TW200840830A - Urethane resin for vibration damping materials and curable composition - Google Patents

Urethane resin for vibration damping materials and curable composition Download PDF

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Publication number
TW200840830A
TW200840830A TW96140074A TW96140074A TW200840830A TW 200840830 A TW200840830 A TW 200840830A TW 96140074 A TW96140074 A TW 96140074A TW 96140074 A TW96140074 A TW 96140074A TW 200840830 A TW200840830 A TW 200840830A
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Taiwan
Prior art keywords
polyol
damping material
vibration damping
urethane resin
vibration
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TW96140074A
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Chinese (zh)
Inventor
Yukio Matsumoto
Hisashi Sato
Makito Nakamura
Takeaki Arai
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Asahi Glass Co Ltd
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Publication of TW200840830A publication Critical patent/TW200840830A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4244—Polycondensates having carboxylic or carbonic ester groups in the main chain containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2350/00—Acoustic or vibration damping material

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

It is intended to provide a method whereby a urethane resin for vibration damping materials, which has a good adhesiveness, excellent vibration damping properties with a large loss coefficient (tand) and a good balance between the modulus of elasticity and the loss coefficient and shows a good elongation, can be produced. It is also intended to provide a one-pack moisture curable composition which has a low viscosity and a good adhesiveness and a cured article of which shows a high breakage strength and a good elongation.; A method of producing a urethane resin for vibration damping materials by reacting a polyol (A) with a polyisocyanate compound (B), characterized in that the above-described polyol (A) contains a polyester polyether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) with an alkylene oxide (c) by using an initiator (a) in the presence of a catalyst (x). A one-pack moisture curable composition comprising as the curable component an isocyanate-ended prepolymer obtained by reacting a polyol (A) having a hydroxyl value of from 10 to 300 mgKOH/g with a polyisocyanate compound (B), characterized in that the above-described polyol (A) contains a polyester polyether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) with an alkylene oxide (c) by using an initiator (a) in the presence of a catalyst (x).

Description

200840830 九、發明說明 【發明所屬之技術ϋ域】 _ __ 本發明係關於一種減振材料用胺基甲酸乙酯樹脂及硬 . 化性組成物。 【先前技術】 隨著近年之住宅建築物等的高氣密化、高隔熱化的要 ρφ 求，有關建物及外壁等之隔音、遮音性能提昇之各式各樣 硏究已如火如荼地進行。如此地，藉由改善建物及外壁等 之隔音、遮音性能，從建物之外部傳遞至室內之噪音係可 充分降低，且室內之噪音係變成相當低之程度。又，於室 內所產生之噪音、或介由牆壁、地板、天花板而進行傳遞 之另一室的噪音等之對策，係藉由硏究隔間壁等之構造， 俾硏究防止室內門之開關聲音、壁面撞擊聲音、步行聲音 、對話等之生活聲音。 i· 但，在上述之方法中係即使可空氣中傳遞之音，亦無 法防止經由牆壁、地板、天花板等之固體表面而傳遞之聲 音、亦即固體傳遞聲音。因此，就如此之固體傳遞聲音之 噪音、振動的對策而言，硏究使用減振橡膠等之減振材料 。減振材料一般係藉使振動之能量擴散至減振材料中，以 防止振動傳遞者。爲發揮減振材料之減振性，必須增大減 振材料之厚度與使用面積。又，在減振材料中係即使可抑 制傳遞固體之振動，亦無法防止經由固體之表面而進行擴 散的振動。 -6 - 200840830 然而，減振材料係將振動能量變換成熱能而進行振動 吸收者，即使很薄，亦可充分發揮性能，故想出使減振材 料貼黏於地板材、壁材等而防止固體傳遞聲音之產生的方 . 法。 * 以減振材料之振動吸收能一般係以損失係數（tan δ )表示，而該損失係數（tan 5 )係以損失彈性率與貯存 彈性率之比（損失彈性率/貯存彈性率）。此tan 大時 Ρφ ，藉由振動能量變換成熱能而被消耗，俾產生振動吸收而 發揮減振性。 減振材料係常使用來作爲壁材、地板材等之被黏體的 貼合層。因此，要求減振材料具有良好的黏著力。 又’於被黏體貼黏減振材料之構造全體的振動吸收能 係以被黏體與減振材料的貯存彈性率與損失係數之積來表 示。一般壁材、地板材等之被黏體的材料係相較於木、纖 維質系之材料或石頭、混凝土系的材料等減振材料所使用 _鲁 的樹脂系的材料，可使用貯存彈性率高的材料。因此，爲 增大被黏體貼黏減振材料之構造全體的振動吸收能，係宜 使用具有高貯存彈性率的材料作爲減振材料。 又，貯存彈性率愈高，以「損失彈性率/貯存彈性率 」所不之損失係數（tan 6 )變小，故宜以貯存彈性率與 損失係數之均衡變良好之方式進行設計。 專利文獻1中係就貼合2片之建築用板的減振性黏著 劑而言記載丙嫌基乳化液系黏著劑。 但，自以往所使用之丙烯基乳化液系黏著劑係延伸不 200840830 佳，故若使用於熱收縮率互異之被黏體的貼合，藉由被黏 體之熱膨脹、收縮而應力集中於被黏體與黏著劑層之界面 ，易產生剝離。 . 又，於專利文獻2中係記載著對聚醚多元醇使聚羧酸 * 酐與單環氧化物反應所製造之聚酯醚多元醇、鏈延長劑、 及異氰酸酯化合物於觸媒等之助劑的存在下反應而製造胺 基甲酸乙酯的方法。有關減振材料係未記載。 胺基甲酸乙酯樹脂係藉由其優異之黏著性及柔軟性， 使用於黏著劑、塗佈材、密封材、地板床、彈性舖裝材、 防水材等之廣泛用途。 在如此之用途中，已知有單液濕氣硬化型之硬化性組 成物，該單液濕氣硬化型之硬化性組成物係含有使原料多 元醇與異氰酸酯化合物反應所得到之異氰酸酯基末端預聚 物，與空氣中或被黏著基材中之水分反應而進行硬化。又 ，原料多元醇係已知有使用聚醚多元醇或聚酯多元醇。 就原料多元醇而言，若使用常溫液體之聚醚多元醇， 因預聚物變成低黏度，故可得到作業性佳之硬化性組成物 。但，適用於建築材料、汽車零件、食品包裝用薄膜之黏 著劑、或使用於防水材用途之情形、依被黏著基材之種類 而有黏著性不充分之情形。例如，對於使用來作爲地板材 或壁材之聚氯化乙烯製薄片、鋁製薄片係黏著性不充分。 另外’使用己二酸系或酞酸系之聚酯多元醇作爲原料 多元醇之情形，係於聚氯化乙烯製薄片、鋁製薄片之黏著 性優，但在己二酸系聚酯多元醇中係因結晶性高，故在常 -8- 200840830 溫下易變成固體，作業性有問題。又，在單液濕氣硬化型 '中因水分易滲透於樹脂內部，濕氣硬化性易變成不充分。 又，酞酸系聚酯多元醇中係無結晶性者之黏度極高，形成 . 預聚物時，進一步成爲高黏度，故在必須大量之溶劑及可 * 塑劑的倂用上有問題。 因此，提出倂用低黏度之聚醚多元醇、與黏著性優之 聚酯多元醇的方法。但，有聚醚多元醇與聚酯多元醇係相 ΡΦ 溶性差，此等之混合物易分離成二層的問題。又，聚醚多 元醇與聚酯多元醇係因反應性互異，故倂用此等時係必須 經過與異氰酸酯化合物以二階段反應而進行預聚物化等之 繁雜步驟。 亦提出使用聚酯多元醇之預聚物與使用聚醚多元醇之 預聚物的方法，但有相溶性不良且進行分離之問題。 專利文獻3、4中係提出一種使用於聚酯多元醇加成 環氧烷之聚酯-聚醚嵌段共聚物作爲黏著劑之方法。但， ρφ 使用聚酯鏈與聚醚鏈之嵌段共聚合鏈所構成的聚合物，故 易凝集，不能充分低黏度化。 如此，於黏著劑用途所使用之硬化性組成物中係期望 黏著性優且黏度低，但很難使此等共存。爲得到大的黏著 力，宜硬化物中之撕裂強度大，爲得到良好的黏著耐久性 ，宜硬化物之延伸良好。 專利文獻1 ··特開平9 - 203 1 53號公報 專利文獻2 :特開平3 097854號公報 專利文獻3 :特表2003 - 5 1 1 5 3 2號公報 200840830 專利文獻4 :特開2004 _ 1 43 3 1 4 【發明內容】 . (發明之揭示） • (發明欲解決之問題） 本發明係有鑑於上述問題點而構 一種可製造黏著性良好、損失係數大 性率與損失係數之均衡佳且延伸亦良 甲酸乙酯樹脂之的製造方法；使用該 聚物、減振材料用單液濕氣硬化型組 液硬化型系統。 又，本發明之目的在於提供一種 同時硬化物中之撕裂強度及延伸良好 成物。 (用以解決問題之手段） 本發明人等之見識係使習知之聚 聚氧烯烴多元醇）與異氰酸酯化合物 甲酸乙酯樹脂，係相較於使用聚酯多 。又，在-40°c以下之低溫中，tan 値調整至常溫附近，必須增加官能基 份數。其中，很難得到大的tan δ， 有其限度。另外，使用聚酯多元醇之 相較於使用聚醚多元醇者，黏著性良 號公報號 成者，目的在於提供 而減振性優，同時彈 好之減振材料用胺基 方法之減振材料用預 成物及減振材料用雙 黏度低、黏著性優， 之單液濕氣硬化性組 醚多元醇（具體上係 反應所製造之聚胺基 元醇時，黏著強度差 δ成爲峰値，將該峰 數或異氰酸酯之使用 於所得到之彈性率亦 胺基甲酸乙酯樹脂係 好，易得到高的彈性 -10- 200840830 率，但因係結晶性，無法得到大的tan 5。 繼而，本發明人等進一步經累積專心硏究之結果，發 現藉由使用聚酯醚多元醇（A 1)作爲與聚異氰酸酯化合物 (B)反應之成分’可解決以往之問題點，可得到減振材 料用胺基甲酸乙酯樹脂，終完成本發明。 本發明係具有下述之要旨者。 (1) 一種減振材料用胺基甲酸乙酯樹脂的製造方法，其 ρφ 爲使多元醇（A)與聚異氰酸酯化合物（B)反應而製造減 振材料用胺基甲酸乙酯樹脂之方法， 其特徵係該多元醇（A)含有··在觸媒（X)的存在下 ，對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（〇 ) 而得到的聚酯醚多元醇（A1 )。 (2 ) —種減振材料用胺基甲酸乙酯樹脂的製造方法，其 爲使多元醇（A)與聚異氰酸酯化合物（b )反應所得到的 異氰酸酯封端預聚物，進行溼氣硬化而製造減振材料用胺 基甲酸乙酯樹脂之方法， 其特徵係該多元醇（A)含有：在觸媒（X)的存在下 ，對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（c ) 而得到的聚酯醚多元醇（A1 )。 (3 ) —種減振材料用胺基甲酸乙酯樹脂的製造方法，其 爲使多元醇（A)與聚異氰酸酯化合物（B)反應所得到的 異氰酸酯封端預聚物所成的主劑成份、與硬化劑成份反應 而製造減振材料用胺基甲酸乙酯樹脂之方法， 其特徵係該多元醇（A )含有：在觸媒（义）的存在下 -11 - 200840830 ，對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（e ) 而得到的聚酯醚多元醇（A1 )。 (4 )如上述（1 )至（3 )項中任一項之減振材料用胺基 甲酸乙酯樹脂的製造方法，其中該觸媒（X)爲複合金屬 氰化物錯合物。 (5)如前述（1)至（4)項中任一項之減振材料用胺基 甲酸乙酯樹脂的製造方法，其中該多元醇（A )含有2種 Ρφ 以上的該聚酯醚多元醇（A1)，而且該2種以上的聚酯醚 多元醇（A 1 )係玻璃轉移溫度互不相同。 (6 )如前述（5)項之減振材料用胺基甲酸乙酯樹脂的製 造方法，其中該多元醇（A)含有：爲該聚酯醚多元醇（ A1)且玻璃轉移溫度爲-6(TC〜-30°C的範圍之第1聚酯醚 多元醇（All)、與爲該聚酯_多元醇（A1)且玻璃轉移 溫度爲-45°C〜-15°C的範圍之第2聚酯醚多元醇（A12) ，而且該第1聚酯醚多元醇（All)與第2聚酯醚多元醇 (A12)的玻璃轉移溫度的差距爲15°C〜40°C的範圍。 (7 )如前述（1 )至（6 )項中任一項之減振材料用胺基 甲酸乙酯樹脂的製造方法，其中該減振材料用胺基甲酸乙 酯樹脂的耗損係數，在10°C〜5 0°C的範圍爲0.1以上。 (8 ) —種減振材料用胺基甲酸乙酯預聚物，其爲使由多 元醇（A)與聚異氰酸酯化合物（B )反應所得到的異氰酸 酯基封端預聚物所成的減振材料用胺基甲酸乙酯預聚物， 其特徵係該多元醇（A)含有：在觸媒（X)的存在下 ，對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（c ) -12- 200840830 而得到的聚酯醚多元醇（A1 )。 (9 ) 一種減振材料用單液溼氣硬化型組成物，其特徵係 含有前述（8 )項之減振材料用胺基甲酸乙酯預聚物。 (1 〇 ) —種減振材料用雙液硬化型組成物系，其特徵係具 有：含有前述（8)之減振材料用胺基甲酸乙酯預聚物之 主劑組成物、與含有硬化劑成份之硬化組成物。 (1 1 ) 一種單液溼氣硬化性組成物，其爲使羥基價i 〇〜 ρφ 3 00mgKOH/g的多元醇（A)與聚異氰酸酯化合物（B )反 應所得到的異氰酸酯基封端預聚物作爲硬化成份之單液溼 氣硬化性組成物， 其特徵系該多元醇（A)含有：在觸媒（X)的存在下 ，對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（^) 而得到的聚酯醚多元醇（A1 )。 (1 2 )如前述（1 1 )項之單液溼氣硬化性組成物，其中對 於則述起始劑（a )共聚合聚竣酸酐（b )及環氧院（c ) 之反應，係在複合金屬氰化物錯合物觸媒的存在下進行。 (1 3 )如前述（1 1 )項或（i 2 )項之單液溼氣硬化性組成 物，其中該聚酯醚多元醇（A1)中之該聚羧酸酐（^)的 含量爲10〜50質量％。 (14) 如前述（11)項至（13)項中任一項之單液淫氣硬 化性組成物，其中該聚羧酸酐（b )爲酞酸酐。 (15) 如前述（11)項至（14)項中任一項之單液溼氣硬 化性組成物，其係使用於黏著用途。 -13- 200840830 (發明之效果） 若依本發明，可得到一種黏著性良好、損失係數大而 減振性優，同時彈性率與損失係數之均衡佳且延伸亦良好 之減振材料用胺基甲酸乙酯樹脂。 若依本發明，可得到一種黏度低、黏著性優，同時硬 化物中之撕裂強度及延伸良好之單液濕氣硬化性組成物。 (用以實施發明之最佳形態） 〔起始劑（a )〕 於製造聚酯醚多元醇（A1)時所使用之起始劑（a) 係宜使用每一分子具有2〜8個活性氫原子之化.合物。可舉 例如多元醇類、聚胺類、烷醇胺類、酚類。 較佳之具體例可舉例如乙二醇、二乙二醇、聚乙二醇 、丙二醇、二丙二醇、及1，4- 丁二醇等之二元醇類；三 羥甲基丙烷、三羥甲基乙烷、及甘油等之三元醇類；季戊 四醇等之四元醇類；山梨糖醇、及二季戊四醇等之六元醇 類；及蔗糖等之八元醇等之多元醇類；乙二胺、六亞甲基 二胺、及甲苯基二胺等之聚胺類·，單乙醇胺、丙醇胺、及 二乙醇胺等之烷醇胺類；雙酚A等之酚類。 又，對此等之多元醇類、聚胺類、烷醇胺類、酚類加 成環氧烷所得到之每一羥基的羥基價換算分子量爲 150〜1 500之聚醚多元醇（羥基價 37〜374mgKOH/g)亦可 倂用作爲起始劑（a )。 每一羥基的羥基價換算分子量爲1 5 0〜1 5 0 0 (羥基價 -14- 200840830 37〜374mgKOH/g)之聚氧四亞甲基多元醇、聚酯多 及聚碳酸酯多元醇等亦可使用作爲起始劑（a)。 多元醇可舉例如以使多元醇類與多價羧縮合反應所 或以多元醇類作爲起始劑，而使內酯單體開環聚合 者。 起始劑（a)係宜多元醇、或以多元醇作爲起 加成環氧烷之每一羥基的羥基價換算分子量爲1 5 〇〜 羥基價37〜374mgKOH/g )的聚醚多元醇。此聚醚多 尤宜爲製造聚酯醚多元醇（A1)時使用複合金屬氰 錯合物觸媒作爲觸媒（X )之情形。 在本發明中，多元醇之羥基價換算分子量係使 JIS K 1 5 5 7之方法所測定的羥基價，使用下述之式 之値。 羥基價換算分子量=( 56 1 00/羥基價）X多元醇 數。 I· 聚酯醚多元醇（A1 )之羥基數係符合於起始齊 之每一分子之活性氫原子數。在本發明中，上述起 a)更宜使用每一分子具有2〜3個的活性氫原子的 ，更宜在本發明中之聚酯醚多元醇（A1)之羥基數 〇 起始劑（a )之使用比率係相對於使用於聚酯 醇（A1)之合成的全原料饋入量之合計宜爲1.〜60 ，更宜爲1 〇〜60質量％。若起始劑（a )之使用比率 範圍的下限値以上，起始劑之特性易顯性，佳。若 元醇、 該聚酯 得到者 所得到 始劑而 1 5 00 ( 元醇係 化合物 用依據 而計算 之羥基 ίί ( a) 始劑（ 化合物 爲2〜3 醚多元 質量％ 爲上述 起始劑 -15- 200840830 (a)之使用比率爲上述範圍的上限値以下，聚酯醚多元 醇中之聚羧酸酐之量多，故所得到之胺基甲酸乙酯樹脂（ 含有減振材料用胺基甲酸乙酯樹脂及預聚物進行濕氣硬化 所得到之硬化物）之機械物性、減振材料、接著性優。 〔聚羧酸酐（b)〕 ’ 本發明中之聚羧酸酐（b )係可舉例如酞酸酐、馬來 酸酐、琥珀酸酐等。尤其，芳香族之聚羧酸酐係凝集力或 極性極高，故非常有助於各種被黏體之黏著性，故佳。尤 宜爲酞酸酐。 上述聚羧酸酐（b )之使用比率係相對於使用於聚酯 醚多元醇（A1)之合成的全原料饋入量之合計宜爲5〜5 0 質量％，更宜爲10〜50質量％，最宜爲15〜40質量％。藉由 使聚羧酸酐（b )之使用比率爲5質量％以上，可提昇所得 到之胺基甲酸乙酯樹脂的機械強度或黏著性。尤其，可使 _ · 聚羧酸酐（b )之上述使用比率爲1 0質量％以上，俾最終 所得到之減振材料用胺基甲酸乙酯樹脂的玻璃轉移溫度（ 以下，有時亦簡略爲Tg )調整至室溫附近。一般，樹脂 之損失係數（tan 6 )係於玻璃轉移溫度附近變大，故若 減振材料用胺基甲酸乙酯樹脂的Tg爲室溫附近，可有效 率地提昇在室溫之減振材料。 進一步，若聚羧酸酐（b)之上述使用比率爲10質量 %以上，機械強度或黏著性良好。藉由使用比率爲5 0質量 %以下，可抑制所得到之聚酯聚醚多元醇（A 1 )的黏度至 200840830 很低。 〔環氧烷（e)〕 於起始劑（a)中，與聚羧酸酐（b) —起聚合之環氧 烷（c )係宜爲碳數2〜4之環氧烷。具體例可舉例如環氧 丙烷、1，2 -環氧丁烷、2,3 -環氧丁烷、及環氧乙烷等。 環氧烷係可只使用1種，亦可倂用2種以上。在本發明中 ρφ 係宜使用環氧乙烷或環氧丙烷。尤宜只使用環氧丙烷。 環氧烷（c)之使用量相對於聚羧酸酐（b)，宜莫耳 比（c/b)爲5 0/50〜95/5，更宜爲5 0/50〜80/20。環氧烷（C )之莫耳比爲上述範圍的下限値以上，可抑制於聚酯醚多 元醇（A1)中聚羧酸酐（b)之未反應物殘存，並降低聚 酯醚多元醇（A 1 )之酸値。藉形成上述範圍的上限値以下 ，所得到之胺基甲酸乙酯樹脂的黏著性、減振性、機械強 度優。 I· 〔觸媒（X )〕 在本發明中之聚酯醚多元醇（A1)係可藉由對上述起 始劑（a )加成聚合聚羧酸酐（b )及環氧烷（c )來製造 ，但就加速聚合反應之速度而言，宜於聚合反應中使用觸 媒（X )。 該觸媒（X )係可適宜使用開環加成聚合觸媒，具體 例係可舉例如氫氧化鉀、氫氧化鉋等之鹼觸媒，複合金屬 氰化物錯合物觸媒；磷腈（PHOSPHAZENE)觸媒等。 -17- 200840830 從得到Mw/Mn之値更小的聚酯醚多元醇（A1 )，尤 宜使用複合金屬氰化物錯合物觸媒。 複合金屬氰化物錯合物係宜對鋅己烷氰鈷酸鹽錯合物 配位有機配位基。 有機配位根宜爲乙二醇二甲基醚、二乙二醇二甲基醚 等之醚類或第三丁基醇之醇類。 觸媒（X )之使用比率係相對於生成物之聚酯醚多元 醇（Α1)，宜爲0.0001〜〇·1質量％，更宜爲0.003〜0.03質 量％。若觸媒（X )之使用比率爲上述範圍的下限値以上， 確實地產生聚合，若爲上述範圍的上限値以下，殘存觸媒 的不良影嚮少。 〔聚酯醚多元醇（Α1)〕 聚酯醚多元醇（Α1 )較佳係觸媒（X )的存在下，相 對於起始劑（a );可使聚羧酸酐（b )及環氧烷（c )進 I· 行共聚合而得到。 聚酯醚多元醇（A 1 )係可依以下之方法調製。首先使 起始劑（a )、聚羧酸酐（b )及觸媒（X )預先投入於反 應容器中，於其中一邊徐緩地加入環氧烷，一邊反應環氧 烷（c )。其時從環氧烷（c )，聚羧酸酐（b )會開環反 應較快，聚羧酸酐（b )係未連續加成反應，故可得到具 有聚竣酸酐（b )與環氧烷（c ) 一莫耳一莫耳地交互地加 成之共聚合鏈的共聚物。 過剩地添加環氧烷（c )，只於末端以嵌段加成環氧 -18- 200840830 烷（c )，俾可降低所得到之聚酯醚多元醇（A1 )的酸價 。聚酯醚多元醇（A1 )之酸價宜爲2.0mgKOH/g以下，更 宜爲1.0mgKOH/g以下，亦可爲0。若聚酯醚多元醇（A1 )之酸價爲上述之上限値以下，與異氰酸酯之反應性佳， 又，所得到之胺基甲酸乙酯樹脂的耐水解性優，故佳。 於聚酯醚多元醇（A1)中，聚羧酸酐（b)與環氧烷 (c ) 一莫耳一莫耳地交互加成之部分，因兩者之比率爲 ρφ 一定，故以起始劑（a )之分子量與末端之環氧烷（c )的 加成量設計全體的構造。 又，即使使酞酸系聚酯多元醇與聚異氰酸酯化合物反 應所得到之預聚物、與使聚醚多元醇與聚異氰酸酯化合物 反應所得到之預聚物進行混合亦無法得到均一的混合物。 又，使聚酯多元醇與聚醚多元醇先混合，即使對此等 之混合物與聚異氰酸酯化合物反應，相溶性亦不充分。即 使使混合物進行預聚物化，若經過時間，易分離，相溶性 |· 不充分。又，使用此預聚物而得到胺基甲酸乙酯樹脂，即 使欲進行製膜，亦無法得到均一的薄片。 聚酯醚多元醇（A1)之羥基價宜爲11〜112mg KOH/g ，尤宜爲22〜80mgKOH/g。亦即每一羥基之羥基價換算分 子量宜爲 500〜5000，尤其 700〜2500。若每一羥基價換算 分子量宜爲5 00以上，所得到之胺基甲酸乙酯樹脂的減振 性、機械物性優，又，於被黏體基材之接著性成爲優者。 又’若每一羥基價換算分子量宜爲5000以下，所得到之 減振材料用胺基甲酸乙酯樹脂的機械物性優，低黏度化亦 -19 - 200840830 可達成。 該聚酯醚多元醇（A1)之氫基價換算分子量的調製係 可藉由適當調整相對於起始劑（a )聚合之聚羧酸酐（^ ) 及環氧院（c )的莫耳數而容易地實施。 又，聚酯醚多元醇（A1)係使從其氫基價換算分子量 除去起始劑（a )之分子量的殘留之分子量以起始劑（a ) »·200840830 IX. Description of the invention [Technical field to which the invention pertains] _ __ The present invention relates to a urethane resin for a vibration damping material and a hardening composition. [Prior Art] With the high airtightness and high heat insulation of residential buildings and the like in recent years, various types of research on sound insulation and sound insulation performance of buildings and outer walls have been carried out in full swing. In this way, by improving the sound insulation and sound insulation performance of the building and the outer wall, the noise transmitted from the outside of the building to the room can be sufficiently reduced, and the noise in the room becomes quite low. In addition, the noise generated in the room or the noise of another room that is transmitted through the wall, the floor, or the ceiling is controlled by the structure of the partition wall, etc. Sounds of life, sounds of walls, sounds of walking, conversations, etc. i. However, in the above method, even if the sound transmitted in the air is transmitted, the sound transmitted through the solid surface of the wall, the floor, the ceiling or the like, that is, the solid sound can not be prevented. Therefore, in the case of countermeasures against noise and vibration of the solid-transmission sound, a vibration-damping material such as a vibration-damping rubber is used. Damping materials generally spread the vibration energy into the damping material to prevent vibration transmission. In order to exert the vibration damping property of the vibration damping material, it is necessary to increase the thickness and the use area of the vibration damping material. Further, in the vibration damping material, even if the vibration of the transmitted solid can be suppressed, the vibration which is diffused through the surface of the solid cannot be prevented. -6 - 200840830 However, the vibration-damping material is a vibration-absorbing material that converts vibration energy into heat energy, and even if it is thin, it can fully exert its performance. Therefore, it is thought that the vibration-damping material is adhered to the floor material, the wall material, etc., and it is prevented. The method by which solids transmit sound. * The vibration absorption energy of the vibration damping material is generally expressed by the loss coefficient (tan δ ), and the loss coefficient (tan 5 ) is the ratio of the loss elastic modulus to the storage elastic modulus (loss elastic modulus / storage elastic modulus). When tan is large, Ρφ is consumed by converting vibration energy into heat energy, and vibration absorption is generated to exhibit vibration damping. The vibration damping material is often used as a bonding layer of a adherend such as a wall material or a flooring material. Therefore, the damping material is required to have good adhesion. Further, the vibration absorption energy of the entire structure of the adherend-adhesive vibration-damping material is expressed by the product of the storage elastic modulus and the loss coefficient of the adherend and the vibration-damping material. Generally, the material of the adherend such as the wall material and the floor material is used as the damping material of the wood, the fiber material, or the material such as the stone or the concrete material. High material. Therefore, in order to increase the vibration absorption energy of the entire structure of the adherend-adhesive vibration-damping material, it is preferable to use a material having a high storage modulus as a vibration-damping material. Further, the higher the storage elastic modulus, the smaller the loss coefficient (tan 6 ) due to the "loss elastic modulus/storage elastic modulus", and therefore it is preferable to design the balance between the storage elastic modulus and the loss coefficient to be good. In Patent Document 1, a absorbing agent-based adhesive is described as a vibration-damping adhesive for bonding two sheets of construction sheets. However, since the propylene-based emulsion-based adhesive system used in the past is not as good as 200840830, it is used for the adhesion of the adherends having different heat shrinkage rates, and the stress is concentrated by the thermal expansion and contraction of the adherend. The interface between the adherend and the adhesive layer is prone to peeling. Further, Patent Document 2 describes a polyester ether polyol, a chain extender, and an isocyanate compound produced by reacting a polycarboxylic acid polyol with a monoepoxide to a catalyst, and the like. A method of producing ethyl urethane by reacting in the presence of a solvent. The damping materials are not described. The urethane resin is widely used for adhesives, coating materials, sealing materials, floor beds, elastic paving materials, and waterproof materials by virtue of its excellent adhesion and flexibility. In such a use, a one-liquid moisture-curing type curable composition containing an isocyanate group-terminated pre-form obtained by reacting a raw material polyol with an isocyanate compound is known. The polymer is hardened by reacting with moisture in the air or in the adhered substrate. Further, as the raw material polyol, a polyether polyol or a polyester polyol is known. In the case of a raw material polyol, when a polyether polyol of a normal temperature liquid is used, since the prepolymer becomes low in viscosity, a workable curable composition can be obtained. However, it is suitable for use in construction materials, automobile parts, adhesives for film for food packaging, or in the case of use for waterproof materials, and in the case where the adhesion is insufficient depending on the type of the substrate to be bonded. For example, the aluminum chloride sheet which is used as a flooring material or a wall material has insufficient adhesion to an aluminum sheet. In addition, in the case where a polyester polyol of adipic acid type or citric acid type is used as a raw material polyol, it is excellent in adhesion of a polyvinyl chloride sheet and an aluminum sheet, but it is excellent in adipic acid type polyester polyol. Since the middle system has high crystallinity, it tends to become solid at a constant temperature of from -8 to 200840830, and there is a problem in workability. Further, in the one-liquid moisture-curing type, moisture is easily penetrated into the interior of the resin, and the moisture hardenability is likely to be insufficient. Further, in the tannic acid-based polyester polyol, the viscosity of the polyester-free polyester is extremely high, and the prepolymer has a high viscosity. Therefore, there is a problem in that a large amount of a solvent and a plasticizer are required. Therefore, a method of using a low-viscosity polyether polyol and a polyester polyol having excellent adhesion is proposed. However, there is a problem that the polyether polyol and the polyester polyol are poor in solubility, and the mixture is easily separated into two layers. Further, since the polyether polyol and the polyester polyol are different in reactivity, it is necessary to carry out a complicated step of prepolymerizing the isocyanate compound in a two-stage reaction. A method of using a prepolymer of a polyester polyol and a prepolymer using a polyether polyol has also been proposed, but has a problem of poor compatibility and separation. Patent Documents 3 and 4 propose a method of using a polyester-polyether block copolymer of a polyester polyol to form an alkylene oxide as an adhesive. However, ρφ uses a polymer composed of a polyester chain and a block copolymer chain of a polyether chain, so that it is easily aggregated and cannot be sufficiently low in viscosity. As described above, in the curable composition used for the adhesive application, it is desired to have excellent adhesion and low viscosity, but it is difficult to coexist. In order to obtain a large adhesive force, the tear strength in the hardened material is large, and in order to obtain good adhesive durability, the hardened material should be well extended. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. 43 3 1 4 [Description of the Invention] (Disclosure of the Invention) • (Problems to be Solved by the Invention) The present invention has a good balance of adhesion, a large loss rate coefficient and a loss coefficient in view of the above problems. And a method for producing an ethyl formate resin; and a single-liquid moisture-curing liquid-curing system using the polymer and the vibration damping material. Further, it is an object of the present invention to provide a tear strength and a good elongation in a simultaneous hardened body. (Means for Solving the Problems) The inventors of the present invention have made the conventional polyoxyalkylene polyols and the isocyanate compound ethyl urethane resin more than the polyester. Further, in the low temperature of -40 ° C or lower, tan 値 is adjusted to near normal temperature, and the number of functional groups must be increased. Among them, it is difficult to obtain a large tan δ, which has its limits. In addition, the use of a polyester polyol is better than that of a polyether polyol, and the purpose of the adhesive is to provide vibration damping properties, and at the same time, the damping material is damped by an amine method. The pre-formed material and the vibration-damping material are low-viscosity and excellent in adhesion, and the single-liquid moisture-curing group ether polyol (the poly-alcoholic alcohol produced by the specific reaction) has a difference in adhesion strength δ. In other words, the number of peaks or the isocyanate used in the obtained elastic modulus is also excellent in the urethane resin, and a high elasticity-10-200840830 ratio is easily obtained. However, due to the crystallinity, a large tan 5 cannot be obtained. Then, the inventors of the present invention have further accumulated their concentration and found that the use of the polyester ether polyol (A 1 ) as a component reacted with the polyisocyanate compound (B) can solve the conventional problems and can be reduced. The present invention has been completed by the use of a urethane resin. The present invention has the following gist. (1) A method for producing a urethane resin for a vibration damping material, wherein ρφ is a polyol ( A) and polyiso A method for producing a urethane resin for a vibration damping material by reacting an acid ester compound (B), characterized in that the polyol (A) contains an initiator (a) in the presence of a catalyst (X) a polyesterether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (A). (2) A method for producing a urethane resin for a vibration damping material, which is A method for producing a urethane resin for a vibration damping material by isocyanate-terminated prepolymer obtained by reacting a polyol (A) with a polyisocyanate compound (b), which is characterized in that the polyol (A) Containing a polyesterether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (c) with respect to the initiator (a) in the presence of a catalyst (X). A method for producing a urethane resin for a vibration damping material, which is a main component and hardened by an isocyanate-terminated prepolymer obtained by reacting a polyol (A) with a polyisocyanate compound (B) a method for producing a urethane resin for a vibration damping material by reacting a component of the agent, characterized by the plurality of (A) contains: a polyesterether polyol obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (e) with respect to the initiator (a) in the presence of a catalyst (Sense) -11 - 200840830 ( A method for producing a urethane resin for a vibration damping material according to any one of the above items (1) to (3), wherein the catalyst (X) is a composite metal cyanide complex. (5) The method for producing a urethane resin for a vibration damping material according to any one of the items (1) to (4), wherein the polyol (A) contains two kinds of the polyester ether of Ρφ or more The polyol (A1) and the two or more polyester ether polyol (A 1 )-based glass transition temperatures are different from each other. (6) A method for producing a urethane resin for a vibration damping material according to the above (5), wherein the polyol (A) contains: the polyesterether polyol (A1) and a glass transition temperature of -6 (The first polyester ether polyol (All) in the range of TC to -30 ° C, and the first in the range of -45 ° C to -15 ° C of the polyester-polyol (A1) and glass transition temperature 2 Polyetherether polyol (A12), and the difference in glass transition temperature between the first polyester ether polyol (All) and the second polyester ether polyol (A12) is in the range of 15 ° C to 40 ° C. (7) The method for producing a urethane resin for a vibration damping material according to any one of the items (1) to (6), wherein a loss coefficient of the urethane resin for the vibration damping material is 10 The range of °C to 50 °C is 0.1 or more. (8) A urethane prepolymer for a vibration damping material obtained by reacting a polyol (A) with a polyisocyanate compound (B) The isocyanate-terminated prepolymer comprises a urethane prepolymer as a damping material, characterized in that the polyol (A) contains: in the presence of a catalyst (X), for a starter ( a) copolymerization A polyester ether polyol (A1) obtained by combining a polycarboxylic acid anhydride (b) and an alkylene oxide (c) -12 to 200840830. (9) A single-liquid moisture-curing composition for a vibration damping material, characterized by The urethane prepolymer for a vibration damping material according to the above item (8). (1 〇) - a two-liquid hardening type composition for a vibration damping material, characterized in that it has a subtraction from the above (8) The main component of the urethane prepolymer of the vibrating material and the hardening composition containing the hardener component. (1 1 ) A one-liquid moisture-curing composition for making the hydroxyl group i 〇 ρ ρφ An isocyanate-terminated prepolymer obtained by reacting a polyol (A) of 300 mg KOH/g with a polyisocyanate compound (B) as a hardening component, a single-liquid moisture-curing composition characterized by the polyol (A) The polyester ether polyol (A1) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (^) with respect to the initiator (a) in the presence of a catalyst (X). (1 2 ) The one-liquid moisture-curing composition according to the above item (1 1), wherein the starting agent (a) is copolymerized with polyanthracene (b) and a ring The reaction of the compound (c) is carried out in the presence of a double metal cyanide complex catalyst. (1 3 ) The single liquid moisture hardening composition according to the above item (1 1) or (i 2 ), The content of the polycarboxylic acid anhydride (^) in the polyester ether polyol (A1) is from 10 to 50% by mass. (14) The single liquid kinky according to any one of the above items (11) to (13) The gas-hardening composition, wherein the polycarboxylic acid anhydride (b) is a phthalic anhydride. The single-liquid moisture-curing composition according to any one of the above items (11) to (14), which is used for Adhesive use. -13- 200840830 (Effect of the Invention) According to the present invention, an amine group for a vibration damping material having good adhesion, a large loss coefficient, and excellent vibration damping property, and having a good balance between an elastic modulus and a loss coefficient and having a good extension can be obtained. Ethyl formate resin. According to the present invention, a single-liquid moisture-curing composition having a low viscosity, excellent adhesion, and a tear strength and a good elongation in the hardness can be obtained. (Best form for carrying out the invention) [Initiator (a)] The initiator (a) used in the production of the polyesterether polyol (A1) preferably has 2 to 8 activities per molecule. Hydrogen atomization. For example, polyhydric alcohols, polyamines, alkanolamines, and phenols are mentioned. Specific preferred examples thereof include glycols such as ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and 1,4-butanediol; trimethylolpropane and trishydroxyl a trihydric alcohol such as ethane or glycerin; a tetrahydric alcohol such as pentaerythritol; a hexahydric alcohol such as sorbitol or dipentaerythritol; and a polyhydric alcohol such as octaol such as sucrose; A polyamine such as an amine, hexamethylenediamine or tolyldiamine, an alkanolamine such as monoethanolamine, propanolamine or diethanolamine; or a phenol such as bisphenol A. Further, each of the hydroxyl groups obtained by adding a polyhydric alcohol, a polyamine, an alkanolamine or a phenol to an alkylene oxide has a polyether polyol having a molecular weight of 150 to 1 500 in terms of a hydroxyl value (hydroxyl value). 37 to 374 mgKOH/g) can also be used as a starter (a). a polyoxytetramethylene polyol, a polyester polypolyol, a polycarbonate polyol, etc. having a molecular weight of 150 to 150 (hydroxyl-14 - 200840830 37 to 374 mgKOH/g) per hydroxyl group. It can also be used as a starter (a). The polyhydric alcohol may, for example, be a ring-opening polymerization of a lactone monomer by a condensation reaction of a polyhydric alcohol with a polyvalent carboxyl group or a polyhydric alcohol as a starting agent. The initiator (a) is preferably a polyhydric alcohol or a polyether polyol having a molecular weight of from 1 to 5 〇 to a hydroxyl group of 37 to 374 mg KOH/g in terms of a hydroxyl group of each hydroxyl group of the alkylene oxide. This polyether is particularly preferably used in the case of producing a polyester ether polyol (A1) using a composite metal cyanide complex catalyst as a catalyst (X). In the present invention, the hydroxyl group-equivalent molecular weight of the polyol is determined by the method of JIS K 1 5 5 7 and the following formula is used. The molecular weight in terms of hydroxyl value = (56 1 00 / hydroxyl number) X number of polyols. I. The number of hydroxyl groups of the polyesterether polyol (A1) corresponds to the number of active hydrogen atoms per molecule of the starting group. In the present invention, the above a) is more preferably a hydroxyl group starting agent (a) having 2 to 3 active hydrogen atoms per molecule, more preferably a polyester ether polyol (A1) in the present invention. The ratio of use is preferably from 1. to 60, more preferably from 1 to 60% by mass based on the total amount of the raw material fed to the synthesis of the polyesterol (A1). If the lower limit of the range of use of the initiator (a) is 値 or more, the characteristics of the initiator are easily dominant. If the alcohol, the polyester obtains the initiator, and 1 500 (the hydroxyl group compound is calculated based on the hydroxy ίί (a) initiator (the compound is 2 to 3 ether, the mass% is the above initiator - 15- 200840830 (a) The use ratio is the upper limit of the above range 値 or less, and the amount of polycarboxylic acid anhydride in the polyester ether polyol is large, so the obtained urethane resin (containing urethane for vibration damping material) The cured product obtained by moisture hardening of the ethyl ester resin and the prepolymer is excellent in mechanical properties, vibration damping material, and adhesion. [Polycarboxylic acid anhydride (b)] The polycarboxylic acid anhydride (b) in the present invention is For example, phthalic anhydride, maleic anhydride, succinic anhydride, etc. In particular, the aromatic polycarboxylic anhydride has a very high cohesive force or polarity, so it is very helpful for the adhesion of various adherends, so it is preferable to use phthalic anhydride. The use ratio of the above polycarboxylic acid anhydride (b) is preferably from 5 to 50% by mass, more preferably from 10 to 50% by mass based on the total amount of the raw material fed to the synthesis of the polyesterether polyol (A1). %, most preferably 15 to 40% by mass. By making polycarboxylic anhydride (b When the use ratio is 5% by mass or more, the mechanical strength or adhesiveness of the obtained urethane resin can be improved. In particular, the above-mentioned use ratio of the polycarboxylic anhydride (b) can be made 10% by mass or more. The glass transition temperature (hereinafter, also abbreviated as Tg) of the urethane resin obtained finally is adjusted to near room temperature. Generally, the resin loss coefficient (tan 6 ) is based on glass transfer. When the temperature is large, the Tg of the urethane resin in the vibration damping material is near room temperature, and the vibration damping material at room temperature can be efficiently raised. Further, if the polycarboxylic anhydride (b) is used in the above ratio When the content is 10% by mass or more, the mechanical strength or the adhesion is good. By using the ratio of 50% by mass or less, the viscosity of the obtained polyester polyether polyol (A 1 ) can be suppressed to be very low to 200840830. (e) In the initiator (a), the alkylene oxide (c) polymerized with the polycarboxylic acid anhydride (b) is preferably an alkylene oxide having a carbon number of 2 to 4. Specific examples include epoxy. Propane, 1,2-butylene oxide, 2,3-butylene oxide, and ethylene oxide The alkylene oxide may be used alone or in combination of two or more. In the present invention, it is preferred to use ethylene oxide or propylene oxide for pφ, and it is preferred to use only propylene oxide. The amount of use relative to the polycarboxylic anhydride (b), the molar ratio (c/b) is from 50 to 50 to 95/5, more preferably from 50 to 50 to 80/20. When the ear ratio is at least the lower limit 上述 of the above range, the unreacted material of the polycarboxylic acid anhydride (b) in the polyester ether polyol (A1) can be suppressed, and the acid oxime of the polyester ether polyol (A 1 ) can be reduced. When the upper limit 値 of the above range is formed, the obtained urethane resin is excellent in adhesion, vibration damping property, and mechanical strength. I· [Catalyst (X)] The polyesterether polyol (A1) in the present invention can be obtained by addition polymerization of the above-mentioned initiator (a) to a polycarboxylic acid anhydride (b) and an alkylene oxide (c). It is manufactured, but in terms of speeding up the polymerization reaction, it is preferred to use a catalyst (X) in the polymerization reaction. The catalyst (X) may suitably use a ring-opening addition polymerization catalyst, and specific examples thereof include an alkali catalyst such as potassium hydroxide or a hydroxide planer, a composite metal cyanide complex catalyst, and a phosphazene ( PHOSPHAZENE) Catalyst, etc. -17- 200840830 A composite metal cyanide complex catalyst is particularly preferably used for obtaining a polyester ether polyol (A1) having a smaller Mw/Mn. The complex metal cyanide complex is preferably a complex organic ligand to the zinc hexane cyanide cobaltate complex. The organic coordination group is preferably an ether such as ethylene glycol dimethyl ether or diethylene glycol dimethyl ether or an alcohol of a third butyl alcohol. The use ratio of the catalyst (X) is preferably 0.0001 to 〇·1% by mass, more preferably 0.003 to 0.03% by mass based on the polyester ether polyol (Α1) of the product. When the use ratio of the catalyst (X) is at least the lower limit 上述 of the above range, polymerization is surely generated, and if it is below the upper limit 上述 of the above range, the residual effect of the residual catalyst is small. [Polyester ether polyol (Α1)] The polyester ether polyol (Α1) is preferably in the presence of a catalyst (X), relative to the starter (a); the polycarboxylic acid anhydride (b) and the epoxy The alkane (c) is obtained by copolymerization of I. The polyester ether polyol (A 1 ) can be prepared in the following manner. First, the initiator (a), the polycarboxylic acid anhydride (b) and the catalyst (X) are previously placed in a reaction vessel, and the alkylene oxide (c) is reacted while slowly adding the alkylene oxide. At this time, from the alkylene oxide (c), the polycarboxylic acid anhydride (b) will open the ring reaction faster, and the polycarboxylic acid anhydride (b) is not continuously added, so that the polyanthracene anhydride (b) and the alkylene oxide can be obtained. (c) a copolymer of a copolymerized chain which is alternately added in a molar manner. Excessive addition of the alkylene oxide (c) results in the addition of the epoxy group -18-200840830 alkane (c) only at the end, which lowers the acid value of the obtained polyester ether polyol (A1). The acid value of the polyester ether polyol (A1) is preferably 2.0 mgKOH/g or less, more preferably 1.0 mgKOH/g or less, and may be 0. When the acid value of the polyester ether polyol (A1) is not more than the above upper limit ,, the reactivity with the isocyanate is good, and the obtained urethane resin is excellent in hydrolysis resistance. In the polyester ether polyol (A1), the polycarboxylate (b) and the alkylene oxide (c) are mutually additively added, and since the ratio of the two is ρφ, the initial The addition amount of the molecular weight of the agent (a) and the alkylene oxide (c) at the terminal is designed as a whole. Further, even if the prepolymer obtained by reacting the tannic acid-based polyester polyol with the polyisocyanate compound and the prepolymer obtained by reacting the polyether polyol with the polyisocyanate compound are mixed, a uniform mixture cannot be obtained. Further, the polyester polyol and the polyether polyol are first mixed, and even if such a mixture reacts with the polyisocyanate compound, the compatibility is insufficient. Even if the mixture is prepolymerized, if it takes time, it is easy to separate, and the compatibility is insufficient. Further, by using this prepolymer to obtain a urethane resin, even if a film is to be formed, a uniform sheet cannot be obtained. The hydroxyl group of the polyesterether polyol (A1) is preferably from 11 to 112 mg KOH/g, particularly preferably from 22 to 80 mgKOH/g. That is, the molecular weight of each hydroxyl group is preferably from 500 to 5,000, especially from 700 to 2,500. When the molecular weight of each of the hydroxyl groups is preferably 500 or more, the obtained urethane resin is excellent in vibration damping property and mechanical properties, and is excellent in adhesion to the adherend substrate. Further, if the molecular weight per hydroxy value is preferably 5,000 or less, the obtained urethane resin for the vibration damping material is excellent in mechanical properties and low in viscosity, and -19 - 200840830 can be achieved. The molecular weight conversion molecular weight of the polyester ether polyol (A1) can be adjusted by appropriately adjusting the number of moles of the polycarboxylic acid anhydride (^) and the epoxy compound (c) polymerized with respect to the initiator (a). It is easy to implement. Further, the polyesterether polyol (A1) is a residual molecular weight which removes the molecular weight of the initiator (a) from its hydrogen group-valent molecular weight as the initiator (a) »·

之官能基數除之値（Μ，）宜爲1〇〇〜3 000，尤宜爲 200〜2000 〇 此處’ 「從氫基價換算分子量除去起始劑之分子量的 殘留之分子量以起始劑（a )之官能基數除之値（Μ，）」 係意指藉由聚羧酸酐（b)及環氧烷（c)的共聚合所形成 之共聚合鏈每一個的平均分子量。 若前述値（M’）爲3 000以下，所得到之聚酯醚多元 醇（A1)的黏度不會太高，而若前述値（M，）爲1〇〇以 上，可顯現良好的黏著性。前述（Μ，）之調整係與上述氫 基價換算分子量之調整同樣地，係可藉由適當調整相對於 起始劑（a)聚合之聚羧酸酐（b)及環氧烷（c)的莫耳 數而容易地實施。 預聚物在60°C中之黏度並無特別限定，但就單液濕氣 硬化性組成物之塗佈性而言，宜爲200 OOmPa · s以下’更 宜爲1 000〜1 5 000mPa· S之範圍。 在本說明書中之黏度的値係依E型黏度計（東機產業 公司製：RE - 8 0U型），以6 0 °C的條件而測定所得到的 値（單元：mPa · s)。 -20- 200840830 聚酯醚多元醇（A1)係可爲1種，亦可爲2種以上。 藉由倂用玻璃轉移溫度（Tg )互異之2種以上，可擴展所 得到之減振材料用胺基甲酸乙酯樹脂的tan (5値變高之溫 度（峰値溫度）的範圍。The functional group number is preferably 〇〇 3 3 3 Μ Μ Μ , , , , 200 200 200 200 200 200 200 200 200 200 200 200 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 「 The functional group number of (a) is 除 (Μ,)" means the average molecular weight of each of the copolymerized chains formed by the copolymerization of the polycarboxylic acid anhydride (b) and the alkylene oxide (c). If the enthalpy (M') is 3,000 or less, the viscosity of the obtained polyesterether polyol (A1) is not too high, and if the enthalpy (M) is 1 Å or more, good adhesion can be exhibited. . The adjustment of the above (Μ) is similar to the adjustment of the molecular weight in terms of the hydrogen base value, and the polycarboxylic acid anhydride (b) and the alkylene oxide (c) which are polymerized with respect to the initiator (a) can be appropriately adjusted. It is easy to implement with a molar number. The viscosity of the prepolymer at 60 ° C is not particularly limited, but in terms of the coatability of the one-liquid moisture-curable composition, it is preferably 200 00 mPa · s or less, and more preferably 1 000 〜 1 5 000 mPa. The scope of S. The enthalpy of the viscosity in the present specification is measured by an E-type viscometer (manufactured by Toki Sangyo Co., Ltd.: RE-8 0U type) at a temperature of 60 ° C (unit: mPa · s). -20- 200840830 The polyester ether polyol (A1) may be one type or two or more types. By using two or more kinds of different glass transition temperatures (Tg), it is possible to expand the range of tan (5値 high temperature (peak temperature) of the obtained urethane resin for the vibration damping material.

具體上，係宜使於聚酯醚多元醇（A 1 )中所含有、且 玻璃轉移溫度爲-60°C〜-30°C的範圍之第1聚酯醚多元醇 (All)、與於聚酯醚多元醇（A1)中所含有、且玻璃轉 移溫度爲-45°C〜-15°C的範圍之第2聚酯醚多元醇（A12 ) ，以該第1聚酯醚多元醇（All)與第2聚酯醚多元醇（ A12)之玻璃轉移溫度的差成爲15t〜40°C的範圍之方式 組合而倂用。藉由倂用如此之（A1 1 )與（A12 )，可得 到在常溫附近具有高的tan 6之減振材料用胺基甲酸乙酯 樹脂。 聚酯醚多元醇（A1)之玻璃轉移溫度（Tg)係藉由適 當調整當調製該（A1)時所使用之聚羧酸酐（b)的使用 比率俾可調節至所希望之溫度。例如，對於不含有聚羧酸 酐（b)之聚氧丙二醇之玻璃轉移溫度（Tg)爲約_7〇°C， 但若使用聚羧酸酐（b) 10質量％而共聚物（聚酯醚多元 醇（A1))，可調節玻璃轉移溫度至-6〇°C以上。 倂用上述（All)與（A12)時，兩者之使用量的質 量比（A11/A12 ) 宜爲 5/95〜95/5 的範圍，更宜爲 20/80〜80/20 〇 〔多元醇（A)〕 -21 - 200840830 多元醇（A)係含有上述聚酯醚多元醇（A1)。 在多元醇（A)的全量中之聚酯醚多元醇（A1)的含 量宜爲30質量％以上，更宜爲50質量％以上。實質上最 宜爲100質量％爲聚醚醚多元醇（A1 ) ° 多元醇（A)之羥基價宜爲10〜3 00mgKOH/g。更宜爲 11 〜112 mgKOH/g，尤宜爲 22 〜80 mgKOH/g。亦即，每一 羥基的氫基價換算分子量宜爲 187〜5610，更宜爲 _· 5 00〜5000，尤宜爲 700〜2500。 多元醇（A)所含有之上述聚酯醚多元醇（A1)以外 的其他之多元醇（A2)係以每一分子的活性氫原子數爲 2〜8個的分子量作爲起始劑，使環氧烷進行開環加成聚合 而得到之聚氧丙烯多元醇、聚氧乙烯多元醇、聚氧乙烯丙 烯多元醇；使多元醇類與多價羧酸縮合反應所得到之聚酯 多元醇；以多元醇類作爲起始劑而使內酯單體開環聚合所 得到之聚酯多元醇；聚氧四亞甲基多元醇；聚碳酸酯多元 ，鲁 醇等。該其他之多元醇（A2 )宜爲羥基數2〜8個的多元醇 ，宜爲2〜3個的多元醇。其他之多元醇（A2 )的羥基價宜 爲10〜3 00 mgKOH/g，更宜爲11〜112 mgKOH/g，尤宜爲 22〜80 mgKOH/g。亦即，每一羥基之羥基價換算分子量宜 爲187〜5610，最爲500〜5000，尤宜爲700〜2500。 多兀醇（A)之全量中的其他多元醇（A2)之含量宜 爲70質量％以下，更宜爲50質量％以下，亦可爲〇。 〔聚異氰酸酯化合物（B)〕 -22- 200840830 於本發明中可使用之聚異氰酸酯化合物（B)(有時 亦僅稱爲聚異氰酸酯（B))係無特別限定，但可舉例如 二苯基甲烷二異氰酸酯、聚苯撐基聚亞甲基聚異氰酸酯、 2，4 -甲苯撐基二異氰酸酯、及2,6 —甲苯撐基二異氰酸酯 等之芳香族聚異氰酸酯化合物；二甲苯撐基二異氰酸酯、 間四甲基二甲苯撐基二異氰酸酯等之芳烷基聚異氰酸酯化 合物；六亞甲基二異氰酸酯、2,2，4 _三甲基六亞甲基二異 I· 氰酸酯等之脂肪族聚異氰酸酯化合物；異佛爾酮二異氰酸 酯及4,4’ -亞甲基雙（環己基異氰酸酯）等之脂環族聚異 氰酸酯化合物；以及，從前述聚異氰酸酯化合物所得到之 胺基甲酸乙酯改性體、縮二脲改性體、脲基甲酸酯、羰二 醯亞胺改性體及三聚異氰酸酯改性體等。 與多元醇（A )之反應性優、及所得到之減振材料用 胺基甲酸乙酯樹脂的黏度、或單液濕氣硬化性組成物之黏 度易變低，故聚異氰酸酯化合物（B)宜爲芳香族二異氰 I# 酸酯及此等之改性體。其中，宜爲二苯基甲烷二異氰酸酯 、聚苯撐基聚亞甲基聚異氰酸酯、2,4-甲苯撐基二異氰. 酸酯、及2,6 -甲苯撐基二異氰酸酯以及此等之改性體。 聚異氰酸酯化合物（B )可一種單獨使用，亦可倂用 2種以上。 〔預聚物〕 本發明中之異氰酸酯基末端預聚物係使多元醇（A) 與聚異氰酸酯化合物（B )反應而得到。 -23 - 200840830 該異氰酸酯基末端預聚物係使上述多元醇（A)與聚 異氰酸酯化合物（B )以莫耳比（異氰酸酯基/羥基）對異 氰酸酯基之羥基成爲1.3〜10.0之方式反應所得到。該莫耳 比係更宜爲1·8〜7.0。該莫耳比未達1.3以上，所生成之預 聚物的黏度變成不太高，而就作業性、濕氣硬化性而言， 佳。又，形成1 0 · 0以下，未反應之聚異氰酸酯化合物（Β )的殘存少，最終所得到之硬化性組成物的硬化物之機械 物性變良好。 異氰酸酯基末端預聚物中之異氰酸酯基含量宜爲 0·5〜20質量％，更宜爲1〜15質量％，尤宜爲1〜12質量％ 。若該異氰酸酯基含量爲〇·5以上，黏度不太高，就作業 性、濕氣硬化性而言，佳。若爲20質量％以下，未反應之 聚異氰酸酯化合物的殘存少，最終所得到之硬化性組成物 的硬化物之機械物性變良好。Specifically, it is preferred to use the first polyester ether polyol (All) contained in the polyester ether polyol (A 1 ) and having a glass transition temperature of from -60 ° C to -30 ° C. a second polyester ether polyol (A12) contained in the polyesterether polyol (A1) and having a glass transition temperature of -45 ° C to -15 ° C, and the first polyester ether polyol ( All) is used in combination with a method in which the difference in glass transition temperature of the second polyester ether polyol (A12) is in the range of 15 t to 40 °C. By using such (A1 1 ) and (A12), a urethane resin for a vibration damping material having a high tan 6 in the vicinity of normal temperature can be obtained. The glass transition temperature (Tg) of the polyesterether polyol (A1) can be adjusted to a desired temperature by appropriately adjusting the use ratio of the polycarboxylic acid anhydride (b) used in the preparation of the (A1). For example, the glass transition temperature (Tg) of the polyoxypropylene glycol not containing the polycarboxylic acid anhydride (b) is about _7 〇 ° C, but if the polycarboxylic anhydride (b) is used in an amount of 10% by mass, the copolymer (polyester ether plural) Alcohol (A1)), the glass transition temperature can be adjusted to above -6 °C. When using the above (All) and (A12), the mass ratio of the two used (A11/A12) should be in the range of 5/95 to 95/5, more preferably 20/80 to 80/20 〇 [multiple Alcohol (A)] -21 - 200840830 The polyol (A) contains the above polyester ether polyol (A1). The content of the polyesterether polyol (A1) in the total amount of the polyol (A) is preferably 30% by mass or more, more preferably 50% by mass or more. In essence, it is preferably 100% by mass of the polyetherether polyol (A1). The hydroxyl group (A) preferably has a hydroxyl group value of 10 to 300 mgKOH/g. More preferably, it is 11 to 112 mgKOH/g, and particularly preferably 22 to 80 mgKOH/g. That is, the hydrogen group-based molecular weight of each of the hydroxyl groups is preferably 187 to 5610, more preferably _·5 00 to 5,000, particularly preferably 700 to 2,500. The polyol (A2) other than the above-mentioned polyester ether polyol (A1) contained in the polyol (A) is a starting point of a molecular weight of 2 to 8 per molecule, and the ring is used as a starting agent. a polyoxypropylene polyol, a polyoxyethylene polyol, a polyoxyethylene propylene polyol obtained by subjecting an oxane to ring-opening addition polymerization; a polyester polyol obtained by condensing a polyol with a polyvalent carboxylic acid; A polyester polyol obtained by ring-opening polymerization of a lactone monomer as a starter; a polyoxytetramethylene polyol; a polycarbonate polyol, a diol, and the like. The other polyol (A2) is preferably a polyol having 2 to 8 hydroxyl groups, preferably 2 to 3 polyols. The hydroxyl value of the other polyol (A2) is preferably from 10 to 300 mgKOH/g, more preferably from 11 to 112 mgKOH/g, particularly preferably from 22 to 80 mgKOH/g. That is, the molecular weight of each hydroxyl group is preferably 187 to 5610, most preferably 500 to 5,000, and particularly preferably 700 to 2,500. The content of the other polyol (A2) in the total amount of the polyterpene alcohol (A) is preferably 70% by mass or less, more preferably 50% by mass or less, and may be hydrazine. [Polyisocyanate compound (B)] -22- 200840830 The polyisocyanate compound (B) (sometimes referred to simply as polyisocyanate (B)) which can be used in the present invention is not particularly limited, and examples thereof include diphenyl group. An aromatic polyisocyanate compound such as methane diisocyanate, polyphenylene polymethylene polyisocyanate, 2,4-tolyl diisocyanate, and 2,6-tolyl diisocyanate; xylylene diisocyanate, An aralkyl polyisocyanate compound such as tetramethylxylylene diisocyanate; an aliphatic group such as hexamethylene diisocyanate or 2,2,4-trimethylhexamethylene diiso I. cyanate a polyisocyanate compound; an alicyclic polyisocyanate compound such as isophorone diisocyanate or 4,4'-methylenebis(cyclohexyl isocyanate); and a urethane modified from the above polyisocyanate compound A modified body, a biuret modified product, an allophanate, a carbonyl diinimide modified product, a trimerized isocyanate modified body, or the like. The polyisocyanate compound (B) is excellent in reactivity with the polyol (A), and the viscosity of the obtained urethane resin for the vibration damping material or the viscosity of the one-liquid moisture-curable composition is apt to be low. It is preferably an aromatic diisocyanide I# acid ester and such modified body. Among them, it is preferably diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, 2,4-tolyl diisocyanate, and 2,6-tolyl diisocyanate, and the like. Modified body. The polyisocyanate compound (B) may be used alone or in combination of two or more. [Prepolymer] The isocyanate group-terminated prepolymer in the present invention is obtained by reacting a polyol (A) with a polyisocyanate compound (B). -23 - 200840830 The isocyanate group-terminated prepolymer is obtained by reacting the above polyol (A) and polyisocyanate compound (B) with a molar ratio (isocyanate group / hydroxyl group) to a hydroxyl group of an isocyanate group of 1.3 to 10.0. . The molar ratio is preferably from 1. 8 to 7.0. When the molar ratio is less than 1.3, the viscosity of the produced prepolymer becomes not too high, and it is preferable in terms of workability and moisture hardenability. Further, when it is 10 or less, the amount of the unreacted polyisocyanate compound (Β) remains small, and the mechanical properties of the cured product of the curable composition finally obtained are improved. The isocyanate group content in the isocyanate group-terminated prepolymer is preferably from 0.5 to 20% by mass, more preferably from 1 to 15% by mass, particularly preferably from 1 to 12% by mass. When the content of the isocyanate group is 〇·5 or more, the viscosity is not so high, and it is preferable in terms of workability and moisture hardenability. When the amount is 20% by mass or less, the residual amount of the unreacted polyisocyanate compound is small, and the mechanical properties of the cured product of the curable composition finally obtained are improved.

〔單液濕氣硬化性組成物〕 本發明之單液濕氣硬化性組成物係使多元醇（A )與 聚異氰酸酯化合物（B )反應所得到的異氰酸酯基末端預 聚物，爲藉由與水分之反應以進行硬化之硬化成分，使該 硬化成分濕氣硬化者，例如，不使用低分子量多元醇或聚 胺等之鏈延長劑或硬化劑而硬化者。 本發明之單液濕氣硬化性組成物係在水分不進入之條 件下進行製造，置入密閉容器，保存，使用時從容器取出 ，塗佈於基材上，藉由曝露於大氣中以使空氣中之水分（ -24- 200840830 濕氣）與硬化成分中之異氰酸酯基反應來硬化。 無特別 添加劑 充分混 本發明之單液濕氣硬化性組成物的製造方法係 限定，但較佳係添加前述必須成分與依需要之各種 ’在減壓下或氮環境下使用混合機等之攪拌裝置而 練而均一地分散以形成組成物。 〔添加劑〕 物中之 依需要而添加於本發明之單液濕氣硬化性組成 添加劑，可舉例如以下者。 (硬化觸媒） 反應或 級胺化 2 -乙 就硬化觸媒而言，可使用促進胺基甲酸乙酯化 尿素反應之公知的觸媒，可舉例如三乙基胺等之三 合物、二丁基錫二月桂酸酯、二辛基錫馬來酸酯、 基己烷酸錫等之有機酸錫或有機酸鉛等。 (可塑劑） 丁基' 、琥珀 二醇聚 就可塑劑而言，可舉例如酞酸二辛基、酞酸二 酞酸二異壬基、己二酸二辛基酯、己二酸二異壬酯 酸異癸酯、油酸丁酯、磷酸三甲苯基酯、己二酸丙 酯、糠油脂肪酸酯等。 (溶劑） 溶劑。 於本發明之單液濕氣硬化性組成物中亦可含有 -25- 200840830 尤其在食品包裝薄膜用之黏著劑用途中宜使用溶劑。 可使用之溶劑可舉例如異石鱲、礦物醇液等之脂肪族 烴類；醋酸乙酯、醋酸丁酯等之醋酸酯類；甲乙酮、甲基 異丁基酮等之酮類；甲苯、二甲苯等之芳香族烴類；二甲 基甲醯胺等之醯胺類。 本發明之單液濕氣硬化性組成物係藉由使用特定之聚 酯醚多元醇（A 1 )以低黏度化，故即使使用溶劑，以少量 之使用可得到良好的黏度。又，亦可使用弱溶劑（Mild Solvent、非芳香族烴系溶劑）。 (塡充劑）[Single liquid moisture-curing composition] The one-liquid moisture-curing composition of the present invention is an isocyanate-based terminal prepolymer obtained by reacting a polyol (A) with a polyisocyanate compound (B), by The moisture is reacted to harden the hardened component, and the hardened component is cured by moisture, for example, without using a chain extender such as a low molecular weight polyol or a polyamine or a hardener. The single-liquid moisture-curing composition of the present invention is produced under the condition that moisture does not enter, is placed in a sealed container, stored, taken out from the container during use, applied to a substrate, and exposed to the atmosphere. The moisture in the air ( -24- 200840830 Moisture) reacts with the isocyanate groups in the hardening component to harden. The method for producing the one-liquid moisture-curing composition of the present invention is not particularly limited, but it is preferred to add the above-mentioned essential components and various kinds of stirring as needed under a reduced pressure or a nitrogen atmosphere. The device is trained to uniformly disperse to form a composition. The single-component moisture-curable composition additive to be added to the present invention in the [additive] may be, for example, the following. (Curing the catalyst) The reaction or the amination of the 2-A, in the case of the hardening catalyst, a known catalyst for promoting the reaction of the ethyl urethane to the urea may be used, and for example, a trimeric compound such as triethylamine may be used. An organic acid tin such as dibutyltin dilaurate, dioctyltin maleate or tin hexanoate or lead acid or the like. (Plasticizer) The butyl ' and amber diol polyaddition plasticizers include, for example, dioctyl phthalate, diisononyl phthalate, dioctyl adipate, diisobutyl adipate. Isodecyl decyl ester, butyl oleate, tricresyl phosphate, propyl adipate, eucalyptus fatty acid ester, and the like. (solvent) Solvent. The single-liquid moisture-curable composition of the present invention may also contain -25- 200840830. It is preferred to use a solvent especially for use in an adhesive for food packaging films. Examples of the solvent to be used include aliphatic hydrocarbons such as isoindazin and mineral alcohol liquid; acetates such as ethyl acetate and butyl acetate; ketones such as methyl ethyl ketone and methyl isobutyl ketone; toluene and An aromatic hydrocarbon such as toluene; or a guanamine such as dimethylformamide. The one-liquid moisture-curing composition of the present invention has a low viscosity by using a specific polyether ether polyol (A 1 ), so that even if a solvent is used, a good viscosity can be obtained with a small amount. Further, a weak solvent (Mild Solvent, a non-aromatic hydrocarbon solvent) can also be used. (塡剂)

於本發明之單液濕氣硬化性組成物係依需要而可調配 塡充材。尤其，在建築材料用黏著劑、塗佈材、密封材、 彈性舖裝材、防水材等之黏著用途中係藉由調配塡充材， 俾於垂直面亦很難垂流，塗佈量均一地安定，黏著性安定 化，故佳。塡充材之具體例可舉例如碳酸鈣、氧化鈦、碳 酸鎂、氧化鎂、氫氧化鎂、氧化鐵、氧化鋅、氧化鋇、碳 酸鋅、碳黑、二氧化矽類、矽藻土等。塡充材之使用量係 硬化性組成物（100質量％)中爲〇〜6〇質量％，宜爲〇〜50 質量％，藉由形成60質量％以下，俾黏著劑之塗佈作業性 佳。 (其他之助劑） 進一步，依需要而可使用搖變性賦予劑、抗氧化劑、 -26 - 200840830 紫外線吸收劑、顏料、消泡劑、耐燃劑、黏著賦予劑等。 搖變性賦予劑可舉例如微粒碳酸鈣、噴霧劑（曰本 Aerosil公司品）、脂肪族醯胺、氫添加蓖麻油等。 抗氧化劑可舉例如丁基羥甲基苯（BHT ) .、丁基羥基 茴香醚（BHA)、二苯基胺、苯二胺、亞磷酸三苯基酯等 紫外線吸收劑可舉例如阻酚系、苯並三唑系、阻胺系 »·The one-liquid moisture-curing composition of the present invention can be formulated with a ceramium filler as needed. In particular, in the adhesive application of adhesives, coating materials, sealing materials, elastic paving materials, and waterproof materials for building materials, it is difficult to sag in a vertical surface by applying a sputum filling material, and the coating amount is uniform. The ground is stable, the adhesion is stable, so it is good. Specific examples of the cerium filling material include calcium carbonate, titanium oxide, magnesium carbonate, magnesium oxide, magnesium hydroxide, iron oxide, zinc oxide, cerium oxide, zinc carbonate, carbon black, cerium oxide, and diatomaceous earth. The amount of use of the ruthenium filler is 〇~6〇% by mass in the curable composition (100% by mass), preferably 〇50% by mass, and the coating workability of the 俾 adhesive is good by forming 60% by mass or less. . (Other additives) Further, a shake imparting agent, an antioxidant, a fluorosorber -26 - 200840830, a pigment, an antifoaming agent, a flame retardant, an adhesion imparting agent, or the like can be used as needed. Examples of the thixotropy-imparting agent include particulate calcium carbonate, a spray (product of Aero本 Aerosil Co., Ltd.), an aliphatic guanamine, hydrogen-added castor oil, and the like. The antioxidant may, for example, be a butyl hydroxymethyl benzene (BHT), a butyl hydroxyanisole (BHA), a diphenylamine, a phenylenediamine or a triphenyl phosphite. , benzotriazole system, hindered amine system»

等。 於顏料中係有無機顏料與有機顏料，無機顏料係可使 用二氧化鈦、氧化鋅、群青、氧化鐵紅、鋅鋇白、氧化鉛 、硫化鎘、氧化鈷、氧化鋁等。有機顏料可舉例如偶氮顏 料、銅酞氰顏料等。 消泡劑可舉例如聚矽氧烷化合物等。 耐燃劑係可使用氯烷基磷酸酯、二甲基/甲基磷酸酯 、銨聚磷酸酯、新戊基溴化-聚醚、溴化聚醚、溴磷化合 物。 黏著賦予劑係可使用萜烯樹脂、酚樹脂、松香樹脂、 二甲苯樹脂。 本發明之單液濕氣硬化性組成物係如後述之實施例所 示般’因低黏度，作業性良好。又，黏著後之剝離強度高 而黏著性優，同時硬化物中之撕裂強度及延伸良好。而且 ’可使用於對廣範圍的材料之黏著用途。 就被黏著基材而言，可使用於木材之外，鋁、鐵、銅 等之金屬材料；聚醯胺、聚對苯二甲酸乙二酯、耐隆、聚 -27- 200840830 丙烯等之樹脂材料；混凝土、瀝青、石材等廣範圍的材料 。此等之被黏著材料之中，宜爲木材；鋁；聚醯胺·，聚對 苯二甲酸乙二酯等之樹脂，尤其，與鋁之黏著性優。 〔減振材料用胺基甲酸乙酯樹脂之製造方法〕Wait. Inorganic pigments and organic pigments are used in the pigments, and titanium oxide, zinc oxide, ultramarine blue, iron oxide red, zinc antimony white, lead oxide, cadmium sulfide, cobalt oxide, aluminum oxide, and the like can be used as the inorganic pigment. The organic pigment may, for example, be an azo pigment or a copper cyanide pigment. The antifoaming agent may, for example, be a polyoxyalkylene compound or the like. As the flame retardant, chloroalkyl phosphate, dimethyl/methyl phosphate, ammonium polyphosphate, neopentyl bromide-polyether, brominated polyether, bromine phosphorus compound can be used. As the adhesion imparting agent, a terpene resin, a phenol resin, a rosin resin, or a xylene resin can be used. The one-liquid moisture-curing composition of the present invention is excellent in workability due to low viscosity as shown in the examples described later. Further, the peel strength after adhesion is high and the adhesion is excellent, and the tear strength and elongation in the hardened material are good. Moreover, ' can be used for adhesion to a wide range of materials. For the adhesive substrate, it can be used for wood, aluminum, iron, copper, etc.; polyamine, polyethylene terephthalate, tron, poly-27-200840830 propylene, etc. Materials; a wide range of materials such as concrete, asphalt, and stone. Among these adhered materials, wood, aluminum, polyamine, polyethylene terephthalate, and the like are preferable, and in particular, adhesion to aluminum is excellent. [Method for Producing Aurethane Resin for Damping Material]

本發明之減振材料用胺基甲酸乙酯樹脂係使用上述多 元醇（A )與聚異氰酸酯化合物（B )來製造。較佳之製造 方法可舉例如下述之3種的方法。 第1製造方法：使多元醇（A)與聚異氰酸酯化合物 (B )與依需要之鏈延長劑及/或硬化劑反應而製造減振材 料用胺基甲酸乙酯樹脂的方法。 第2製造方法：使多元醇（A)與聚異氰酸酯化合物 (B )反應而得到異氰酸酯基末端預聚物，然後使該預聚 物溼氣硬化而製造減振材料用胺基甲酸乙酯樹脂之方法。 第3製造方法··使多元醇（A )與聚異氰酸酯化合物 (B)反應而得到異氰酸酯基末端預聚物，使該預聚物所 構成之主劑成份與硬化劑成份反應而製造減振材料用胺基 甲酸乙酯樹脂之方法。 (第1製造方法） 在上述第1製造方法中係以異氰酸酯基/羥基就莫耳 比成爲1.2〜0.7，較佳係成爲1.1〜0.9之方式，使多元醇 (A)與聚異氰酸酯（B)與依需要之鏈延長劑及/或硬化 劑反應而製造減振材料用胺基甲酸乙酯樹脂（硬化物）° -28 - 200840830 本方法係就一次注入法（one shot )而言適用公知之 方法而實施。一次注入法係使多元醇（A)與聚異氰酸酯 化合物（B )與依需要之鏈延長劑及/或硬化劑反應同時地 加入而製造聚胺基甲酸乙酯樹脂之方法，亦可一起使用觸 媒。The urethane resin for a vibration damping material of the present invention is produced by using the above polyol (A) and a polyisocyanate compound (B). The preferred production method is, for example, the following three methods. The first production method is a method for producing a urethane resin for a vibration damping material by reacting a polyol (A) with a polyisocyanate compound (B) with an optional chain extender and/or a curing agent. In the second production method, the polyol (A) is reacted with the polyisocyanate compound (B) to obtain an isocyanate group-terminated prepolymer, and then the prepolymer is moisture-cured to produce a urethane resin for a vibration damping material. method. In the third production method, the polyol (A) is reacted with the polyisocyanate compound (B) to obtain an isocyanate group-terminated prepolymer, and the main component of the prepolymer is reacted with a hardener component to produce a vibration damping material. A method using a urethane resin. (First Manufacturing Method) In the first production method, the polyol (A) and the polyisocyanate (B) are obtained such that the isocyanate group/hydroxy group has a molar ratio of 1.2 to 0.7, preferably 1.1 to 0.9. A urethane resin (cured product) for producing a vibration damping material by reacting with a chain extender and/or a hardener as needed. -28 - 200840830 This method is applicable to one shot. Implemented by the method. The one-shot method is a method in which a polyol (A) and a polyisocyanate compound (B) are simultaneously reacted with an optional chain extender and/or a hardener to produce a polyurethane resin, and may be used together. Media.

在本方法中’於前述反應器中，除前述多元醇（A) 及聚異氰酸酯化合物（B)之外，亦可同時地加入不與多 元醇（A)與聚異氰酸酯化合物（B)之任一起反應之其他 聚合物。 •h述其他之聚合物係只要不具有與異氰酸酯基及羥基 之一者或兩者反應之官能基者即可。具體例可舉例如苯乙 烯一異戊二烯橡膠等之以往公知的苯乙烯系（共）聚合物 、丙烯系共聚物、乙烯一丙烯共聚物、改性聚矽氧樹脂等 。此等係可一種單獨使用亦可混合兩種以上而使用。 上述其他之聚合物的使用比率系宜相對於多元醇（A )與聚異氰酸酯化合物（B)與其他之聚合物的合計1〇〇 質量份，宜爲200質量份以下，更宜爲1〇〇質量份以下。 亦可爲〇。 鏈延長劑及/或硬化劑係可使用公知之鏈延長劑及/或 硬化劑。一般所謂鏈延長劑係於一分子中具有2個可與異 氰酸酯基加成反應之官能基的比較低分子量之化合物，所 謂硬化劑係於一分子中具有3個可與異氰酸酯基加成反應 之官能基的比較低分子量之化合物。兩者之分子量宜爲 1 122以下者，更宜爲1 000以下，尤宜爲600以下者。 -29 - 200840830 鏈延長劑及/或硬化劑之化學構造並無特別限定’但 具體上可舉例如以下者。 鏈延長劑舉例如二醇類例如乙二醇、二乙二醇、三乙 二醇、丙二醇、二丙二醇、三丙二醇、1，4 一丁二醇、1，6 一己二醇、異戊二醇，1，4一環己烷二甲醇、及1，4 一二羥 基環己烷等。此等之中，宜爲乙二醇、丙二醇、1，4 一丁 二醇及1，6—己二醇，尤宜爲1，4 一丁二醇。In the present process, in addition to the aforementioned polyol (A) and the polyisocyanate compound (B), it may be added simultaneously with the polyol (A) and the polyisocyanate compound (B). Other polymers that react. • The other polymer system may be any one which does not have a functional group which reacts with one or both of an isocyanate group and a hydroxyl group. Specific examples thereof include conventionally known styrene-based (co)polymers such as styrene-isoprene rubber, propylene-based copolymers, ethylene-propylene copolymers, and modified polyfluorene-oxygen resins. These may be used alone or in combination of two or more. The use ratio of the above other polymers is preferably 1 part by mass, more preferably 200 parts by mass or less, more preferably 1 part by mass based on the total of the polyol (A) and the polyisocyanate compound (B) and the other polymer. Below the mass. It can also be awkward. As the chain extender and/or the hardener, a known chain extender and/or a hardener can be used. Generally, a chain extender is a relatively low molecular weight compound having two functional groups capable of reacting with an isocyanate group in one molecule. The so-called hardener has three functional groups capable of reacting with an isocyanate group in one molecule. A relatively low molecular weight compound. The molecular weight of the two should preferably be 1 122 or less, more preferably 1 000 or less, and particularly preferably 600 or less. -29 - 200840830 The chemical structure of the chain extender and/or the hardener is not particularly limited, but specific examples thereof include the following. Chain extenders include, for example, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,6-hexanediol, isoprene glycol 1,4-cyclohexanedimethanol, and 1,4-dihydroxycyclohexane. Among these, ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol are preferable, and 1,4-butanediol is particularly preferable.

又，鏈延長劑係亦可使用胺鏈延長劑。尤佳之胺鏈延 長劑係可舉例如芳香族胺例如甲苯二胺之各種異性體及衍 生物、及亞甲基二苯胺。尤其，藉電子或立體效果，與異 氰酸酯基的加成反應比較慢，具有取代基之芳香族胺可舉 例如4,4’-亞甲基雙（2-氯苯胺）、4,4’-亞甲基雙（3-氯-2,6-二乙基苯胺）、二乙基甲苯胺、及亞甲基二苯胺。 硬化劑係可舉例如甘油、三羥甲基丙烷，二乙醇胺、 及三乙醇胺等之多官能多元醇及聚胺等。 在本方法中，於多元醇（A )與聚異氰酸酯化合物（B )反應之系中依需要亦可添加塡充材及各種添加劑。具體 上係混合多元醇（A )與依需要所選擇之塡充材及各種添 加劑，於該混合物中添加聚異氰酸酯（B )而反應。 塡充材係可廣泛使用以往公知之塡充材，但可舉例如 一般之碳酸鈣、碳黑、泥土、滑石、氧化鈦、生石灰、高 嶺土、沸石、矽藻土、氯化乙烯糊劑樹脂 '中空玻璃珠、 中空偏氯乙烯樹脂、中空丙烯腈/甲烯丙烯腈樹脂等，可 單獨或混合而使用。 -30- 200840830 塡充材之調·配比率係無特別限制，相對於聚合物成份 100重量份，宜爲50〜1000質量份，更宜爲10 0〜500質 量份。 進一步，爲調整黏度、物性，依需要而可調配可塑劑 、賦予接著劑、賦予黏著劑、安定劑、蠘、抗老化劑、紫 外線吸收劑、光安定劑、搖變劑、著色劑等之各種添加劑Further, an amine chain extender can also be used as the chain extender. Further preferred amine chain extenders are, for example, various anisotropes and derivatives of aromatic amines such as toluenediamine, and methylene diphenylamine. In particular, the addition reaction with an isocyanate group is relatively slow by an electron or a stereoscopic effect, and the aromatic amine having a substituent may, for example, be 4,4'-methylenebis(2-chloroaniline) or 4,4'- Methyl bis(3-chloro-2,6-diethylaniline), diethyltoluidine, and methylene diphenylamine. Examples of the curing agent include polyfunctional polyols such as glycerin, trimethylolpropane, diethanolamine, and triethanolamine, and polyamines. In the method, a ruthenium filler and various additives may be added as needed in the reaction between the polyol (A) and the polyisocyanate compound (B). Specifically, the mixed polyol (A) and optionally the ruthenium and various additives are added, and the polyisocyanate (B) is added to the mixture to be reacted. As the ruthenium filler, a conventionally known ruthenium filler can be widely used, and examples thereof include general calcium carbonate, carbon black, clay, talc, titanium oxide, quicklime, kaolin, zeolite, diatomaceous earth, and chlorinated vinyl paste resin. Hollow glass beads, hollow vinylidene chloride resin, hollow acrylonitrile/methene acrylonitrile resin, etc., may be used singly or in combination. -30- 200840830 The adjustment and ratio of the ruthenium filler are not particularly limited, and are preferably 50 to 1000 parts by mass, more preferably 10 to 500 parts by mass, per 100 parts by weight of the polymer component. Further, in order to adjust the viscosity and the physical properties, a plasticizer, an adhesive, an adhesive, a stabilizer, a cockroach, an anti-aging agent, an ultraviolet absorber, a light stabilizer, a shaker, a colorant, etc. may be blended as needed. additive

賦予接著劑係可使用矽烷偶合劑、羰醯亞胺化合物等 ，安定劑係可使用阻酚系化合物、三唑系化合物等。著色 劑可舉例如鈦白粉、碳黑、氧化鐵紅等。 賦予黏著劑可舉例如松香酯樹脂、萜烯樹脂、萜烯酣 樹脂、石油樹脂（脂肪族系、芳香族系、脂環族系、共聚 合系、香豆素茚樹脂系），烷基酚樹脂、二甲苯樹脂等。 賦予黏著劑可舉例如松香酯樹脂、萜烯樹脂、萜烯酣 樹脂、石油樹脂（脂肪族系、芳香族系、脂環族系、共聚 合系、香豆素茚樹脂系），烷基酚樹脂、二甲苯樹脂等。 (第2製造方法） 在上述第2製造方法中係以異氰酸酯基/羥基就莫耳 比成爲1.3〜5.0，較佳係成爲1·8〜4.5之方式，使多元醇 (A)與聚異氰酸酯（Β )而得到異氰酸酯基末端預聚物。 使該異氰酸酯基末端預聚物與環境中之水分反應而硬化胃 可得到減振材料用胺基甲酸乙酯樹脂（硬化物）。 較佳係使含有該異氰酸酯基末端預聚物之減振材料 -31 - 200840830 單液濕氣硬化型組成物在水分不進入之條件下進行製造， 置入密閉容器，保存，使用時從容器取出，塗佈於被黏著 基材上，藉由曝露於大氣中俾濕氣硬化而製造減振材料用 胺基甲酸乙酯樹脂。該減振材料用單液濕氣硬化型組成物 係可使用來作爲塗佈型之減振性黏著劑。A decane coupling agent, a carbonyl sulfimide compound, etc. can be used for the adhesive agent, and a phenol-resistant compound, a triazole type compound, etc. can be used for a stabilizer. The coloring agent may, for example, be titanium white powder, carbon black or iron oxide red. Examples of the adhesive to be added include a rosin ester resin, a terpene resin, a terpene resin, and a petroleum resin (aliphatic, aromatic, alicyclic, copolymer, and coumarin resin), and alkylphenol. Resin, xylene resin, etc. Examples of the adhesive to be added include a rosin ester resin, a terpene resin, a terpene resin, and a petroleum resin (aliphatic, aromatic, alicyclic, copolymer, and coumarin resin), and alkylphenol. Resin, xylene resin, etc. (Second Manufacturing Method) In the second production method, the polyol (A) and the polyisocyanate are used in such a manner that the isocyanate group/hydroxy group has a molar ratio of 1.3 to 5.0, preferably 1.8 to 4.5.异) to obtain an isocyanate-based terminal prepolymer. The isocyanate-based terminal prepolymer is reacted with moisture in the environment to harden the stomach to obtain a urethane resin (cured product) for the vibration-damping material. Preferably, the vibration-damping material containing the isocyanate-terminated prepolymer-31 - 200840830 is prepared by a single-liquid moisture-curing composition, placed in a closed container, stored, and taken out from the container during use. The urethane resin for damping materials is produced by being applied to an adherent substrate and hardened by exposure to moisture in the atmosphere. The vibration damping material can be used as a coating type vibration damping adhesive with a one-liquid moisture-curing composition.

調製上述異氰酸酯基末端預聚物時，若上述異氰酸酯 基/羥基之莫耳比爲1 · 3以上，所得到之預聚物的分子量被 適度地抑制至很小，黏度變低，故就作業性、溼氣硬化性 而S ’佳。另外，若爲5.0以下，未反應之聚異氰酸酯（ B )的殘存少，最終所得到之減振材料用胺基甲酸乙酯樹 脂的機械物性變良好。 本方法所使用之異氰酸酯基末端預聚物係宜異氰酸酯 基含量爲〇·5〜1〇質量％，更宜爲1〜7質量％。該異氰酸 酯基含量爲〇 · 5質量％以上，預聚物之貯存安定性及溼氣 硬化後之減振性胺基甲酸乙酯樹脂的機械物性優，若爲1 〇 質量％以下，溼氣硬化後之減振性胺基甲酸乙酯樹脂之延 伸、減振性優。 前述減振材料用單液濕氣硬化型組成物中係亦可含有 使多元醇（A)與聚異氰酸酯（B)反應而成之異氰酸酯基 末端預聚物以外之其他聚合物。該其他之聚合物宜使用玻 璃轉移溫度與前述異氰酸酯基末端預聚物相異之聚合物， 藉此’可擴展所得到之減振材料用胺基甲酸乙酯樹脂的 tan (5之値變高之溫度（峰値）溫度）之範圍。 該其他之聚合物係只要爲不含有與前述異氰酸酯基末 -32- 200840830 端預聚物中之異氰酸酯基反應的官能基者即可。具體例係 可舉例如與前述第1製造方法中之其他的聚合物之例同樣 者0 該其他之聚合物的使用比率係相對於異氰酸酯基末端 預聚物與其他之聚合物的合計之100質量份宜爲200質量 份，更宜爲100質量份以下，亦可爲0。When the isocyanate group-terminated prepolymer is prepared, when the molar ratio of the isocyanate group to the hydroxyl group is 1.3 or more, the molecular weight of the obtained prepolymer is moderately suppressed to a small value, and the viscosity is lowered, so workability is obtained. , moisture hardening and S 'good. In addition, when it is 5.0 or less, the residual of the unreacted polyisocyanate (B) is small, and the mechanical properties of the urethane resin obtained by the final damping material are improved. The isocyanate group-terminated prepolymer used in the method preferably has an isocyanate group content of 〇·5 to 1% by mass, more preferably 1 to 7% by mass. The content of the isocyanate group is 5% by mass or more, and the storage stability of the prepolymer and the mechanical properties of the vibration-damping urethane resin after moisture curing are excellent, and if it is 1% by mass or less, moisture hardening The vibration-absorbing urethane resin is excellent in elongation and vibration damping. The single-liquid moisture-curing composition for a vibration damping material may further contain a polymer other than the isocyanate-based terminal prepolymer obtained by reacting the polyol (A) with the polyisocyanate (B). The other polymer is preferably a polymer having a glass transition temperature different from that of the above-mentioned isocyanate-based terminal prepolymer, whereby the obtained damping material is obtained by using a tan of a urethane resin. The range of temperature (peak temperature). The other polymer may be any one which does not contain a functional group which reacts with the isocyanate group in the above-mentioned isocyanate-32-200840830 terminal prepolymer. Specific examples are, for example, the same as the examples of the other polymers in the first production method. The use ratio of the other polymers is 100% based on the total of the isocyanate-based terminal prepolymer and other polymers. The amount is preferably 200 parts by mass, more preferably 100 parts by mass or less, or 0.

又，於前述減振材料用單液濕氣硬化型組成物中依需 要而可調配前述塡充材及各種添加劑。 (第3製造方法） 在使本發明之多元醇（A)與聚異氰酸酯化合物（B) 反應而異氰酸酯基末端預聚物係如前述第2製造方法般， 除可與環境中之水分反應而溼氣硬化外，如前述第3製造 方法般，亦可與硬化劑成份反應而硬化。 換言之，前述第3之製造方法係使異氰酸酯基/羥基 之莫耳比成爲1.3〜5.0，較佳爲1.8〜4.5的狀態下，使多元 醇（A)與聚異氰酸酯（B)反應，得到異氰酸酯基末端預 聚物’以該異氰酸酯基末端預聚物爲主劑成分，與硬化劑 成分反應可得到減振材料用胺基甲酸乙酯樹脂（硬化物） 較佳係製造含有該異氰酸酯基末端預聚物之主劑組成 物與含有硬化劑成份之硬化劑組成物分別具有之減振材料 用雙液硬化型系統，使用時，混合主劑組成物與硬化劑組 成物’使該混合物塗佈於被黏著基材，在常溫下，或依需 -33- 200840830 要而加熱硬化以製造減振材料用胺基甲酸乙酯樹脂。該雙 液硬化型系統係可使用來作爲塗佈型之減振性黏著劑。 主劑組成物宜在水分不進入之條件下進行製造，置入 密閉容器，保存，使用時從容器取出而與硬化劑組成物混 合。又，硬化反應時係宜在密閉容器中或氮氣等之情性氣 體流通化等以不吸收大氣中之水分的條件下實施。 調製上述異氰酸酯基末端預聚物時，若上述異氰酸酯 基/羥基之莫耳比爲1 · 3以上，所得到之預聚物的分子量被 適度地抑制至很小，黏度變低，故就作業性、硬化性而言 ，佳。另外，若爲5.0以下，未反應之聚異氰酸酯（B ) 的殘存少，最終所得到之減振材料用胺基甲酸乙酯樹脂的 機械物性變良好。Further, the above-mentioned enamel filler and various additives may be blended in the single-liquid moisture-curing composition for a vibration damping material as needed. (Third Production Method) The polyol (A) of the present invention is reacted with the polyisocyanate compound (B), and the isocyanate group-terminated prepolymer is wetted by reaction with moisture in the environment as in the second production method. In addition to the gas hardening, as in the third production method described above, it may be reacted with the hardener component to be hardened. In other words, in the third production method, the polyol (A) and the polyisocyanate (B) are reacted in a state in which the molar ratio of the isocyanate group to the hydroxyl group is from 1.3 to 5.0, preferably from 1.8 to 4.5, to obtain an isocyanate group. The terminal prepolymer is prepared by reacting the isocyanate-based terminal prepolymer with the hardener component to obtain a vibration-damping material. The urethane resin (hardened product) is preferably made of the isocyanate-based terminal prepolymer. The main component composition and the hardener composition containing the hardener component respectively have a two-liquid hardening type system for damping materials, and when used, the mixed main component and the hardener composition 'coat the mixture to be Adhesive substrate, at room temperature, or as needed -33- 200840830 heat hardening to make urethane resin for damping materials. This two-liquid hardening type system can be used as a coating type vibration damping adhesive. The composition of the main agent is preferably produced under conditions in which moisture does not enter, placed in a closed container, stored, and taken out from the container at the time of use to be mixed with the hardener composition. Further, in the case of the hardening reaction, it is preferred to carry out the reaction in a sealed container or a gas such as nitrogen gas, so as not to absorb moisture in the atmosphere. When the isocyanate group-terminated prepolymer is prepared, when the molar ratio of the isocyanate group to the hydroxyl group is 1.3 or more, the molecular weight of the obtained prepolymer is moderately suppressed to a small value, and the viscosity is lowered, so workability is obtained. In terms of hardenability, it is good. In addition, when it is 5.0 or less, the residual of the unreacted polyisocyanate (B) is small, and the mechanical properties of the urethane resin finally obtained by the vibration damping material are improved.

本方法所使用之異氰酸酯基末端預聚物係宜異氰酸酯 基含量爲0 · 5〜1 0質量％，更宜爲1〜7質量％。該異氰酸 酯基含量爲〇·5質量％以上，所得到之減振材料用胺基甲 酸乙酯樹脂的機械物性優，若爲10質量％以下，所得到之 減振材料用胺基甲酸乙酯樹脂之延伸及減振性優。 硬化劑成份係可使用公知之鏈延長劑及/或硬化劑， 可使用與前述第1方法之鏈延長劑及/或硬化劑同樣者。 尤其，製造熱塑性之減振材料用胺基甲酸乙酯樹脂時 ，宜只使用鏈延長劑，不使用硬化劑，但在可維持熱塑性 之範圍，亦可倂用少量之硬化劑。 硬化劑成份之使用量係宜（主劑成份中之異氰酸酯基 )/(硬化劑中之羥基）的莫耳比爲0.7〜1.2的範圍，更 -34- 200840830 宜爲0.9〜1 .1的範圍。若爲此比率之範圍內，進行充分交 聯，所得到之減振材料用胺基甲酸乙酯樹脂的機械物性良 好。 於前述雙液硬化型系統之主劑組成物或硬化劑組成物 中，亦可含有使多元醇（A)與聚異氰酸酯（B)反應而構 成之異氰酸酯基末端預聚物以外之其他聚合物。就其他之 聚合物而言宜使用玻璃轉移溫度與前述異氰酸酯基末端預 I· 聚物相異之聚合物，藉此，可擴展所得到之減振材料用胺 基甲酸乙酯樹脂的tan 5値變高之溫度（峰値溫度）的範 圍。 該其他之聚合物係只要不含有與前述異氰酸酯基末端 預聚物中之異氰酸酯基反應的官能基者即可。具體上，可 舉例如與在前述第1製造方法中之其他聚合物的例子相同 者0The isocyanate group-terminated prepolymer used in the method preferably has an isocyanate group content of from 0.5 to 10% by mass, more preferably from 1 to 7% by mass. The content of the isocyanate group is 5% by mass or more, and the obtained urethane resin for the vibration damping material is excellent in mechanical properties, and if it is 10% by mass or less, the obtained urethane resin for the vibration damping material is obtained. The extension and vibration damping are excellent. As the hardener component, a known chain extender and/or a hardener can be used, and the same chain extender and/or hardener as the above first method can be used. In particular, when a urethane resin for a thermoplastic vibration-damping material is produced, it is preferred to use only a chain extender and no hardener, but a small amount of a hardener may be used in a range in which thermoplasticity can be maintained. The amount of the hardener component is preferably (the isocyanate group in the main component) / (the hydroxyl group in the hardener) has a molar ratio of 0.7 to 1.2, and more preferably -34 to 200840830 is in the range of 0.9 to 1.1. . If it is sufficiently crosslinked within the range of this ratio, the mechanical properties of the obtained urethane resin for the vibration damping material are good. The main component composition or the hardener composition of the two-liquid curing type system may further contain a polymer other than the isocyanate group-terminated prepolymer which is formed by reacting the polyol (A) with the polyisocyanate (B). For other polymers, it is preferred to use a polymer having a glass transition temperature different from that of the above-mentioned isocyanate group-terminated prepolymer, whereby the tan 5 胺 of the obtained urethane resin for the vibration damping material can be expanded. The range of the temperature (peak temperature) that goes high. The other polymer may be any one which does not contain a functional group which reacts with the isocyanate group in the above-mentioned isocyanate group-terminated prepolymer. Specifically, it can be exemplified as the same as the examples of the other polymers in the first manufacturing method described above.

該其他之聚合物的使用比率係相對於異氰酸酯基末端 預聚物與其他之聚合物的合計之100質量份宜爲200質量 份以下，更宜爲100質量份以下，亦可爲0。 又，於前述雙液硬化型系統之主劑組成物或硬化劑組 成物中，依需要而可調配前述塡充材及各種添加劑。 若依本發明之方法，就與聚異氰酸酯化合物（B)反 應之成份而言，藉由使用特定之聚酯醚多元醇（A1)，如後 述之實施例所示般，接著性良好，在廣溫度範圍中tan δ大 而減振性優，同時彈性率亦高而彈性率與tan 6之均衡佳 ，且延伸亦良好之減振材料用胺基甲酸乙酯樹脂。 -35- 200840830 具體上係可得到在10〜50°C範圍tan 5 (損失係數 )爲〇_1以上之具有良好的減振性之減振材料用胺基甲酸 乙酯樹脂。如此地，若在廣溫度範圍中tan 5大，在室內 、室外使用減振材料時，即使暴露於各種之溫度條件下亦 可安定得到良好的減振性。The use ratio of the other polymer is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, or 0 or less, based on 100 parts by mass of the total of the isocyanate group-terminated prepolymer and the other polymer. Further, in the main component composition or the hardener composition of the two-liquid curing type system, the above-mentioned enamel filler and various additives may be blended as needed. According to the method of the present invention, by using a specific polyester ether polyol (A1) as a component which reacts with the polyisocyanate compound (B), as shown in the examples described later, the adhesion is good and wide. In the temperature range, the tan δ is large and the vibration damping property is excellent, and the elastic modulus is also high, and the elastic ratio is well balanced with tan 6, and the damper material is excellent in the vibration damping material. -35- 200840830 Specifically, a urethane resin for a vibration damping material having a good damping property in a range of 10 to 50 ° C and a tan 5 (loss coefficient) of 〇_1 or more can be obtained. As described above, when the tan 5 is large in a wide temperature range, when the vibration damping material is used indoors or outdoors, good vibration damping properties can be obtained even when exposed to various temperature conditions.

尤其，就聚酯醚多元醇（A1)而言，藉由倂用玻璃轉 移溫度（Tg )互異之2種以上，可擴展所得到之減振材料 用胺基甲酸乙酯樹脂的tan (5値變高之溫度（峰値溫度） 的範圍，例如，可得到在10〜50°C之常溫的範圍中tan δ (損失係數）爲0.2以上，更宜爲0.3以上之具有優異的 減振性之減振材料用胺基甲酸乙酯樹脂。 又’依本發明之方法所使用的減振材料用胺基甲酸乙 酯樹脂，係黏著性良好，適宜作爲減振性黏著劑。例如可 使用來作爲貼合石膏板、合板、刨花板、纖維板、木毛水 泥板、可撓性板、矽酸鈣板、混泥土、岩板、ALC板、銅 板等的黏著劑，可對貼合此等而構成之建築用複合板賦予 減振性能。 尤其，若使用上述單液濕氣硬化型組成物或雙液硬化 型系統而製造減振材料用胺基甲酸乙酯樹脂之型態，可適 宜使該組物或系統作爲塗佈型之減振性黏著劑，且作業个生 佳。 【實施方式】 實施例 -36-In particular, in the case of the polyester ether polyol (A1), the tantalum of the urethane resin for the vibration-damping material can be expanded by using two or more different glass transition temperatures (Tg). In the range of the temperature at which the enthalpy is high (peak temperature), for example, tan δ (loss coefficient) in the range of normal temperature of 10 to 50 ° C is 0.2 or more, and more preferably 0.3 or more, and excellent vibration damping property is obtained. A urethane resin for the vibration damping material. The urethane resin used for the vibration damping material used in the method of the present invention has good adhesion and is suitable as a vibration damping adhesive. As an adhesive for gypsum board, plywood, particle board, fiberboard, wood wool board, flexible board, calcium silicate board, concrete, rock board, ALC board, copper board, etc., it can be laminated. The composite panel for construction imparts vibration damping performance. In particular, if the above-described one-liquid moisture-curing composition or the two-liquid-curing system is used to produce a type of urethane resin for a vibration-damping material, the group can be suitably used. Object or system as a coating type damping adhesive And a raw good job. [Embodiment Example] -36-

200840830 以下，表示實施例而具體地說明本發明。 係不限定於以下之實施例。又’在以下之例中 別聲明，「份」係表示「質量份」。 在以下之例中使用來作爲原料之多元醇係 分子量爲羥基價換算分子量。 • PPG- 1 000 (簡稱）：使用丙二醇作爲起岁 KOH觸媒而製造之羥基價112mgKOH/g、分子 I# 聚氧丙二醇。 • PPG-2000 (簡稱）：使用丙二醇作爲起多 KOH觸媒而製造之羥基價56mgKOH/g、分子邏 氧丙二醇。 • PBA (簡稱）：羥基價56|1^尺011^、分子量 (丁二醇）己二酸酯二醇、日本Polyurethane 、製品名·· N i ρ ρ ο 11 a η 4 0 1 0 • IP/MPD (簡稱）：羥基價 56mgKOH/g、分 ϊ 聚（3-甲基戊二醇）異酞酸酯二元醇、Kur ay 品名P-2030 〔製造例1:聚酯醚二醇（A1-1)之調製〕 在本例中係使用鋅己烷氰鈷酸酯-第三丁 作爲觸媒（X )，聚氧丙二醇作爲起始劑（a ) 爲聚羧酸酐（b )、環氧丙烷作爲環氧烷（c ) 醚二醇（A1-1 )。 亦即，於具備攪拌機及氮導入管之耐壓反 但，本發明 ，只要無特 如以下般， 台劑，使用 量 1 0 0 0之 台劑，使用 t 2000之聚 2000之聚 工業公司製 1量2000之 公司製、商 基醇錯合物 ，酞酸酐作 而製造聚酯 應器內，投 -37- 200840830200840830 Hereinafter, the present invention will be specifically described by way of examples. It is not limited to the following examples. Also, in the following examples, "parts" means "parts by mass". The polyol used as a raw material in the following examples has a molecular weight in terms of a hydroxyl value. • PPG-1 000 (abbreviation): propylene glycol 112gKOH/g, molecular I# polyoxypropylene glycol produced using propylene glycol as a KOH catalyst. • PPG-2000 (abbreviation): propylene glycol is used as a multi-KOH catalyst to produce a hydroxyl group of 56 mg KOH/g and molecular oxypropylene glycol. • PBA (abbreviation): hydroxyl price 56|1^foot 011^, molecular weight (butanediol) adipate diol, Japanese Polyurethane, product name · N i ρ ρ ο 11 a η 4 0 1 0 • IP /MPD (abbreviation): hydroxyl group 56 mgKOH/g, hydrazine poly(3-methylpentanediol) isodecanoate diol, Kur ay product name P-2030 [Production Example 1: Polyester ether diol (A1) -1) Modulation] In this example, zinc hexane cyanocyanate-third is used as the catalyst (X), polyoxypropylene glycol is used as the initiator (a) is polycarboxylate (b), epoxy Propane is used as the alkylene oxide (c) ether diol (A1-1). In other words, the pressure resistance of the mixer and the nitrogen introduction tube is reversed. However, the present invention is not limited to the following, and the amount of the agent used in the system is 100%. 1 quantity of 2000 company, commercial base alcohol complex, phthalic anhydride for the manufacture of polyester, cast -37- 200840830

入聚氧丙二醇（PPG- 1 000 )之2000g。然後，將酞酸酐（ PA)之800g(5.4莫耳）投入於上述反應容器內而攪拌。 然後加入鋅己烷氰鈷酸酯-第三丁基醇錯合物（DMC-TBA 錯合物）的〇.4g，進一步徐緩地加入環氧丙烷（p〇 )的 1 200g(20.6莫耳），同時並在氮氣環境下，130°C下反應 7小時。然後確認反應容器內壓之降低停止後，從反應容 器移去生成物，得到於聚氧丙二醇之末端聚合酞酸酐及環 氧丙烷之聚酯醚二醇（A1-1)(羥基價58.3mgKOH/g)。 從此聚酯醚二醇（A1-1)的1 H-NMR測定結果。確認出此 二元醇（A1-1)具有酞酸酐及環氧丙烷之聚合鏈。 在本例中，起始劑（a )之羥價、（a ) 、( b ) 、( c )、（x)之各成份的使用量（饋入質量）及（c)/(b) 之質量比、以及所得到之聚酯醚二醇（A 1 - 1 )中之含量、 羥基價、羥基價換算分子量、「從羥基價換算分子量除去 起始劑之分子量的殘留之分子量以起始劑之官能基數除之 値（M’）」、玻璃轉移溫度、酸價及黏度之各値表示於表 1中。 黏度之値係依據JIS K1557(1 970年版）之方法，使 用E型黏度計而以25 °C之條件進行測定所得到之値（單 元：m P a · s )。 玻璃轉移溫度（Tg )係使用微分熱分析機（DSC : S II公司製、製品名：EXSTAR-DSC-6200 )裝置，冷卻至_ 100°C後，以5°C /分進行昇溫之條件下進行測定。 -38- 200840830 〔製造例2〜5:聚酯醚二元醇（A1-2〜5)之調製〕 使起始劑（a )之羥價、及（a ) 、（ b ) 、（ c )、（ x)之各成份的使用量變更成如表1般以外，其餘係與製 造例1同樣做法而得到聚酯醚二元醇（A1-2〜5)。 與製造例1同樣地起始劑（a )之羥價、（&)、（5 )、(c) 、（X)之各成份的使用量及（c)/(b)之莫耳 比、以及所得到之聚酯醚二元醇（A 1 -2〜5 )中的各物性値 表7K於表1中。 〔表1〕 製造例1 製造例2 製造例3 製造例4 製造例5 聚酯醚多元醇(A1) A1-1 A1-2 A1-3 A1-4 A1-5 配合 起始劑(a)之羥基價 (mgKOH/g) 112 160 112.2 160 112 起始劑⑻之饋入質量(g) 2000 1435 1913 700 2000 (c)/(b)饋入量之莫耳比 79/21 75/25 59/41 82/18 63/37 P〇(c)之饋入質量(g) 1200 1451 899 2100 800 P〇(b)之饋入質量(g) 800 1214 1588 1200 1200 觸媒(X)饋入質量(g) 0.40 0.40 0.44 0.40 0.40 (A1冲(b)之含有量(質量％) 20 30 36 30 30 (A1) 之性 狀 羥基價(mgKOH/g) 58.3 59.0 50.0 31.0 57.6 羥基價換算分子量 1930 1900 2200 3600 1948 M， 464 599 600 1449 474 玻璃轉移溫度(。C ) -56 -42 -33 -43 -42 酸價(mgKOH/g) 0.11 0.14 0.82 0.17 0.14 黏度(mPa· s/25°C ) 4,500 26,200 超過励，000 70,000 24,5002000 g of polyoxypropylene glycol (PPG-1 000). Then, 800 g (5.4 mol) of phthalic anhydride (PA) was placed in the above reaction vessel and stirred. Then, 4 g of zinc hexane cyanocyanate-tert-butyl alcohol complex (DMC-TBA complex) was added, and 1 200 g (20.6 mol) of propylene oxide (p〇) was further slowly added. At the same time, the reaction was carried out at 130 ° C for 7 hours under a nitrogen atmosphere. After confirming that the decrease in the internal pressure of the reaction vessel was stopped, the product was removed from the reaction vessel to obtain a polyester ether diol (A1-1) of phthalic anhydride and propylene oxide at the end of the polyoxypropylene glycol (hydroxyl price: 58.3 mgKOH/ g). From the results of 1 H-NMR measurement of the polyester ether diol (A1-1). It was confirmed that the diol (A1-1) had a polymer chain of phthalic anhydride and propylene oxide. In this example, the hydroxyl value of the initiator (a), the amount of each component (a), (b), (c), (x) used (feed quality) and (c)/(b) The mass ratio, the content of the obtained polyester ether diol (A 1 - 1 ), the valence of the hydroxyl group, the molecular weight of the hydroxy group, and the molecular weight of the residual molecular weight of the starting agent removed from the molecular weight of the hydroxy group as the initiator The functional groups are divided by the enthalpy (M')", the glass transition temperature, the acid value, and the viscosity, which are shown in Table 1. The viscosity is determined by the method of JIS K1557 (1970) using an E-type viscometer and measuring at 25 °C (unit: m P a · s). The glass transition temperature (Tg) was obtained by using a differential thermal analyzer (DSC: manufactured by S II, product name: EXSTAR-DSC-6200), and cooled to _100 ° C, and then heated at 5 ° C /min. The measurement was carried out. -38- 200840830 [Production Examples 2 to 5: Preparation of Polyester Ether Diol (A1-2 to 5)] The hydroxyl value of the initiator (a), and (a), (b), (c) The amount of each component of (x) was changed to the same as in the case of Table 1, and the polyester ether diol (A1-2 to 5) was obtained in the same manner as in Production Example 1. In the same manner as in Production Example 1, the hydroxyl group content of the initiator (a), the amount of each of the components (&), (5), (c), and (X), and the molar ratio of (c)/(b). And the physical properties of the obtained polyester ether diol (A 1 -2 to 5) are shown in Table 1. [Table 1] Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Polyesterether polyol (A1) A1-1 A1-2 A1-3 A1-4 A1-5 Mixing initiator (a) Hydroxyl valence (mgKOH/g) 112 160 112.2 160 112 Feeder quality of starter (8) (g) 2000 1435 1913 700 2000 (c)/(b) Moir ratio of feedstock 79/21 75/25 59/ 41 82/18 63/37 P〇(c) Feed quality (g) 1200 1451 899 2100 800 P〇(b) Feed quality (g) 800 1214 1588 1200 1200 Catalyst (X) feed quality ( g) 0.40 0.40 0.44 0.40 0.40 (content of A1 punch (b) (% by mass) 20 30 36 30 30 (A1) Properties of hydroxy group (mgKOH/g) 58.3 59.0 50.0 31.0 57.6 Molecular weight in terms of hydroxyl value 1930 1900 2200 3600 1948 M, 464 599 600 1449 474 Glass transition temperature (.C) -56 -42 -33 -43 -42 Acid value (mgKOH/g) 0.11 0.14 0.82 0.17 0.14 Viscosity (mPa· s/25°C) 4,500 26,200 Exceeding Reward, 000 70,000 24,500

M’=(羥基價換算分子-起始劑之分子量）/官能基數 〔實施例1 :減振材料用胺基甲酸乙酯預聚物（P 1 )之製 -39- 200840830 造〕 ， 使多元醇（A)與聚異氰酸酯（B)反應而製造異氰酸 酯基末端預聚物（減振材料用胺基甲酸乙酯預聚物）° 於附有1升玻璃製之攪拌的反應槽中，投入製造例1 所製造之聚酯醚二元醇（A1-1)的100重量份。於該反應 槽中投入作爲聚異氰酸酯化合物（B)之4,4’_二苯基甲烷 二異氰酸酯（日本Polyurethane工業股份公司製、商品名 :Millionate MT、異氰酸酯基含量33.6質量％ :以下稱爲 MDI )的32.6重量份。 以氮氣取代反應槽內之後，以每分鐘1〇〇旋轉攪拌內 容物，同時並使反應槽昇溫至90 °C，保持90 °C 4小時。取 出反應後之內容物的一部分測定異氰酸酯基（以下，有時 省略爲NCO)含量，確認出理論上所計算之含量以下而使 反應終止，得到異氰酸酯基末端預聚物（P 1 )。M'=(hydroxyl value-converted molecule-starter molecular weight)/functional group number [Example 1: Damping material made of urethane prepolymer (P 1 )-39-200840830] The alcohol (A) is reacted with the polyisocyanate (B) to produce an isocyanate-based terminal prepolymer (a urethane prepolymer for a vibration-damping material). It is put into a reaction tank with a stirring of 1 liter of glass. Example 1 100 parts by weight of the polyester ether diol (A1-1) produced. 4,4'-diphenylmethane diisocyanate which is a polyisocyanate compound (B) was put in the reaction tank (manufactured by Japan Polyurethane Industrial Co., Ltd., trade name: Millionate MT, isocyanate group content: 33.6 mass%: hereinafter referred to as MDI 32.6 parts by weight. After replacing the inside of the reaction vessel with nitrogen, the contents were stirred at 1 Torr per minute while the reaction vessel was heated to 90 ° C and maintained at 90 ° C for 4 hours. A part of the content after the reaction was taken out, and the content of the isocyanate group (hereinafter sometimes omitted as NCO) was measured, and the theoretically calculated content was determined to be or less, and the reaction was terminated to obtain an isocyanate group-terminated prepolymer (P 1 ).

將預聚物調製時之調配（單位：質量份）、異氰酸酯 基/羥基（NCO/OH )的莫耳比、以及所得到之預聚物（ρι )中的異氰酸酯基含量表示於表2中。 〔實施例2〜5 :減振材料用胺基甲酸乙酯預聚物（P2〜5 ) 之製造〕 使用製造例2〜4所製造之聚酯醚二醇（A1-2〜4)而製 造異氰酸酯基末端預聚物（減振材料用胺基甲酸乙酯預聚 物）。 亦即，於實施例1中，將聚酯醚多元醇（A1 )之種類 -40- 200840830 、聚異氰酸酯化合物（B)之MDI的調配量變更成表2所 示般以外，其餘係與實施例1同樣做法而得到異氰酸酯基 末端胺基甲酸乙酯預聚物（P2〜5 )。 又將預聚物調製時之異氰酸酯基/羥基的莫耳比、以 及所得到之預聚物（P 1 )中的異氰酸酯基含量表示於表2 中。於表中調配欄之數字的單位爲重量份。The formulation (unit: parts by mass) of the prepolymer, the molar ratio of the isocyanate group/hydroxy group (NCO/OH), and the isocyanate group content in the obtained prepolymer (ρι) are shown in Table 2. [Examples 2 to 5: Production of urethane prepolymer (P2 to 5) for damping materials] Manufactured using the polyester ether diols (A1-2 to 4) produced in Production Examples 2 to 4 Isocyanate-based terminal prepolymer (ethyl urethane prepolymer for damping materials). That is, in Example 1, the blending amount of the polyester ether polyol (A1) type -40-200840830 and the polyisocyanate compound (B) MDI was changed to the same as shown in Table 2, and other examples and examples were given. In the same manner, an isocyanate-terminated ethyl urethane prepolymer (P2 to 5) was obtained in the same manner. Further, the molar ratio of the isocyanate group/hydroxy group at the time of preparing the prepolymer and the isocyanate group content in the obtained prepolymer (P 1 ) are shown in Table 2. The unit of the number in the allocation column in the table is the weight.

〔比較例1、2〕 於實施例1中，取代聚酯醚二醇（A1 -1 )’比較例1 中係使用P P G - 2 0 0 0 (玻璃轉移溫度：-7 0 °c )作爲起始劑 。在比較例2中係使用PB A。聚異氰酸酯化合物（B)之 MDI的調配量變更成表2所示般。其他係與實施例1同樣 做法而得到異氰酸酯基末端胺基甲酸乙酯預聚物（Q 1、2 〔表2〕 實施例1 實施例2 實施例3 奮施例4 實施例5 比較例1 比較例2 AM 100 50 A1-2 100 A1-3 100 50 配合 A1-4 100 PPG-2000 100 PBA 100 MDI 32.6 33.0 30.7 31.5 26.3 30.6 31.8 NCC >/OH夕莫耳比 2.5 2.5 2.7 2.6 3.8 2.4 2.5 NCO含有量 償量％) 4.96 5.01 5.02 4.96 4.93 4.76 5.07 預聚物 _ P1 P2 P3 P4 P5 〇1 02 -41- 200840830 〔減振材料用胺基甲酸乙酯樹脂的製造及評估〕 將實施例1〜5及比較例1、2得到之異氰酸酯基末端 預聚物（P1〜P5)及（Ql、Q2)塗佈於2軸延伸聚丙烯膜 (OPP膜）上，形成厚100/zm之未硬化的塗膜。繼而， 使該未硬化之塗膜於溫度20°C、相對濕度60%的環境下放 置一週，藉空氣中之水分而使塗膜硬化，俾得到胺基甲酸 乙酯樹脂薄膜。 在比較例3中係市售作爲塗佈型減振材料組成物之丙 烯基乳化液系黏著劑（製品名：HC-025、Cemedine公司 製、含有塡充劑）塗佈於OPP薄膜上，形成厚100 μ m之 塗膜。繼而，使該塗膜於溫度20 °C、相對濕度60%的環境 下放置一週，使塗膜中之水分揮發而得到硬化薄膜。[Comparative Examples 1 and 2] In Example 1, in place of the polyester ether diol (A1 -1 )', in Comparative Example 1, PPG - 2 0 0 0 (glass transition temperature: -7 0 °c) was used. Starting agent. In Comparative Example 2, PB A was used. The blending amount of the MDI of the polyisocyanate compound (B) was changed as shown in Table 2. In the same manner as in Example 1, an isocyanate-terminated ethyl urethane prepolymer was obtained (Q 1 , 2 [Table 2] Example 1 Example 2 Example 3 Excited Example 4 Example 5 Comparative Example 1 Example 2 AM 100 50 A1-2 100 A1-3 100 50 with A1-4 100 PPG-2000 100 PBA 100 MDI 32.6 33.0 30.7 31.5 26.3 30.6 31.8 NCC >/OH oxime ratio 2.5 2.5 2.7 2.6 3.8 2.4 2.5 NCO Content of replenishment %) 4.96 5.01 5.02 4.96 4.93 4.76 5.07 Prepolymer _ P1 P2 P3 P4 P5 〇1 02 -41- 200840830 [Manufacture and evaluation of urethane resin for damping materials] Example 1~ 5 and the isocyanate group-terminated prepolymers (P1 to P5) and (Q1, Q2) obtained in Comparative Examples 1 and 2 were coated on a 2-axis stretched polypropylene film (OPP film) to form an unhardened layer having a thickness of 100/zm. Coating film. Then, the uncured coating film was allowed to stand in an environment of a temperature of 20 ° C and a relative humidity of 60% for one week, and the coating film was cured by moisture in the air to obtain a urethane resin film. In Comparative Example 3, a propylene-based emulsion-based adhesive (product name: HC-025, manufactured by Cemedine Co., Ltd., containing a chelating agent) which is commercially available as a coating-type vibration-damping material composition was applied onto an OPP film to form A film with a thickness of 100 μm. Then, the coating film was allowed to stand in an environment of a temperature of 20 ° C and a relative humidity of 60% for a period of time to volatilize the water in the coating film to obtain a cured film.

有關上述所得到之各薄膜以啞鈴切刀切割成特定形狀 而從OPP薄膜剝離而製成試驗片，測定表3所示之物性。 亦即，亦依據JIS K6253 ( 1 997年版）之方法測定A硬度 。依據JIS K73 1 1 ( 1 99 5年版）而進行抗拉試驗，測定延 伸 100%時之抗拉彈性率（100%M、單位 MPa )、延伸 3 00%時之抗拉彈性率（3 00%厘、單位]^1?&)、抗拉強度（ Ts、單位MPa )及撕裂延伸（單位％ )。測定玻璃轉移溫 度。結果表示於表3.中。 又，爲評估減振性，對於上述所得到之各薄膜從OPP 薄膜剝離而製成試驗片，藉動態黏彈性測定裝置（S Π公 司製、製品名：EXSTAR DMS6100 )，以抗拉模式測定損 -42- 200840830 失係數（tan (5 )。使用將薄膜切割成長度20mm、寬度 10mm、厚度100# m者作爲評估試樣。損失係數係以ιΗζ 之頻率在-1 〇 〇〜1 2 0 °C之範圍進行測定，對於溫度依存性 進行評估。1 0〜5 0 °c之測定結果表示於表3中。 進一步.，對於上述所得到之各薄膜使用與上述損失係 數同樣之評估試樣而藉動態黏彈性測定裝置，測定2 5 °C之 貯存彈性率（彈性：Pa )。結果表示於表3中。Each of the films obtained above was cut into a specific shape by a dumbbell cutter, and peeled off from the OPP film to prepare a test piece, and the physical properties shown in Table 3 were measured. That is, the A hardness is also measured in accordance with the method of JIS K6253 (1998 edition). Tensile test was carried out according to JIS K73 1 1 (1 99 5 years), and the tensile modulus at 100% elongation (100% M, unit MPa) and tensile modulus at 300% elongation (300%) were measured. PCT, unit]^1?&), tensile strength (Ts, unit MPa) and tear extension (unit%). The glass transition temperature was measured. The results are shown in Table 3. In addition, in order to evaluate the vibration damping property, each of the obtained films was peeled off from the OPP film to prepare a test piece, and the dynamic viscoelasticity measuring device (manufactured by S. Co., Ltd., product name: EXSTAR DMS6100) was used to measure the damage in a tensile mode. -42- 200840830 Loss factor (tan (5). Use the film to be cut into length 20mm, width 10mm, thickness 100# m as the evaluation sample. The loss coefficient is at -1 〇〇~1 2 0 ° at the frequency of ιΗζ The range of C was measured, and the temperature dependence was evaluated. The measurement results of 10 0 to 50 ° C are shown in Table 3. Further, for each of the films obtained above, the same evaluation sample as the above loss coefficient was used. The storage elastic modulus (elasticity: Pa) at 25 ° C was measured by a dynamic viscoelasticity measuring device. The results are shown in Table 3.

爲評估黏著性，分別使用於實施例1〜5及比較例1、 2得到之異氰酸酯基末端預聚物（P 1〜P 5及Q 1、Q2 )及比 較例3所使用之丙烯基乳化液系黏著劑，俾貼合由木材所 構成之2片的試驗片。 亦即，分別使上述預聚物（P1〜P5及Ql、Q2 )及丙 烯基乳化液系黏著劑塗佈於由木材所構成之試驗片上成爲 縱X橫X厚爲 25mmx25mmxlmm。塗佈後載置由寬爲 25mm 之木材所構成的試驗片，以手輕壓。再於溫度23 °C、相對 溼度爲60%的槽內放置1周而使上述預聚物及丙烯基乳化 液系黏著劑。 藉以下之剪斷試驗評估如此所得到之試料的黏著力。 剪斷試驗係使用拉抗試驗機（東洋Baldwin公司製、製品 名：Tensilon VTM-DI -200 )，以抗拉速度5 0mm/分之條件 ，測定剪斷剝離強度。以剪斷剝離強度之測定値作爲黏著 力（單位：N/m2 )表示於表3中。 -43- 200840830To evaluate the adhesion, the isocyanate group-terminated prepolymers (P 1 to P 5 and Q 1 and Q 2 ) obtained in Examples 1 to 5 and Comparative Examples 1 and 2, respectively, and the propylene-based emulsion used in Comparative Example 3 were used. An adhesive is applied to the test pieces of two pieces made of wood. Namely, the prepolymers (P1 to P5 and Q1, Q2) and the alkenyl emulsion-based adhesive were applied to a test piece made of wood to have a vertical X-axis X thickness of 25 mm x 25 mm x 1 mm. After coating, a test piece composed of wood having a width of 25 mm was placed and lightly pressed by hand. Further, the prepolymer and the propylene-based emulsion-based adhesive were placed in a tank having a temperature of 23 ° C and a relative humidity of 60% for one week. The adhesion of the sample thus obtained was evaluated by the following shear test. The shearing test was carried out using a tensile tester (manufactured by Toyo Baldwin Co., Ltd., product name: Tensilon VTM-DI-200), and the shear peel strength was measured at a tensile speed of 50 mm/min. The measurement of the shear peel strength is shown in Table 3 as the adhesive force (unit: N/m2). -43- 200840830

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比較例3 丙烯系 95(含塡充劑） 1 義 寸 cn o P 0.26 0.60 0.82 0.84 0.70 0.57 3xl08 7.6xl05 比較例2 (N 〇 ON I 1 23.6 § P Os 1 0.10 1 0.10 0.10 0.10 0.09 0.09 7x108 29.8xl05 | 比較例1 〇 ON (N (N 00 (N r-H On | lioo | | -40°c 1 0.11 0.08 0.07 0.06 0.05 0.05 2xl07 7.6xl05 實施例5 to Oh m 00 o r-H t-H 00 cn 1460 P 寸 1 1.05 1 1 0.54 1 0.37 0.27 0.19 0.16 lxlO7 6.3xl05 實施例4 2 § 寸 <N 〇\ 54.4 o r < 1 0.38 1 丨 I·% 1 1.34 1.19 0.88 0.77 2xl07 7.8xl05 實施例3 m Oh (N 00 vd 24.4 51.3 450 | 25°c | 0.10 0.18 0.43 s 1.29 0.72 lx!09 16.6xl05 實施例2 (N Oh oo ON CN cn 〇< 65.3 P H 1 0-14 1 0.51 0.76 1.14 0.67 0.33 9xl07 10.6xl05 實施例1 Oh (N o (N 卜 cn 42.0 1670^I P in 0.98 1 0.61 1 0.50 0.35 0.24 0.15 lxlO7 8.0xl05 預聚物 A硬度 貨 Oh i O o Oh 〇 | Ts(MPa) 破裂延伸(％) 玻璃轉移溫度 tan δ 10°C tan δ 2 0°C tan ά 25〇C tan δ 3 0°C tan 5 4 0°C tan δ 5 0°C 貯存彈性率(Pa) 真 W 薄膜 ίΓχΑΐΙ» tH -44- 200840830 認爲一般具有減振效果者係可謂損失係數（tan 6 ) 爲〇·1以上，損失係數爲0.1以上之溫度範圍愈廣者，溫 度依存性愈小，具有良好的減振性。 Ι·Comparative Example 3 Propylene 95 (containing ruthenium) 1 寸 cn o P 0.26 0.60 0.82 0.84 0.70 0.57 3xl08 7.6xl05 Comparative Example 2 (N 〇 ON I 1 23.6 § P Os 1 0.10 1 0.10 0.10 0.10 0.09 0.09 7x108 29.8 Xl05 | Comparative Example 1 〇 ON (N (N 00 (N rH On | lioo | | -40°c 1 0.11 0.08 0.07 0.06 0.05 0.05 2xl07 7.6xl05 Example 5 to Oh m 00 o rH tH 00 cn 1460 P inch 1 1.05 1 1 0.54 1 0.37 0.27 0.19 0.16 lxlO7 6.3xl05 Example 4 2 § inch <N 〇\ 54.4 or < 1 0.38 1 丨I·% 1 1.34 1.19 0.88 0.77 2xl07 7.8xl05 Example 3 m Oh (N 00 Vd 24.4 51.3 450 | 25°c | 0.10 0.18 0.43 s 1.29 0.72 lx!09 16.6xl05 Example 2 (N Oh oo ON CN cn 〇< 65.3 PH 1 0-14 1 0.51 0.76 1.14 0.67 0.33 9xl07 10.6xl05 Example 1 Oh (N o (N cn 42.0 1670^IP in 0.98 1 0.61 1 0.50 0.35 0.24 0.15 lxlO7 8.0xl05 prepolymer A hardness goods Oh i O o Oh 〇 | Ts (MPa) rupture extension (%) glass transition temperature Tan δ 10°C tan δ 2 0°C tan ά 25〇C tan δ 3 0°C tan 5 4 0°C tan δ 5 0°C Storage Elasticity (Pa) True W Film ΓχΑΐΙ tH -44- 200840830 It is considered that the general damping effect is that the loss coefficient (tan 6 ) is 〇·1 or more, and the temperature range with a loss coefficient of 0.1 or more is wider, the temperature dependence is smaller, and the vibration damping is good. Sex.

在實施例1〜5所得到之薄膜系任一者均涵蓋10〜50 °C之廣溫度範圍而維持損失係數0.1以上，顯示良好的減 振性，同時25°C之貯存彈性率任一者均高達1x1 07Pa以上 ，彈性率與tan (5之均衡佳。破裂延伸亦亦良好。又，依 實施例1〜5之預聚物的硬化物（減振性用胺基甲酸乙酯樹 脂）而黏著木材之試驗片時之黏著力亦良好。 然而，使聚醚多元醇與聚異氰酸酯化合物反應所得到 之比較例1的薄膜係損失係數低而減振性不充分。 使聚酯多元醇與聚異氰酸酯化合物反應所得到之比較 例2的薄膜係損失係數低而破裂延伸亦差。若薄膜之破裂 延伸不佳，使用於熱收縮率互異之被黏體的貼合時易產生 剝離。 使用丙烯乳化液系黏著劑之比較例3係黏著性、貯存 彈性率及tan (5任一者均良好，但破裂延伸差。 〔實施例1 1 :單液濕氣硬化性組成物之製造〕 於具備攪拌機及氮氣導入管之反應容器內，饋入製造 例1得到之聚酯醚二醇（A1-1 )的75 3 g、與作爲聚異氰 酸酯化合物（B )的MDI之247g，在氮氣環境下80°C反 應4小時。異氰酸酯基/羥基（莫耳比）爲2·52。 取出反應後之內容物的一部分而測定異氰酸酯基（以 -45- 200840830 下，有時省略爲NCO )含量，確認理論上所計算之含量以 下而停止反應而移出，得到NCO含量4.95質量％、在60 °C下之黏度33 0 0( mP a· s)的異氰酸酯基末端預聚物。 使用此作爲單液濕氣硬化性組成物 〔實施例1 2 :單液濕氣硬化性組成物之製造〕 在實施例11中將聚酯醚二醇（A1-1)變更成聚酯醚 ΙΦ 二醇（A1-5 )以外，其餘係與實施例1 1同樣做法而得到 異氰酸酯基末端預聚物。異氰酸酯基/羥基（莫耳比）爲 2·50 〇 所得到之異氰酸酯基末端預聚物的NCO含量係4.87 質量％、在60°C之黏度爲llOOO(mPa.s)。使用此作爲 單液濕氣硬化性組成物。 〔實施例1 3 :單液濕氣硬化性組成物（含有添加劑）之製 I· 造〕 於實施例11所得到之異氰酸酯基末端預聚物中添加 添加劑而製造單液濕氣硬化性組成物。 亦即，於實施例11所得到之異氰酸酯基末端預聚物 之43 0g中，加入作爲可塑劑之二異壬基酞酸酯50g、作爲 溶劑之甲苯70g、作爲塡充材之重質碳酸鈣（白石工業公 司製：NS-400以下相同）400g及微粒合成碳酸鈣（白石 工業公司製：白豔華CCR以下相同）50g而混練者作爲單 液濕氣硬化性組成物。 -46 -Any of the film systems obtained in Examples 1 to 5 covers a wide temperature range of 10 to 50 ° C and maintains a loss coefficient of 0.1 or more, exhibiting good vibration damping properties, and at the same time, storage elastic modulus at 25 ° C. Both are up to 1x1 07Pa or more, and the elastic modulus is good with tan (5 is good. The crack elongation is also good. Moreover, the cured product of the prepolymer according to Examples 1 to 5 (the damping property is made of urethane resin) The adhesion of the test piece to the wood was also good. However, the film of Comparative Example 1 obtained by reacting the polyether polyol with the polyisocyanate compound had a low loss coefficient and insufficient vibration damping property. The film of Comparative Example 2 obtained by the reaction of the isocyanate compound had a low loss coefficient and a poor elongation at break. When the film was not broken, the film was easily peeled off when it was bonded to the adherend having different heat shrinkage rates. Comparative Example 3 of the emulsion-based adhesive is adhesiveness, storage elastic modulus, and tan (5 is good, but the crack elongation is poor. [Example 1 1 : manufacture of single-liquid moisture-curable composition] Mixer and nitrogen 75 3 g of the polyester ether diol (A1-1) obtained in Production Example 1 and 247 g of MDI as the polyisocyanate compound (B) were fed into the reaction vessel in the tube, and reacted at 80 ° C in a nitrogen atmosphere. The isocyanate group/hydroxyl group (mole ratio) was 2.52. A part of the content after the reaction was taken out, and the content of the isocyanate group (hereinafter, -45-200840830, sometimes omitted) was confirmed, and the theoretical calculation was confirmed. When the content is less than the content, the reaction is stopped and removed, and an isocyanate-based terminal prepolymer having an NCO content of 4.95 mass% and a viscosity of 3300 (mPa·s) at 60 ° C is obtained. This is used as a one-liquid moisture hardening composition. [Example 1 2: Production of single-liquid moisture-curing composition] In Example 11, the polyester ether diol (A1-1) was changed to a polyester ether Ι Φ diol (A1-5), and the rest was An isocyanate-based terminal prepolymer was obtained in the same manner as in Example 11. The isocyanate group-hydroxyl group (mole ratio) was 2·50 〇. The obtained isocyanate group-terminated prepolymer had an NCO content of 4.87 mass% at 60°. The viscosity of C is llOOO (mPa.s). Use this as a single liquid moisture hardening [Example 1 3: Preparation of a single-liquid moisture-curing composition (containing an additive) I. Production] Adding an additive to the isocyanate-based terminal prepolymer obtained in Example 11 to produce a single-liquid moisture hardening In the 43 0 g of the isocyanate group-terminated prepolymer obtained in Example 11, 50 g of diisodecyl phthalate as a plasticizer and 70 g of toluene as a solvent were added as a ruthenium. 400 g of heavy calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd.: NS-400 or less) and 50 g of finely synthesized calcium carbonate (manufactured by Shiraishi Kogyo Co., Ltd.: the following is the same as Cyan CCR), and the kneader was a one-liquid moisture-curing composition. -46 -

200840830 〔實施例1 4 :單液濕氣硬化性組成物（含有添加劑） 造〕 於實施例1 2所得到之異氰酸酯基末端預聚物之 中，加入與實施例1 3相同之添加劑而混練者作爲骂 氣硬化性組成物。 〔實施例1 5 :單液濕氣硬化性組成物（含有添加劑） 造〕 在實施例11中將聚酯醚二醇（A1-1)之使用』 成624g，將二苯基甲烷二異氰酸酯之使用量變更成 以外，其餘係與實施例11同樣做法而得到異氰酸| 端預聚物。異氰酸酯基/羥基（莫耳比）爲4.83。戶 之異氰酸酯基末端預聚物的NCO含量係9.92質量 60°C 之黏度爲 1 800 ( mPa · s )。 於所得到之預聚物4 3 0 g中，加入與實施例1 3 \ 添加劑而混練者作爲單液濕氣硬化性組成物。 〔實施例1 6 :單液濕氣硬化性組成物（含有添加劑） 造〕 在實施例12中將聚酯醚二醇（A1-5 )之使用j 成622 g，將二苯基甲烷二異氰酸酯之使用量變更成 以外，其餘係與實施例1 2同樣做法而得到異氰酸画 端預聚物。異氰酸酯基/羥基（莫耳比）爲4.74。戶j 的製 430g 液濕 的製 變更 376g 基末 得到 、在 同之 的製 變更 3 78g 基末 得到 -47- 200840830 之異氰酸酯基末端預聚物的NCO含量係9.90質量％、在 60°C 之黏度爲 6000 (mPa*s)。 於所得到之預聚物4 3 〇 g中，加入與實施例1 3相同之 添加劑而混練者作爲單液濕氣硬化性組成物。 〔比較例1 1〕 使用不具有酯基之聚醚多元醇取代聚酯醚多元醇（A1 )而調製單液濕氣硬化性組成物。 亦即，於實施例11中，使用聚氧丙二醇（PPG-2000 )取代製造例1所得到之聚酯醚二醇（A1_l)外，其餘係 與實施例11同樣做法而得到異氰酸酯基末端預聚物。異 截酸醋基/經基（旲耳比）爲2.57。所得到之異氰酸酯基 末端預聚物的NCO含量係4.96質量。/。、在“它之黏度爲 8 5 0 ( mP a · s )。使用此作爲單液濕氣硬化性組成物。200840830 [Example 14: Single-liquid moisture-curing composition (containing additive)] The same additive as in Example 13 was added to the isocyanate-based terminal prepolymer obtained in Example 12, and the kneader was added. As a heric hardening composition. [Example 1 5: single-liquid moisture-curing composition (containing an additive)] In Example 11, the use of the polyester ether diol (A1-1) was 624 g, and diphenylmethane diisocyanate was used. The isocyanate end-polymer was obtained in the same manner as in Example 11 except that the amount used was changed. The isocyanate group/hydroxyl group (Mohr ratio) was 4.83. The NCO content of the isocyanate-based terminal prepolymer is 9.92 mass and the viscosity at 60 ° C is 1 800 (mPa · s). To the obtained prepolymer of 430 g, a compound which was kneaded with the Example 1 3 \ additive was added as a one-liquid moisture-curing composition. [Example 1 6: single-liquid moisture-curing composition (containing an additive)] In Example 12, the use of the polyester ether diol (A1-5) was 622 g, and diphenylmethane diisocyanate was used. The isocyanate terminal prepolymer was obtained in the same manner as in Example 12 except that the amount used was changed. The isocyanate group/hydroxyl group (Mohr ratio) was 4.74. 430 g of the liquid of the product was changed to 376 g of the liquid, and the NCO content of the isocyanate-based terminal prepolymer of -47-200840830 was 9.90 mass% at 60 ° C. The viscosity is 6000 (mPa*s). To the obtained prepolymer 4 3 〇 g, the same additives as in Example 13 were added, and the kneader was used as a one-liquid moisture-curing composition. [Comparative Example 1 1] A single-liquid moisture-curable composition was prepared by substituting a polyester ether polyol (A1) with a polyether polyol having no ester group. That is, in Example 11, except that the polyether propylene glycol (PPG-2000) was used instead of the polyester ether diol (A1_1) obtained in Production Example 1, the same procedure as in Example 11 was carried out to obtain an isocyanate group terminal prepolymerization. Things. The isocyanate/base group (the molar ratio) was 2.57. The resulting isocyanate-based terminal prepolymer had an NCO content of 4.96 mass. /. "It has a viscosity of 850 (mP a · s). Use this as a one-component moisture-curing composition.

〔比較例1 2〕 使用己二酸系聚酯多元醇取代聚酯醚多元醇（A1)而 調製單液濕氣硬化性組成物。 亦即，於實施例1 1中，使用聚（丁二醇）己二酸酯 二醇（PBA )取代製造例1所得到之聚酯醚二醇（A1-1 ) 外，其餘係與實施例1 1同樣做法而得到異氰酸酯基末端 預聚物。異氰酸酯基/羥基（莫耳比）爲2.57。所得到之 異氰酸酯基末端預聚物的N C Ο含量係4.9 0質量％、在6 0 它之黏度爲1 0000 ( mPa · s )。使用此作爲單液濕氣硬化 -48- 200840830 性組成物。 〔比較例1 3〕 使用酞酸系聚酯多元醇取代聚酯醚多元醇（A1)而調 製單液濕氣硬化性組成物。 亦即，於實施例11中，使用聚（3 -甲基戊二醇）異 酞酸酯二醇（IP/MPD )取代製造例1所得到之聚酯醚二醇 ΙΦ (A1-1)外，其餘係與實施例11同樣做法而得到異氰酸 酯基末端預聚物。異氰酸酯基/羥基（莫耳比）爲2.57。 所得到之異氰酸酯基末端預聚物的NCO含量係4.98質量 °/〇、在60°C之黏度爲ZSOOOCmPa.s)。使用此作爲單液 濕氣硬化性組成物。 〔比較例1 4〕[Comparative Example 1 2] A single-liquid moisture-curable composition was prepared by substituting an adipic acid-based polyester polyol for the polyester ether polyol (A1). That is, in Example 11, except that the poly(butanediol) adipate diol (PBA) was used instead of the polyester ether diol (A1-1) obtained in Production Example 1, the remaining examples and examples 1 1 An isocyanate-based terminal prepolymer was obtained in the same manner. The isocyanate group / hydroxyl group (mole ratio) was 2.57. The obtained isocyanate group-terminated prepolymer had a N C Ο content of 4.90 mass% and a viscosity of 60 10,000 (mPa · s). Use this as a one-component moisture hardening -48- 200840830 sex composition. [Comparative Example 1 3] A one-component moisture-curable composition was prepared by substituting a polyesterether polyol (A1) with a capric acid-based polyester polyol. That is, in Example 11, poly(3-methylpentanediol)isodecanoate diol (IP/MPD) was used instead of the polyester ether diol Φ (A1-1) obtained in Production Example 1. The same procedure as in Example 11 was carried out to obtain an isocyanate group-terminated prepolymer. The isocyanate group / hydroxyl group (mole ratio) was 2.57. The resulting isocyanate-based terminal prepolymer had an NCO content of 4.98 mass ° / 〇 and a viscosity at 60 ° C of ZSOOOCmPa.s). This was used as a one-part moisture-curing composition. [Comparative Example 1 4]

使用酞酸系聚酯多元醇與聚醚多元醇之混合物取代聚 酯醚多元醇（A1 )而調製單液濕氣硬化性組成物。' 亦即，於具備攪拌機及氮氣導入管之反應容器內，投 入IP/MPD之3 79g與PPG-2000之3 78 g而混合進一步饋 入二苯基甲烷二異氰酸酯243g，在氮氣環境下80 °C反應4 小時。異氰酸酯基/羥基（莫耳比）爲2.57。取出反應後 之內容物的一部分而測定NCO含量，確認理論上所計算 之含有量以下而停止反應而移出，得到NCO含量4·99質 量％、在60°C下之黏度5500 (mPa*s)的異氰酸酯基末 端預聚物。使用此作爲單液濕氣硬化性組成物 -49- 200840830 <評估> 〔硬化物（薄膜）之物性〕 使上述實施例及比較例得到之單液濕氣硬化性組成物 於雙軸延伸聚丙烯薄膜（OPP薄膜）上以薄塗器塗佈成膜 厚5 00 // m，以20 °c、相對溼度60 °C之條件培養1週，溼 氣硬化。所得到之薄膜以啞鈴切刀切割成特定形狀而從 OPP薄膜剝離以製成試驗片，測定以下之物性。 測定延伸 1〇〇%時之抗拉彈性率（1〇〇%Μ、單位MPa )、延伸 3 00°/。時之抗拉彈性率（3 00%M、單位 MPa )、 抗拉撕裂強度（Ts、單位MPa)及撕裂延伸（E、單位％ )之各物性。物性測定條件係依據 JIS-K731 1，使用抗拉 試驗機作爲測定機器，以啞鈴3號作爲試驗片，以抗拉速 度2 0 0mm/分之條件進行。測定結果表示於表4中。A single-liquid moisture-curable composition was prepared by substituting a polyester ether polyol (A1) with a mixture of a tannic acid-based polyester polyol and a polyether polyol. That is, in a reaction vessel equipped with a stirrer and a nitrogen inlet pipe, 3 79 g of IP/MPD and 3 78 g of PPG-2000 are mixed and further fed with 243 g of diphenylmethane diisocyanate, 80 ° under nitrogen atmosphere. C reacted for 4 hours. The isocyanate group / hydroxyl group (mole ratio) was 2.57. A part of the content after the reaction was taken out, and the NCO content was measured, and the theoretically calculated content was determined to be less than the theoretical amount, and the reaction was stopped and removed to obtain an NCO content of 4.99 mass% and a viscosity of 5500 (mPa*s) at 60 °C. Isocyanate based terminal prepolymer. Use of this as a one-liquid moisture-curing composition-49-200840830 <Evaluation> [Physical properties of cured product (film)] The single-liquid moisture-curing composition obtained in the above Examples and Comparative Examples was biaxially stretched. The polypropylene film (OPP film) was coated with a thin coater to a film thickness of 500 00 m, and cultured at 20 ° C and a relative humidity of 60 ° C for 1 week, and the film was hardened by moisture. The obtained film was cut into a specific shape by a dumbbell cutter and peeled off from the OPP film to prepare a test piece, and the following physical properties were measured. The tensile modulus (1〇〇%Μ, unit MPa) at an elongation of 1% was measured, and the elongation was 300°/. Tensile elastic modulus (300% M, unit MPa), tensile tear strength (Ts, unit MPa) and tear elongation (E, unit%) of various physical properties. The physical property measurement conditions were carried out in accordance with JIS-K731 1, using a tensile tester as a measuring machine, and dumbbell No. 3 as a test piece, at a tensile speed of 200 mm/min. The results of the measurements are shown in Table 4.

〔黏著性試驗〕 依據JIS K_68 3 3，依以下之方法進行單液濕氣硬化性 組成物的黏著試驗。 (試驗試料製成） 於25mm寬xlOOmm長x4mm厚之木質合板（以下，略 稱爲Veneer)的一端部25mmx25mm之位置，以杓刀塗佈 單液濕氣硬化性組成物成爲0.2mm之厚度。於該塗佈部份 之上，使25mm寬xlOOmm長X2mm厚之鋁製板（以下略稱 -50-[Adhesiveness test] According to JIS K_68 3 3, the adhesion test of the one-liquid moisture-curable composition was carried out in the following manner. (Prepared by test sample) The single-liquid moisture-curable composition was applied to a thickness of 0.2 mm at a position of 25 mm x 25 mm at one end of a 25 mm wide x 100 mm long x 4 mm thick wood plywood (hereinafter, abbreviated as Veneer). On the coated portion, an aluminum plate of 25 mm wide x 100 mm long and X 2 mm thick (hereinafter abbreviated as -50-

200840830 爲A1)的一端部25mmx25mm，以膠合板（Veneer 一端與A 1之另一端挾住前述塗佈部份而互相對向 載置以手輕壓，進一步以挾時治具挾持固定。再以 相對溼度50%的條件培養1週而硬化，得到試驗試淨 (剝離試驗） 對於所得到之試驗試料，使用拉抗試驗機 B a 1 d w i η 公司製、製品名：T e n s i 1 ο η V Τ Μ - ΠΙ - 2 0 0 ) 拉速度50mm/分之條件，測定剪斷剝離強度（單位 )。其結果表示於表3中。 又，以目視觀察剝離後之剝離狀態而評估。結 於表4中。於表4中「AF」表示界面剝離。又， 數値）」係以面積的比率表示剝離狀態者，例如 係黏著部份之全面積之中的8 0%於A 1與硬化性組 界面剝離，20%於膠合板（Veneer)與硬化性組成 面剝離。表4中之該面積的比率之値係對於3個試 進行同樣之剝離試驗時的平均値。 )的另 之方式 2 3〇C 、 (東洋 ，以抗 ：N/m2 果表示 「AL ( 「AL80 成物之 物的界 驗試料 •51 - 200840830 〔表4〕 Ι· 單液硬化性 組成物之黏 度(mPa · s) 薄膜之物性 接著性( 膠合板） 100M (MPa) 300M (MPa) Ts (MPa) E (%) 剪斷剝離強 度(N/m2) 剝離狀態 實施例11 3,300 2.0 3.7 42.0 670 17.2x10s AF AL90 實施例12 11,000 2.9 9.3 65.3 520 25·7χ105 AFAL90 實施例13 賺 • 供 18.4χ105 AF AL80 實施例14 - • 21.4χ105 AFAL70 實施例15 一 • • • 20.1χ105 AF AL80 實施例16 擊 讎 27.8χ105 AF AL70 比較例” 850 2.2 2.8 9.1 1,100 7.9χ105 AF AL100 比較例12 10,000 丨 • 23.6 80 lS.OxlO5 AF ALI00 比較例13 25,000 • • 38.4 10 18.5χ105 AFAL100 比較例14 5,500(分離） 霉 • - • 咖 •200840830 is one end of A1) 25mmx25mm, with plywood (Veneer end and the other end of A 1 hold the coating part and put it against each other to lightly press it, further fix it with 挟 治. 50% of the conditions were cultured for 1 week and hardened, and the test was tested (peeling test). For the obtained test sample, a tensile tester B a 1 dwi η company, product name: T ensi 1 ο η V Τ Μ - ΠΙ - 2 0 0 ) The shear peel strength (unit) was measured under the conditions of a pulling speed of 50 mm/min. The results are shown in Table 3. Moreover, it evaluated by visually observing the peeling state after peeling. See Table 4. In Table 4, "AF" indicates interface peeling. Further, the number of 値)) indicates the peeling state by the ratio of the area, for example, 80% of the total area of the adhesive portion is peeled off from the interface between the A 1 and the sclerosing group, and 20% is in the veneer and the sclerosing property. The composition surface is peeled off. The ratio of the area in Table 4 is the average enthalpy of the same peel test for the three tests. Another way 2 3〇C, (Toyo, anti-: N/m2 fruit means "AL ("AL80 substance test sample • 51 - 200840830 [Table 4] Ι · Single-liquid hardening composition Viscosity (mPa · s) Physical properties of the film (plywood) 100M (MPa) 300M (MPa) Ts (MPa) E (%) Shear peel strength (N/m2) Peeling state Example 11 3,300 2.0 3.7 42.0 670 17.2x10s AF AL90 Example 12 11,000 2.9 9.3 65.3 520 25·7χ105 AFAL90 Example 13 Earnings • For 18.4χ105 AF AL80 Example 14 - • 21.4χ105 AFAL70 Example 15 One • • • 20.1χ105 AF AL80 Example 16 Killing 27.8χ105 AF AL70 Comparative Example 850 2.2 2.8 9.1 1,100 7.9χ105 AF AL100 Comparative Example 12 10,000 丨• 23.6 80 lS.OxlO5 AF ALI00 Comparative Example 13 25,000 • • 38.4 10 18.5χ105 AFAL100 Comparative Example 14 5,500 (Separation) Mildew • - • Coffee •

從實施例1 1、1 2及比較例1 1〜1 4之結果，由本發明 之預聚物所構成之實施例U、1 2的單液濕氣硬化性組成 物係易以低黏度使用，使該構之組成物硬化而得到之薄膜 ，係延伸優且破裂強度亦良好。又，剪斷剝離強度高且接 著性亦優。 對於此而使用聚醚多元醇所調製之預聚物所構成的比 較例1 1係黏度低且薄膜之延伸良好，但薄膜之破裂強度 及接著性差。 使用聚酯多元醇所調製之預聚物所構成的比較例1 2、 13係黏著性良好，但硬化物（薄膜）之延伸及破裂強度差 。若薄膜之延伸不佳，則使用於熱收縮率互異之被黏體的 貼合時易產生剝離。 使用聚醚多元醇與聚酯多元醇的混合物所調製之預聚 -52- 200840830 物所構成的比較例1 4之組成物，係若放置，液體會分離 ，於2軸延伸聚丙烯薄膜（OPP薄膜）上以薄塗器塗佈成 膜厚500 /z m，均無法得到均一之薄片。因此，在比較例 1 4中，係不進行薄膜物性及黏著性之評估。 如實施例1 3〜1 6般，若調製碳酸鈣等之添加劑，可賦 予防垂流等之特性，同時並可謀求製品之成本降低。在實 施例13〜16中係即使添加劑，剪斷強度亦高，黏著性良好 I· ，可看出作爲黏著劑無實用上問題。又，若添加碳酸鈣， 成爲非牛頓流體，無法測定黏度，故無法測定黏度。 產業上之利用可能性 本發明之減振材料用胺基甲酸乙酯樹脂，係黏著性良 好、損失係數大且減振性優，同時彈性率與損失係數之均 衡佳且延伸亦良好。From the results of Examples 1 1 and 2 2 and Comparative Examples 1 1 to 4, the single-liquid moisture-curing composition of Examples U and 12 composed of the prepolymer of the present invention was easily used at a low viscosity. The film obtained by hardening the composition of this structure is excellent in elongation and good in burst strength. Moreover, the shear peel strength is high and the adhesion is excellent. The comparative example 1 1 composed of the prepolymer prepared by using the polyether polyol has a low viscosity and a good film extension, but the film has poor fracture strength and adhesion. In Comparative Examples 1 and 2, which were composed of a prepolymer prepared by using a polyester polyol, the adhesion was good, but the elongation (strength) of the cured product (film) was poor. If the film is not stretched well, it is likely to be peeled off when the adherend of the adherend having different heat shrinkage rates is used. The composition of Comparative Example 14 composed of a mixture of a polyether polyol and a polyester polyol prepared by prepolymerization-52-200840830, if placed, the liquid is separated, and the 2-axis extended polypropylene film (OPP) The film was coated with a thin coater to a film thickness of 500 /zm, and a uniform sheet could not be obtained. Therefore, in Comparative Example 14, evaluation of film physical properties and adhesion was not performed. When the additives such as calcium carbonate are prepared as in the case of Examples 1 to 3, the characteristics such as the anti-flowing property can be imparted, and the cost of the product can be reduced. In Examples 13 to 16, even if the additive was used, the shear strength was high and the adhesion was good I·, and it was found that there was no practical problem as an adhesive. Further, when calcium carbonate is added to form a non-Newtonian fluid, the viscosity cannot be measured, and thus the viscosity cannot be measured. INDUSTRIAL APPLICABILITY The urethane resin for a vibration damping material of the present invention has good adhesion, a large loss coefficient, and excellent vibration damping properties, and has a good balance between an elastic modulus and a loss coefficient and a good elongation.

又，本發明之單液濕氣硬化性組成物係適宜於黏著用 途，具體上宜使用於要求黏著劑、塗佈材、密封材、彈性 鋪裝材或防水材等與基材良好的黏著性之用途。 對於木材、金屬（尤其鋁）及樹脂之黏著性優，故適 於建築材料之黏著劑；汽車零件之黏著劑·，及食品包裝薄 膜等的積層中之黏著劑等。 又，2006年10月27日所申請、日本專利申請案 2006-292432號及日本專利申請案2006-292433號之說明 書、申請專利範圍、及摘要的全部內容引用於此，摘錄作 爲本發明之說明書揭示。 -53 -Moreover, the single-liquid moisture-curing composition of the present invention is suitable for adhesive use, and is particularly preferably used for adhesion to a substrate such as an adhesive, a coating material, a sealing material, an elastic paving material or a waterproof material. Use. It is excellent for adhesion to wood, metal (especially aluminum) and resin, and is therefore suitable for adhesives for building materials; adhesives for automotive parts, and adhesives for laminates such as food packaging films. The entire contents of the specification, the patent application, and the abstract of the Japanese Patent Application No. 2006-292432 and the Japanese Patent Application No. 2006-292433, the entire contents of reveal. -53 -

Claims (1)

200840830 十、申請專利範圍 1· 一種減振材料用胺基甲酸乙酯樹脂的製造方法， 其爲使多元醇（A)與聚異氰酸酯化合物（B )反應而製造 減振材料用胺基甲酸乙酯樹脂之方法，其特徵係該多元醇 (A)含有：在觸媒（χ)的存在下，對於起始劑（a)共 聚合聚羧酸酐（b)及環氧烷（c)而得到的聚酯醚多元醇 (A1 ) 〇 2 · —種減振材料用胺基甲酸乙酯樹脂的製造方法， 其爲使多元醇（A )與聚異氰酸酯化合物（B )反應所得到 的異氰酸酯封.端預聚物，進行溼氣硬化而製造減振材料用 胺基甲酸乙酯樹脂之方法，其特徵係該多元醇（A )含有 :在觸媒（X)的存在下，對於起始劑（a)共聚合聚羧酸 酐（b )及環氧烷（c )而得到的聚酯醚多元醇（a 1 )。200840830 X. Patent Application No. 1. A method for producing a urethane resin for a vibration damping material, which comprises reacting a polyol (A) with a polyisocyanate compound (B) to produce a urethane for a vibration damping material A resin method characterized in that the polyol (A) comprises a copolymerization of a polycarboxylic acid anhydride (b) and an alkylene oxide (c) with respect to the initiator (a) in the presence of a catalyst (χ). Polyetherether polyol (A1) 〇2 · A method for producing a urethane resin for a vibration damping material, which is an isocyanate ester obtained by reacting a polyol (A) with a polyisocyanate compound (B) A method for producing a urethane resin for a vibration damping material by moisture curing, characterized in that the polyol (A) contains: in the presence of a catalyst (X), for a starter (a) A polyesterether polyol (a 1 ) obtained by copolymerizing a polycarboxylic acid anhydride (b) and an alkylene oxide (c). 3 · —種減振材料用胺基甲酸乙酯樹脂的製造方法， 其爲使多元醇（A )與聚異氰酸酯化合物（B )反應所得到 的異氰酸酯封端預聚物所成的主劑成份、與硬化劑成份反 應而製造減振材料用胺基甲酸乙酯樹脂之方法，其特徵係 該多元醇（A)含有：在觸媒（X)的存在下，對於起始劑 (a)共聚合聚羧酸酐（b)及環氧烷（c)而得到的聚醋 醚多元醇（A1)。 4·如申請專利範圍第丨至3項中任一項之減振材料 用胺基甲酸乙酯樹脂的製造方法，其中該觸媒（X)爲複 合金屬氰化物錯合物。 5 ·如申請專利範圍第1至4項中任一項之減振材料 -54- 200840830 用胺基甲酸乙酯樹脂的製造方法，其中該多元醇（ 有2種以上的該聚酯醚多元醇（A1)，而且該2種 聚酯醚多元醇（A1)係玻璃轉移溫度互不相同。 6·如申請專利範圍第5項之減振材料用胺基 酯樹脂的製造方法，其中該多元醇（A)含有：爲 醚多元醇（A1)且玻璃轉移溫度爲-6〇。(：〜_3〇。〇的 第1聚酯醚多元醇（All)、與爲該聚酯醚多元醇 | Φ 且玻璃轉移溫度爲_45°c〜-15°C的範圍之第2聚酯 醇（A12)，而且該第1聚酯醚多元醇（A11)與| 酯醚多元醇（A12)的玻璃轉移溫度的差距爲15艺 的範圍。 7 ·如申請專利範圍第1至6項中任一項之減 用胺基甲酸乙酯樹脂的製造方法，其中該減振材料 甲酸乙酯樹脂的耗損係數，在；I 〇 t〜5 〇它的範圍爲 上。 8 · —種減振材料用胺基甲酸乙酯預聚物，其 多元醇（A )與聚異氰酸酯化合物（b )反應所得到 酸酯基封端預聚物所成的減振材料用胺基甲酸乙酯 ，其特徵係該多兀醇（A)含有：在觸媒（χ)的存 對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷（ 得到的聚酯醚多元醇（A1)。 9 · 一種減振材料用單液溼氣硬化型組成物， 係含有申請專利範圍第8項之減振材料用胺基甲酸 聚物。 A )含 以上的 甲酸乙 該聚酯 範圍之 (A1 ) 醚多元 $ 2聚 〜40〇。 振材料 用fl女某 0·1以 爲使由 的異氰 預聚物 在下， :C )而 其特徵 乙酯預 -55- 200840830 1 〇 · —種減振材料用雙液硬化型組成物系統，其特徵 係具有：含有申請專利範圍第8項之減振材料用胺基甲酸 乙酯預聚物之主劑組成物、與含有硬化劑成份之硬化組成 物。A method for producing a urethane resin for a vibration damping material, which is a main component of an isocyanate-terminated prepolymer obtained by reacting a polyol (A) with a polyisocyanate compound (B), A method for producing a urethane resin for a vibration damping material by reacting with a hardener component, characterized in that the polyol (A) comprises: copolymerization of the initiator (a) in the presence of a catalyst (X) A polyacetate polyol (A1) obtained by polycarboxylate (b) and alkylene oxide (c). The method of producing a urethane resin according to any one of claims 3 to 3, wherein the catalyst (X) is a composite metal cyanide complex. 5. The vibration damping material according to any one of claims 1 to 4, wherein the polyol (there are two or more kinds of the polyester ether polyol), the method for producing a urethane resin (A1), and the two polyester ether polyol (A1)-based glass transition temperatures are different from each other. 6. The method for producing an amine ester resin for a vibration-damping material according to claim 5, wherein the polyol (A) contains: an ether polyol (A1) and a glass transition temperature of -6 Å. (: 〜3 〇. The first polyester ether polyol (All) of 〇, and the polyester ether polyol Φ And the glass transition temperature is the second polyester alcohol (A12) in the range of _45 ° c ~ -15 ° C, and the glass transition of the first polyester ether polyol (A11) and | ester ether polyol (A12) The method of manufacturing the reduced urethane resin according to any one of claims 1 to 6, wherein the damping factor of the vibration-damping material ethyl urethane resin, In the range of I 〇t~5 〇, it is above. 8 · A kind of urethane prepolymer with damping material, its polyol (A ) The hydroxyurethane used for the vibration-damping material obtained by reacting the polyisocyanate compound (b) with the acid-ester-terminated prepolymer obtained by the reaction of the polyisocyanate compound (b) is characterized in that the polyterpene alcohol (A) contains: a catalyst (χ) The starting agent (a) copolymerizes the polycarboxylic acid anhydride (b) and the alkylene oxide (the obtained polyester ether polyol (A1). 9 · A single-liquid moisture-curing composition for a vibration damping material, which contains an application The amino acid carboxylic acid polymer of the vibration damping material of the eighth item of the patent range A) contains the above formic acid B. The polyester range (A1) ether is more than 2 ～40 〇. The vibration material is determined by the female girl 0·1. The isocyanide prepolymer is made of :C) and its characteristic ethyl ester pre-55-200840830 1 〇·- a two-liquid hardening type composition system for damping materials, which has the following features: The vibration damping material of the eighth item is composed of a main component of a urethane prepolymer and a hardening composition containing a hardener component. 1 1 · 一種單液溼氣硬化性組成物，其爲使羥基價i 0〜 300mgKOH/g的多元醇.（a)與聚異氰酸酯化合物（B)反 應所得到的異氰酸酯基封端預聚物作爲硬化成份之單液溼 氣硬化性組成物，其特徵系該多元醇（A )含有：對於起 始劑（a )共聚合聚羧酸酐（15)及環氧烷（（〇而得到的 聚酯醚多元醇（A1 )。 1 2.如申請專利範圍第1 1項之單液溼氣硬化性組成 物，其中對於起始劑（a )共聚合聚羧酸酐（b )及環氧烷 (c)之反應，係在複合金屬氰化物錯合物觸媒的存在下 進行。 1 3 .申請專利範圍第1 1項或1 2項之單液溼氣硬化性 組成物，其中該聚酯醚多元醇（A1)中之該聚羧酸酐（b )的含量爲1 〇〜5 0質量％。 14.如申請專利範圍第11項至13項中任一項之單液 溼氣硬化性組成物，其中該聚羧酸酐（b )爲酞酸酐。 1 5 .如申請專利範圍第1 1項至1 4項中任一項之單液 溼氣硬化性組成物，其係使用於黏著用途。 -56- 200840830 七 無 ·· 明 說 單 簡 號 為符 圖件 表元 代之 定圖 .指表 :案代 圖本本 表、、 代} } 定一二 b曰 無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學 式：無 -5-1 1 A single-liquid moisture-curing composition which is an isocyanate-terminated prepolymer obtained by reacting a polyol having a hydroxyl group of i 0 to 300 mgKOH/g. (a) with a polyisocyanate compound (B). a single-liquid moisture-curing composition of a hardening component characterized in that the polyol (A) comprises: a copolymerization of a polycarboxylic acid anhydride (15) and an alkylene oxide (starting agent) for the initiator (a) Ether polyol (A1). 1 2. The single-liquid moisture-curing composition of claim 1 wherein the polycarboxylate (b) and the alkylene oxide (c) are copolymerized with the initiator (a). The reaction is carried out in the presence of a composite metal cyanide complex catalyst. 1 3. A single-liquid moisture-curing composition of claim 1 or 12, wherein the polyester ether is plural The content of the polycarboxylic acid anhydride (b) in the alcohol (A1) is from 1 to 50% by mass. 14. The one-liquid moisture-curing composition according to any one of claims 11 to 13, Wherein the polycarboxylic anhydride (b) is phthalic anhydride. The single-liquid moisture-curing group according to any one of claims 1 to 14 Object, which is used for adhesive purposes. -56- 200840830 七无·············································· No. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: no -5-
TW96140074A 2006-10-27 2007-10-25 Urethane resin for vibration damping materials and curable composition TW200840830A (en)

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