / carboxyl) or hydroxylamidine at the same level, it will be the same as the original solution 1, 2 -When the content (purity) of 1,2-BG contained in BG is 70% by weight or more and 95% by weight or less, compared with the case of using 1,2-BG, which is a special grade of test reagent with a purity of 99.5% by weight or more, A polyester polyol having a low viscosity and a high solubility of the foaming agent can be obtained. (3) Comparison results of Example 3 and Comparative Example 2 Even if it is a part of the raw material alcohol, a solution other than the original liquid 1, 2_B (} is used. Alcohol (two at this time Ethylene glycol), and polyester polyols with low viscosity and high solubility of the blowing agent can still be produced. (4) Comparison results of Example 4 and Comparative Example 3 and Example 14 Even if the raw material is an aromatic carboxylic acid, When terephthalic acid is used instead of phthalic acid or phthalic anhydride, polyester polyols with low viscosity and high solubility of the foaming-37- (34) (34) 200415170 agent can also be prepared. In addition, even if a part of the raw material aromatic carboxylic acid is replaced with a fatty acid carboxylic acid (succinic acid in this case), a polyester polyol having a lower viscosity and a high solubility of a blowing agent can be obtained. Due to its low viscosity and easy handling, the polyester polyol of the present invention has high compatibility with foaming agents, especially with HFC-245fa and / or HFC-3 65mfc. Therefore, it can be useful as a raw material polyol for polyurethane, especially a rigid polyurethane foam. In addition, the instructions of the description of the present invention are cited and included as the subject of this application. Japanese Patent Application No. 2002-313420 (2002 2002) Those who filed an application on May 28) will have the full contents of the manual.