TW483905B

TW483905B - A thermoplastic polyurethaneurea resin for melt spinning and the method for the preparation thereof

Info

Publication number: TW483905B
Application number: TW089102565A
Authority: TW
Inventors: Pyeon-No Ahn; Dong-Kyun Lee
Original assignee: Sk Chemicals Co Ltd
Priority date: 1998-11-06
Filing date: 2000-02-11
Publication date: 2002-04-21
Also published as: KR20000034038A; WO2000032855A1; EP1137830A1; JP2002531636A; KR100307214B1; CN1331764A

Abstract

There is disclosed a polyurethaneurea resin consisting of a polymer represented by the following chemical formula I: [A-O-(O)C-NH-D-NH-C(O)-NH-D-NH-C-(O)-O]n, wherein a represents an organopolyol residue having a number average molecular weight of approximately 500 to 5,000 and a weight average molecular weight/number average molecular weight (Mw/Mn) of 1.5 to 2.5 with the number of functional groups ranging from 1.8 to 2.2, D represents an aromatic organodiisocyanate residue ranging, in the number of functional groups, from 1.8 to 2.2, and n represents the number of repeat units. This resin is superior in thermal resistance and elastic recovery, so that it is suitable to melt spinning to make useful elastic fibers.

Description

經濟部智慧財產局員工消費合作社印製 483905 A7 ___ B7 五、發明說明（\) 發明背景發明領域本發明一般而言係關於一種聚胺基甲酸酯之彈性體，尤指具高抗熱性與商彈性回復力之熱塑性聚胺基甲酸酷尿素樹脂。本發明同時關於一種製備此一熱塑性聚胺基甲酸酯樹脂之方法。習知技藝說明如此領域中所廣泛知悉者，彈性纖維典型上由四種紡紗技術所製：乾式紡紗、溼式紡紗、化學紡紗、以及融熔紡紗。其中’最廣泛使用者爲乾式紡紗技術，其最終亦得到最好的物性。可舉之例有美國專利第4,973,64?與 5,362,432號中所揭示者。然而在紡紗時’傳統乾式紡紗必須將用以進行溶液聚合以製造聚胺基甲酸酯樹脂溶液之溶劑除去或蒸發掉。因此，需要有複雜的設備。同時，除去或蒸發掉之溶劑所造成如水污染或空氣污染等環境污染之高危險性使得需要一高效設備來回收溶劑，因而明顯增加設備上的投資。因此，彈性纖維之製造成本比任何其它纖維來得高，而限制了彈性纖維的應用性。當用以製造與皮膚直接接觸的布料時，如泳裝、運動衣、內衣、連身內衣、貼身衣服、長襪、短襪等等，若溶劑未完全除去，則利用此乾式紡紗所製之彈性纖雉對皮膚或呼吸器官會有不良影響。 .. J 3 二__ 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） S , ^ · I-----I ^---------^ ^ (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483905 A7 _ B7 五、發明說明（y) 乾式紡紗之另一缺點爲雛縮。因爲由乾式紡紗所製之彈性纖維係以聚胺基甲酸酯-尿素鍵爲基礎，故其抗熱性與彈性回復上表現優異，但在織布修整期間會持續皺縮，因而難以計算最終的寬度，使得彈性與穿戴的舒適性變差。同時’由該織布所製之產品在水洗之後顯示持續縮水。除了乾式紡紗所發生之所有問題外，溼式紡紗與化學紡紗另有難以控制製程條件的問題，且在紡得彈性纖維之物性上差異頗大。爲此原因，溼式紡紗與化學紡紗僅作部分使用。因此，對於彈性纖維製程進行廣泛的硏究，以避免傳統技術所遭遇到的問題，如龐大的設備投資、溶劑回收、環境污染、高製造成本、溶劑殘留的負面影響、修整與水洗時之持續皺縮、控制製程條件之困難性等。基本上，硏究方向爲在不使用任何溶劑下製造彈性纖維。結果，發展出一種融熔紡紗方法，其中使單體材料進行融熔整體聚合，並透過一擠製器紡製。爲了完成此融熔紡紗程序，必須符合一些前提。首先，因爲該融熔紡紗方法，如同其名稱所示，包括一經加熱之融熔步驟，以及一經噴嘴之紡紗步驟，因此在此方法中可取得之樹脂必爲熱塑性。同時，該樹脂可融熔至一足夠的程度，因爲若在加熱時留有未熔物，會造成纖維在紡製中斷裂。然而，滿足這些先決條件的樹脂無法像在乾式紡紗、溼式紡紗與化學紡紗中所用之樹脂般包含豐富的交聯，因此，它們在增加所得彈性纖維之抗熱性方面有所限制。 4 電， ---------；¾.--------訂---------線· f請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）經濟部智慧財產局員工消費合作社印製 483905 A7 _____________B7 五、發明說明（^) 一舟又而曰’ 一聚胺基甲酸酯硬節(hard segment)之熔點範圍爲190°C至230°C，而一尿素硬節於250-290°C熔化。因此，具有之尿素鍵愈多，彈性體之抗熱性愈高。於乾式結紗中用以形成尿素鍵之脂肪族一級胺，以一過高之速率與有機異氰酸酯反應，達成這些材料之均相混合。除非材料經均相混合，否則由聚胺基甲酸酯與尿素所製得之該聚胺基甲酸酯樹脂無法於一擠製器中熔化至可用以進行融熔紡紗的程度，因爲脂肪族一級胺會在融熔物大體聚合時進行交聯。由於此反應控制上的困難，目前尙未發展出工業上可行之融熔製程。近來，已引入關於此領域之進一步硏究。例如，韓國早期公開專利第98-702182號揭示反應性極低之脂肪族有機異氰酸酯，以控制尿素鍵之反應速率。根據此專利，由有機異氰酸酯所製得之預聚物在溫度上降低，並加入助熔劑，接著與脂肪族一級胺反應。由於缺乏苯環，如此製得之聚合物在抗熱性方面相信並不如傳統技術之聚合物好。此外，該有機異氰酸酯比傳統芳香族有機異氰酸酯更高的價格自然成爲所揭方法商業化之障礙。目前融熔紡紗所用之樹脂大部分係以聚胺基甲酸酯鍵爲基礎：〇胺基甲酸酯鍵 5 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公4 ) ------------裝--------^---------線l· , (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（f ) 另一方面，溼式及/或化學紡紗用之樹脂係以聚胺基甲酸酯-尿素鍵爲基礎： ^ -NH-C-NH- 胺基甲酸醋-尿素鍵該以聚胺基甲酸酯鍵爲基礎之樹脂由於氫鍵較弱’因此在抗熱性方面比該以聚胺基甲酸酯-尿素鍵爲基礎之樹脂差。較弱的氫鍵導致較差的抗熱性與彈性回復（electric recovery)，而使彈性纖維値降低。爲此原因，融熔紡紗方法並不普及。爲了克服這些問題，已作了很多努力，因而在熱塑性聚胺基甲酸酯樹脂之聚合與融熔紡紗技術兩方面均有長足的進展。整體而言，現在硏究朝兩方面進行：在聚合階段，改變起始物，以製得具有足以因應融熔紡紗所需之抗熱性與彈性；以及在紡紗階段，加入作爲交聯劑之預聚物，以引入基甲酸酯聯結。已知可提供最優良彈性纖維物性之傳統聚合技術之一係以該聚醇組分，亦即一聚胺基甲酸酯樹脂之軟節（S0ft segment)之組成與分子量之控制爲基礎。例如，爲了得到高彈性回復力與抗熱性，該聚醇組分之組成與分子量界定如下：」匕碳原子總數 ~酯鍵數~ 6 本紙張尺度適用中國國家標準（CNS)A4規格（21〇 X 297公爱） l·----------- ^-----------------線 f (請先閱讀背面之注意事項再填寫本頁) 483905 A7 _____ B7 五、發明說明（<) 0.03<—2SM_<〇2 碳原子總數一· (請先閱讀背面之注意事項再填寫本頁) 關於此聚合之技術揭露於美國專利第5,290,905與 5,3 10,852號以及韓國早期公開專利第9〇_1843〇，91-16808 與93-701645號中，所有均揭示透過分子量之增加所致之聚醇結晶化，因而改善彈性回復力與抗熱性。經濟部智慧財產局員工消費合作社印製至於紡紗階段之技術，當於特殊設計之反應器中所製備之熱塑性聚胺基甲酸酯彈性體被融熔紡製時，進給交聯劑，如美國專利第5,391，682號以及韓國早期公開專利第 94-701414號所揭。據報導該熱塑性聚胺基甲酸酯樹脂係於一預聚物製程中製得。詳細言之，首先於一反應槽中使用一穿孔的板子，並於一高速混合器中與一鏈偶合劑混合而製得一預聚物。然後將該混合物進給入一雙螺旋擠製器中，於一最高溫度250_260°C下平均停留約6分鐘。根據此技術，據說可製得具極少數小質量粒子之高分子量聚胺基甲酸酯彈性體，其分子量分佈在一窄範圍內。其次，於一紡紗器中交聯紡製該熱塑性聚胺基甲酸酯樹脂，該紡紗器係連接至一配有可於該擠製器末端進給該預聚物之設施之靜相混合器，如此製得彈性纖維。然而，因爲約花費2小時來製造預聚物，有耗時太久的缺點。此外，在250-260°C下於該雙軸擠製器中停留6分鐘，無可避免地使得該熱塑性聚胺基甲酸酯樹脂變黃，並部份造成旁反應’產生膠狀粒子（小質量，魚眼）。如以上 7 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） 483905 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（卜）文件所陳，該膠狀粒子於一紡紗過濾器中被補捉，因而增加塡充壓力，且自一噴嘴逸出之該膠狀粒子會使彈性纖維於纏繞在線軸上時無法延伸，因而無法連續製造彈性纖維，故其成爲縮短纖維之一因素。雖然諸多專利提出各種不同的反應條件以減少膠狀粒子，但總是會產生一些。在靜相混合器幫助下進行交聯紡紗的同時，一熱塑性聚胺基甲酸酯樹脂首先於一擠製器中熔化，接著於該靜相混合器中加入一預聚物以進行一交聯反應。在文章中表示於加入之預聚物量在15個重量百分比時得到最佳的結果。如上所述’目前已發展出之融熔紡紗相關技術可大致分爲兩類：聚醇的適量結晶以誘發出硬節與軟節間之最大相分離，以及利用交聯預聚物以誘發出紡紗時之基甲酸酯交聯。然而’發現由這些方法製備之彈性纖維在抗熱性與彈性回復的表現上較那些由傳統溼式紡紗或乾式紡紗技術所製備者差。發明槪述本案發明人在考量此背景技術之各種優缺點下，發展出以聚fee基甲酸醋爲基質之彈性纖維。因此，從排除基本限制的方向進行硏發，並消除此排除時所可能產生的問題〇該硏發之首要考量因素爲不使用任何溶劑。在製備彈性纖維時使用溶劑會伴隨環境污染問題，如水與空氣污染，其解決方式爲需要一額外的污染防治設備，因而增加彈 8 •本紙張尺度適用中國國豕標準（CNS)A4規格（210 X 297公爱） ------------I ^--------^ ---------線 * (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（q) 性纖維的成本。此外，所使用之溶劑若殘留在彈性纖維內，總是有傷害身體的高可能性。因此，溼式紡紗、乾式紡紗、以及化學紡紗這些在聚合時使用溶劑的技術，都被排除在外。彈性纖維的生產成本亦列入考慮。價格是大力推廣彈性纖維之最重要因素之一。在未來，認爲將以提供使用者更舒適感覺的方式來發展製衣業。彈性纖維布料爲最適合此目的者。因此，爲了使彈性纖維布料普及化，彈性纖維的製造成本必須從現今的水平大幅降低考慮的最後因素爲投資在製造彈性纖維的錢量。由於紡紗製程在時間與空間方面無法分開進行之故，傳統乾式紡紗、溼式紡紗或化學紡紗技術均需要大規模的投資。就此三種考量，所達成的結論爲融熔紡紗技術最適合於製造彈性纖維。目前所用之融熔紡紗技術若可符合以上的考量，則會得到物性不足的彈性纖維，因此並不如先前所提之技術普及。在本案發明人對彈性纖維重覆進行深入且徹底的硏究之後，最後發現，聚胺基甲酸酯尿素樹脂視其硬節而定，可表現出優良的物性，包括抗熱性與彈性回復力。因此，本發明之一目的在於提供一種新穎的熱塑性聚胺基甲酸酯樹脂，其可進行融熔紡紗，以得到高抗熱性與彈性回復之彈性纖維。本發明之另一目的在於提供一種製備此一熱聚胺基甲酸酯樹脂之方法。 9 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ----I---— — — ILM.· 1 I--I I I 訂-! — 111 — · (請先閱讀背面之注意事項再填寫本頁) 483905 經濟部智慧財產局員工消費合作社印製 A7 _____B7___ 五、發明說明（3 ) 根據本發明之一方面，提供一種聚胺基甲酸酯尿素樹脂，其包含以下化學式I所代表之聚合物： [A-0-(0)C-NH-D-NH-C(0)-NH-D-NH-C (O)-O] n [I] 其中A代表一有機聚醇殘基，具有約500至5,000之數目平均分子量以及1.5至2.5之重量平均分子量/數目平均分子量(Mw/Mn)，而官能基數在1.8至2.2之範圍內，D 代表一芳香族有機二異氰酸酯殘基，其官能基數在1.8至 2.2之範圍內，而η代表重覆單元的數目。根據本發明之另一方面，提供一種製備具有該化學式 I之聚胺基甲酸酯尿素樹脂之方法，其包括之步驟有：使一有機聚醇與過量的有機二異氰酸酯反應得到一預聚物，該有機聚醇具有約500至5,000之數目平均分子量以及1.5 至2.5之重量平均分子量/數目平均分子量(Mw/Mn)，而官能基數在1·8至2.2之範圍內，該芳香族有機二異氰酸酯之官能基數在1.8至2.2之範圍內·，使該預聚物之部分二異氰酸酯基胺化；使該殘留異氰酸酯基與新得到胺基間之兩分子反應，以製得一尿素官能基，透過此使該預聚物之兩分子線性接合；以及使該含尿素雙預聚物聚合。發明之詳細說明本發明係關於一種具有以下化學式I重覆單元之聚胺基甲酸酯尿素樹脂： [A-0-(0)C-NH-D-NH-C(0)-NH-D-NH-C(0)-0]n [I] 其中A代表一有機聚醇殘基，而D代表一芳香族有機 10 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） ' ' (請先閱讀背面之注意事項再填寫本頁) 装---- 訂- -------線· 經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（1 ) 二異氰酸酯殘基。如式中所見者，該重覆單元之特徵在於兩個芳香族有機二異氰酸酯基團透過一個尿素聯結物彼此連結，而一尿素架橋於一芳香族有機二異氰酸酯基團與一有機聚醇基團間。該芳香族有機二異氰酸酯殘基D之官能基數在1.8至 2.2之範圍內。較佳者，該芳香族有機異氰酸酯具有500或更少的數目平均分子量。該芳香族有機異氰酸酯之實例，舉例說明而非用以限制，包括二苯基_4,4’-異氰酸酯(MDI) 與對亞苯基二異氰酸酯。該有機聚醇殘基A具有約500至5,000之數目平均分子量，而較佳爲1，〇〇〇至2,000。具有1.8至2.2之官能基數，因而該有機聚醇殘基A具有1.5至2.5之重量平均分子量/數目平均分子量(Mw/Mn)，而較佳爲1.8至2.2，並選自脂肪族聚酯聚醇、脂肪族聚醚聚醇、脂肪族聚己內酯聚醇、脂肪族碳酸酯聚醇、以及脂肪族矽氧烷聚醇。聚醚聚醇，如聚四亞甲基醚二醇、聚丙二醇與聚亞乙基亞丙基二醇；聚酯聚醇，如聚亞乙基己二酸酯、聚亞乙基亞丁基己二酸酯、聚亞己基己二酸酯、聚亞丁基亞己基己二酸酯與聚3-甲基-亞戊基己二酸酯；聚己內酯聚醇；六亞甲基碳酸醋聚醇；以及二甲基砂氧院聚醇。在包含化學式I之重覆單元之樹脂中，該有機聚醇殘基A係爲一軟節(soft segment)，而其餘的部分，亦即-〇-(0)C-NH-D-NH-C(0)-NH-D-NH-C(0)-0-則作爲硬節（hard 11 +^尺度適用中國國家標準7cNS)A4規格（210 X 297公H 一 1« I--— — — — — — I — 裝---！111 訂 — — — — 1 — !- - (請先閱讀背面之注意事項再填寫本頁) 483905 A7 B7 五、發明說明（\ σ) segment) 〇另一方面，傳統乾式與溼式紡紗用之彈性樹脂具有由以下化學式II所代表之硬節： -0-(0)C-NH-D-NH-C(0)-NH-R「NH-C(0)-NH-D-NH-0(〇)-〇 [II] 其中，D爲一有機二異氰酸酯，而I爲一脂肪鏈。就融熔紡紗用的傳統彈性樹脂而言，其硬節由以下化學式ΠΙ所代表： -0-(0)C-NH-D-NH-C(0)-0-R2-0-C(0)-NH-D-NH-C(0)-0 [III] 其中，D爲一有機二異氰酸酯，而R2爲一脂肪鏈。在兩個異氰酸酯基之間，如式中所見者，在乾式紡紗與溼式紡紗用之傳統彈性樹脂之硬節中者爲兩個尿素聯結物，而在融熔紡紗用之傳統彈性樹脂之硬節中者爲兩個聚胺基甲酸酯聯結物。此係歸因於乾式紡紗或溼式紡紗用之彈性樹脂係利用脂肪族二胺作爲鏈偶合劑合成而得，而融熔紡紗用之彈性樹脂係利用脂肪族二醇或芳香族二醇合成而得之事實。當比較化學式I、II與III時，本發明彈性樹脂中之硬節顯然相當不同於傳統彈性樹脂中者。在兩個芳香族異氰酸酯基團間僅留有一個尿素聯結。因爲一芳香族苯環直接連至本發明彈性樹脂硬節中之尿素基團上，此結構特性使得化學式I之硬節在塡充方面遠比化學式II與III之傳統硬節優異，因而伴隨抗熱性與彈性回復上之大幅改善。 12 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線· 經濟部智慧財產局員工消費合作社印製經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（u) 同時，本發明關於一種製備此一融熔紡紗用彈性樹脂之方法。根據本發明之方法包括(a)—預聚物生成程序，（b)—胺化程序，（c)-尿素官能基生成程序，以及(d)—聚合物生成程序。該預聚物生成程序可以一連續型式或一批式型式進行〇在一批式型式程序中，例如，將一選定當量比之有機聚醇與芳香族有機二異氰酸酯進給入一配有攪拌器與溫度控制器之反應器中，然後於80-12(TC，較佳9(M00°C下使之反應2-3小時。在一連續型式程序中，例如，利用一針型混合頭使一有機聚醇與一芳香族有機二異氰酸酯均勻混合’同時在一配有錶計之設備幫助下以固定比率連續進給’且所得之混合物通過一高速針混合器型式之反應器’以連續產生預聚物。該混合物於該高速針混合器下停留2至30分鐘’較佳 3至10分鐘。在該預聚物生成程序中，該有機聚醇與芳香族有機二異氰酸酯較佳以下式1所代表之當量比進給· <芳香族有機二氰酸酯當量< 2 5 - 有機聚醇當量 - · [1] 13 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公愛） ------------ 衣--------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 483905 A7 B7 五、發明說明（該芳香族有機二異氰酸酯對有機聚醇當量比之範圍適合於提供彈性纖維所必須具有的物性。在此範圍內，該彈性纖維的蕭爾硬度(Shore hardness)範圍在65A至85A，而延展範圍比從550%至900%。例如，若當量比低於5，會得到延展比良好但抗熱性不佳的聚合物。另一方面，若當量比超過2.5，則所得之聚合物表現出良好的抗熱性，但延展比不足。一最適的當量比可根據所用芳香族有機二異氰酸酯與有機聚醇之分子量而作一些調整。如此製得之預聚物，當加入H2O時，會進行一系列胺官能基形成反應以及一尿素聯結反應，以製得一聚合物。較佳於胺官能基形成反應中使用無雜質的純水或蒸餾水。然而，若需要特別控制物性，可合倂H20加入一額外的鏈偶合劑。可取得之鏈偶合劑爲具有400或更小分子量，並具有1.8-2.2之羥基官能基數者。當合併使用鏈偶合劑時，或比單獨使用Ηβ時提供較差的抗熱性與彈性回復力。該二醇型式之鏈偶合劑之代表例包括乙二醇、I，1 2 3-丁二醇、丙二醇、1，6-己二醇、3-甲基-l，5-戊二醇。較佳者，該預聚物與H20係以下式2所代表之當量比加入： (請先閲讀背面之注意事項再填寫本頁) 裝--------訂---------線· 經濟部智慧財產局員工消費合作社印製 1 2 14 3 本紙張尺度適用中國國家標準（CNS)A4規袼（210 X 297公釐） 483905 經濟部智慧財產局員工消費合作社印製 A7 BZ__一五、發明說明（\)) 例如，若H20之當量比低於1.8，則所產生胺之當量會超過剩餘NCO之當量，因此無法得到高分子量之預聚物。另一方面，若當量比超過2.2，則剩餘NCO之當量大於所產生胺之當量，因而產生很多與基甲酸酯或二縮聯結物相關之交聯，而喪失了熱塑性之性質。實驗數據顯示，當NCO當量對H20當量之當量比爲2.0時，可製得最長的高分子量直鏈。該聚合物生成程序可以一連續型式或一批式型式進行。在一批式型式程序中，在攪拌下加入該預聚物與一定量之H20。該攪拌直到C02不斷裂才停止。當氣泡被除去而反應黏度增加時，使反應於一熱空氣烘箱中之一小盤上老化。該熱空氣烘箱較佳於120-17(TC下加熱。該烘箱較佳使用加熱之氮氣甚於含氧之空氣。氧氣容易造成預聚物於老化期間變黃。該老化之預聚物斷裂成片，然後以一擠製II 製成小球。在一連續型式程序中，該預聚物與H20於高速混合g貞處立即混合，並於螺旋式安裝之多軸反應擠製器中反應，以產生二氧化碳與一含尿素鍵之產物。透過一真空排氣孔連續移除該二氧化碳，並擠製產物使之成爲小球狀。 (A)預聚物生成反應Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 ___ B7 V. Description of the Invention (\) BACKGROUND OF THE INVENTION Field of the Invention The present invention relates generally to a polyurethane elastomer, especially a highly heat resistant and Thermoplastic polyurethane polyurethane resin with elastic resilience. The invention also relates to a method for preparing such a thermoplastic polyurethane resin. Description of known techniques As is widely known in this field, elastic fibers are typically made by four spinning technologies: dry spinning, wet spinning, chemical spinning, and melt spinning. Among them, the most widely used is the dry spinning technology, which finally obtains the best physical properties. Examples include those disclosed in U.S. Patent Nos. 4,973,64? And 5,362,432. However, at the time of spinning, 'conventional dry spinning must remove or evaporate the solvent used for solution polymerization to make a polyurethane resin solution. Therefore, complicated equipment is required. At the same time, the high risk of environmental pollution such as water pollution or air pollution caused by removed or evaporated solvents makes the need for an efficient equipment for solvent recovery, thereby significantly increasing the investment in equipment. Therefore, the manufacturing cost of elastic fibers is higher than any other fiber, which limits the applicability of elastic fibers. When used to make fabrics that come into direct contact with the skin, such as swimwear, sportswear, underwear, bodysuits, tights, stockings, socks, etc., if the solvent has not been completely removed, use this dry spinning Elastic fibers can have adverse effects on the skin or respiratory organs. .. J 3 二 __ This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) S, ^ · I ----- I ^ --------- ^ ^ ( Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 _ B7 V. Description of the Invention (y) Another disadvantage of dry spinning is shrinkage. Because the elastic fibers made from dry spinning are based on polyurethane-urea bonds, they have excellent heat resistance and elastic recovery, but they will continue to shrink during the trimming of the fabric, making it difficult to calculate the final Width, making the elasticity and wearing comfort worse. At the same time, the product made from the woven fabric showed continuous shrinkage after washing. In addition to all the problems that occur with dry spinning, wet spinning and chemical spinning have other problems that make it difficult to control the process conditions, and the physical properties of the elastic fibers produced are quite different. For this reason, wet spinning and chemical spinning are only partially used. Therefore, extensive research has been conducted on the elastic fiber manufacturing process to avoid the problems encountered by traditional technologies, such as huge equipment investment, solvent recovery, environmental pollution, high manufacturing costs, negative effects of solvent residues, and continuity during trimming and washing Shrinkage, difficulty in controlling process conditions, etc. Basically, the research direction is to make elastic fibers without using any solvent. As a result, a melt-spinning method has been developed in which monomer materials are melt-polymerized as a whole and spun through an extruder. In order to complete this melt spinning process, some prerequisites must be met. First, because the melt spinning method, as its name implies, includes a heating melting step and a nozzle spinning step, the resin obtainable in this method must be thermoplastic. At the same time, the resin can be fused to a sufficient degree, because if unmelted matter is left during heating, the fibers will break during spinning. However, resins meeting these prerequisites cannot contain as much cross-linking as resins used in dry spinning, wet spinning, and chemical spinning, and therefore they have limitations in increasing the heat resistance of the resulting elastic fibers. 4 electricity, ---------; ¾ .-------- order --------- line · f Please read the notes on the back before filling this page) Standards apply to China National Standard (CNS) A4 specifications (210 X 297 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 _____________ B7 V. Description of the invention (^) One boat and one's polyurethane The hard segment has a melting point ranging from 190 ° C to 230 ° C, while a urea hard segment melts at 250-290 ° C. Therefore, the more urea bonds there are, the higher the heat resistance of the elastomer. The aliphatic primary amines used to form urea bonds in dry knot yarns react with organic isocyanates at an excessively high rate to achieve homogeneous mixing of these materials. Unless the materials are homogeneously mixed, the polyurethane resin made from polyurethane and urea cannot be melted in an extruder to the extent that it can be used for melt spinning because of the fat The primary primary amines are crosslinked when the melt is substantially polymerized. Due to the difficulty in controlling this reaction, currently no industrially feasible fusion process has been developed. Recently, further research into this field has been introduced. For example, Korean Early Laid-Open Patent No. 98-702182 discloses an aliphatic organic isocyanate having extremely low reactivity to control the reaction rate of urea bonds. According to this patent, a prepolymer made from an organic isocyanate is reduced in temperature, added with a flux, and then reacted with an aliphatic primary amine. Due to the lack of a benzene ring, the polymer thus obtained is believed to be inferior to conventional polymers in terms of heat resistance. In addition, the higher price of this organic isocyanate than traditional aromatic organic isocyanates naturally becomes an obstacle to the commercialization of the disclosed method. Most of the resins currently used for melt-spun yarns are based on polyurethane bonds: 〇 Urethane bond 5 This paper size applies to China National Standard (CNS) A4 (210 X 297 male 4)- ----------- install -------- ^ --------- line l ·, (please read the precautions on the back before filling this page) Printed by the Consumer Affairs Cooperative of the Property Bureau 483905 A7 B7 V. Description of the Invention (f) On the other hand, the resins for wet and / or chemical spinning are based on polyurethane-urea bonds: ^ -NH- C-NH-urethane-urea bond The resin based on polyurethane bond is weaker in hydrogen bonding, so it is more heat resistant than the polyurethane-urea bond Poor resin. The weaker hydrogen bonds result in poorer heat resistance and electrical recovery, which reduces the elastic fiber mass. For this reason, the melt spinning method is not popular. In order to overcome these problems, many efforts have been made, and therefore, there have been considerable advances in both the polymerization of thermoplastic polyurethane resins and the melt spinning technology. In general, research is now proceeding in two directions: during the polymerization stage, changing the starting material to produce heat resistance and elasticity sufficient for melt spinning; and during the spinning stage, adding it as a crosslinking agent Prepolymer to incorporate carbamate linkages. One of the conventional polymerization techniques known to provide the best physical properties of elastic fibers is based on the control of the composition and molecular weight of the polyol component, that is, the soft segment of a polyurethane resin. For example, in order to obtain high elastic resilience and heat resistance, the composition and molecular weight of the polyol component are defined as follows: "Total number of carbon atoms ~ number of ester bonds ~ 6 This paper size applies the Chinese National Standard (CNS) A4 specification (21〇 X 297 public love) l · ----------- ^ ----------------- line f (Please read the precautions on the back before filling in this page ) 483905 A7 _____ B7 V. Description of the invention (<) 0.03 < —2SM_ < 〇2 The total number of carbon atoms One (Please read the precautions on the back before filling this page) The technology of this polymerization is disclosed in US Patent No. Nos. 5,290,905 and 5,3 10,852 and Korean Early Published Patent Nos. 90_1843, 91-16808, and 93-701645 all reveal that the polyhydric alcohol crystallizes due to an increase in molecular weight, thereby improving elastic recovery and Heat resistance. The technology of printing at the spinning stage by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, when the thermoplastic polyurethane elastomer prepared in a specially designed reactor is melt-spun, the crosslinking agent is fed, Such as disclosed in U.S. Patent No. 5,391,682 and Korean Early Public Patent No. 94-701414. The thermoplastic polyurethane resin is reported to be made in a prepolymer process. In detail, a prepolymer was first prepared by using a perforated plate in a reaction tank and mixing with a chain coupling agent in a high-speed mixer. The mixture is then fed into a twin-screw extruder and stays on average for about 6 minutes at a maximum temperature of 250-260 ° C. According to this technique, it is said that a high-molecular-weight polyurethane elastomer having a small number of small-mass particles can be produced, and the molecular weight distribution is within a narrow range. Second, the thermoplastic polyurethane resin is cross-linked and spun in a spinner, which is connected to a stationary phase equipped with a facility capable of feeding the prepolymer at the end of the extruder. A mixer, so as to obtain elastic fibers. However, since it takes about 2 hours to produce the prepolymer, there is a disadvantage that it takes too long. In addition, staying in the biaxial extruder at 250-260 ° C for 6 minutes inevitably makes the thermoplastic polyurethane resin yellow, and partially causes side reactions to generate colloidal particles ( Small mass, fisheye). As mentioned above, the paper size of this paper applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 483905 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (b) The colloidal particles It is trapped in a spinning filter, thus increasing the filling pressure, and the colloidal particles escaping from a nozzle will prevent the elastic fiber from extending when it is wound on the bobbin, so it cannot continuously manufacture the elastic fiber. Become a factor in shortening fibers. Although many patents propose various reaction conditions to reduce colloidal particles, some are always produced. While cross-linked spinning is performed with the help of a static mixer, a thermoplastic polyurethane resin is first melted in an extruder, and then a prepolymer is added to the static mixer to perform a cross-linking.联反应。 Reaction. It is stated in the article that the best results are obtained when the amount of prepolymer added is 15% by weight. As mentioned above, the currently developed melt-spinning related technologies can be roughly divided into two categories: the appropriate amount of crystallization of polyalcohol to induce maximum phase separation between hard and soft knots, and the use of crosslinked prepolymers to induce Carbamate cross-linking during spinning. However, it has been found that the elastic fibers prepared by these methods are inferior in heat resistance and elastic recovery performance to those prepared by conventional wet spinning or dry spinning techniques. Summary of the Invention The inventors of the present invention, considering various advantages and disadvantages of this background technology, developed an elastic fiber based on a polyester based on formic acid. Therefore, carry out the development from the direction of ruling out the basic restrictions and eliminate the problems that may arise during the exclusion. The first consideration of this development is that no solvents are used. The use of solvents in the preparation of elastic fibers will accompany environmental pollution problems, such as water and air pollution. The solution is to require an additional pollution prevention device, and therefore increase the elasticity. 8 • This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public love) ------------ I ^ -------- ^ --------- line * (Please read the precautions on the back before filling in this Page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 B7 V. Description of the invention (q) Cost of sex fiber. In addition, if the solvent used remains in the elastic fibers, there is always a high possibility of harm to the body. Therefore, wet spinning, dry spinning, and chemical spinning are excluded from the use of solvents during polymerization. Production costs for elastic fibers are also considered. Price is one of the most important factors in vigorously promoting elastic fibers. In the future, it is believed that the garment industry will be developed in a way to provide users with a more comfortable feeling. Elastane cloth is the most suitable for this purpose. Therefore, in order to popularize the elastic fiber cloth, the manufacturing cost of the elastic fiber must be greatly reduced from the current level. The last factor considered is the amount of money invested in manufacturing the elastic fiber. Because the spinning process cannot be separated in time and space, traditional dry spinning, wet spinning, or chemical spinning technologies all require large-scale investments. From these three considerations, it was concluded that melt-spinning technology is most suitable for making elastic fibers. If the currently used melt-spinning technology can meet the above considerations, elastic fibers with insufficient physical properties will be obtained, so it is not as popular as the previously mentioned technology. After the inventor of the present case conducted in-depth and thorough research on the elastic fiber, it was finally found that the polyurethane urea resin can show excellent physical properties, including heat resistance and elastic restoring force, depending on its rigidity. . Therefore, an object of the present invention is to provide a novel thermoplastic polyurethane resin which can be melt-spun to obtain elastic fibers having high heat resistance and elastic recovery. Another object of the present invention is to provide a method for preparing the thermal polyurethane resin. 9 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) ---- I ---- — — ILM. · 1 I--III Order-! — 111 — · (Please read first Note on the back, please fill out this page again) 483905 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 _____B7___ 5. Description of the Invention (3) According to one aspect of the present invention, a polyurethane urea resin is provided, which includes the following Polymer represented by Chemical Formula I: [A-0- (0) C-NH-D-NH-C (0) -NH-D-NH-C (O) -O] n [I] where A represents one Organic polyol residues having a number average molecular weight of about 500 to 5,000 and a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 2.5, and the number of functional groups in the range of 1.8 to 2.2, D represents an aromatic organic The number of functional groups of the diisocyanate residue is in the range of 1.8 to 2.2, and η represents the number of repeating units. According to another aspect of the present invention, a method for preparing a polyurethane urea resin having the chemical formula I is provided. The method includes the steps of: reacting an organic polyol with an excess of an organic diisocyanate to obtain a prepolymer. The organic polyol has a number average molecular weight of about 500 to 5,000 and a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 2.5, and the number of functional groups is in the range of 1.8 to 2.2. The number of functional groups of the isocyanate is in the range of 1.8 to 2.2, so that a part of the dipolymer of the prepolymer is aminated; the residual isocyanate group is reacted with two molecules between the newly obtained amine group to obtain a urea functional group, Through this, the two molecules of the prepolymer are linearly joined; and the urea-containing double prepolymer is polymerized. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyurethane urea resin having a repeating unit of the following chemical formula I: [A-0- (0) C-NH-D-NH-C (0) -NH-D -NH-C (0) -0] n [I] where A represents an organic polyalcohol residue, and D represents an aromatic organic 10 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) ) '' (Please read the precautions on the back before filling out this page) Packing ---- Ordering-------- Line · Printed by the Intellectual Property Bureau Staff Consumer Cooperatives of the Ministry of Economic Affairs 483905 A7 B7 V. Description of the invention ( 1) Diisocyanate residue. As seen in the formula, the repeating unit is characterized in that two aromatic organic diisocyanate groups are connected to each other through a urea linker, and a urea bridges an aromatic organic diisocyanate group and an organic polyol group between. The number of functional groups of the aromatic organic diisocyanate residue D is in the range of 1.8 to 2.2. Preferably, the aromatic organic isocyanate has a number average molecular weight of 500 or less. Examples of the aromatic organic isocyanate are by way of illustration and not limitation, and include diphenyl-4,4'-isocyanate (MDI) and p-phenylene diisocyanate. The organic polyol residue A has a number average molecular weight of about 500 to 5,000, and preferably 1,000 to 2,000. It has a functional group number of 1.8 to 2.2, so the organic polyalcohol residue A has a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 2.5, preferably 1.8 to 2.2, and is selected from aliphatic polyester poly Alcohols, aliphatic polyether polyols, aliphatic polycaprolactone polyols, aliphatic carbonate polyols, and aliphatic siloxane polyols. Polyether polyols, such as polytetramethylene ether glycol, polypropylene glycol and polyethylene propylene glycol; polyester polyols, such as polyethylene adipate, polyethylene butylene Diesters, polyhexylene adipates, polybutylene hexylene adipates, and poly3-methyl-pentyl adipates; polycaprolactone polyols; hexamethylene carbonate carbonate polymer Alcohol; and dimethyl sand oxygen polyalcohol. In the resin containing the repeating unit of Chemical Formula I, the organic polyalcohol residue A is a soft segment, and the remaining part, namely, -0- (0) C-NH-D-NH- C (0) -NH-D-NH-C (0) -0- is used as a hard section (hard 11 + ^ scale applies Chinese national standard 7cNS) A4 specifications (210 X 297 male H a 1 «I ---- — — — — I — Install ---! 111 Order — — — — 1 —!--(Please read the notes on the back before filling out this page) 483905 A7 B7 V. Description of the invention (\ σ) segment) 〇Other On the one hand, the elastic resins for traditional dry and wet spinning have a hard knot represented by the following chemical formula II: -0- (0) C-NH-D-NH-C (0) -NH-R "NH- C (0) -NH-D-NH-0 (〇) -〇 [II] where D is an organic diisocyanate and I is a fatty chain. For a traditional elastic resin for melt spinning, its The hard segment is represented by the following chemical formula II: -0- (0) C-NH-D-NH-C (0) -0-R2-0-C (0) -NH-D-NH-C (0)- 0 [III] where D is an organic diisocyanate and R2 is a fatty chain. Between two isocyanate groups, as seen in the formula, traditional elastic resins for dry spinning and wet spinning Among the hard knots are two urea junctions, while in the traditional elastic resins used for melt spinning, the two are polyurethane joints. This is due to dry spinning or wet spinning. The elastic resin used for spinning is synthesized by using aliphatic diamine as a chain coupling agent, and the elastic resin used for melt spinning is synthesized by using aliphatic diol or aromatic diol. When comparing chemical formula I For II, II and III, the hard joints in the elastic resin of the present invention are obviously quite different from those in the traditional elastic resin. There is only one urea linkage between the two aromatic isocyanate groups. Because an aromatic benzene ring is directly connected to the On the urea group in the hard joint of the elastic resin, this structural characteristic makes the hard joint of the chemical formula I far superior to the traditional hard joints of the chemical formulas II and III, so it is accompanied by a significant improvement in heat resistance and elastic recovery. This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling out this page) Order --------- Line · Intellectual Property Bureau Staff, Ministry of Economic Affairs Consumer Cooperative Print Printed by the Consumers' Cooperative of the Ministry of Economics and Intellectual Property of the Ministry of Education 483905 A7 B7 V. Description of the invention (u) Meanwhile, the present invention relates to a method for preparing the elastic resin for melt-spinning. The method according to the present invention includes (a)- Polymer generation procedure, (b) —amination procedure, (c) —urea functional group generation procedure, and (d) —polymer generation procedure. The prepolymer generation program can be performed in a continuous or batch type. In a batch type program, for example, a selected equivalent ratio of an organic polyol and an aromatic organic diisocyanate is fed into a mixer equipped with a stirrer. And a temperature controller in a reactor, and then react at 80-12 ° C, preferably 9 ° C (M00 ° C) for 2-3 hours. In a continuous type procedure, for example, using a needle-type mixing head to make a The organic polyol and an aromatic organic diisocyanate are uniformly mixed 'while continuously fed at a fixed ratio with the help of a metered device' and the resulting mixture is passed through a high-speed needle mixer type reactor to continuously produce pre- The polymer stays under the high-speed needle mixer for 2 to 30 minutes, preferably 3 to 10 minutes. In the prepolymer generation process, the organic polyol and the aromatic organic diisocyanate are preferably represented by the following formula 1. Representative equivalent ratio feed < Aromatic organic dicyanate equivalent < 2 5-Organic polyol equivalent- · [1] 13 This paper size applies to China National Standard (CNS) A4 (210 X 297) ) ------------ Clothing ---- ---- Order --------- Line · (Please read the precautions on the back before filling this page) 483905 A7 B7 V. Description of the invention (The ratio of the aromatic organic diisocyanate to the equivalent of organic polyol The range is suitable for providing the physical properties necessary for an elastic fiber. Within this range, the Shore hardness of the elastic fiber ranges from 65A to 85A, and the elongation ratio ranges from 550% to 900%. For example, if the equivalent ratio Below 5, a polymer with a good elongation ratio but poor heat resistance will be obtained. On the other hand, if the equivalent ratio exceeds 2.5, the polymer obtained will exhibit good heat resistance, but the elongation ratio will be insufficient. An optimum equivalent ratio Some adjustments can be made according to the molecular weight of the aromatic organic diisocyanate and organic polyol used. When the prepolymer thus prepared, when H2O is added, a series of amine functional group formation reactions and a urea coupling reaction are performed to obtain A polymer. It is better to use pure water or distilled water without impurities in the amine functional group formation reaction. However, if special physical properties need to be controlled, an additional chain coupling agent can be added with H20. The available chain coupling agent is Those having a molecular weight of 400 or less and having a hydroxyl functional group number of 1.8-2.2. When a chain coupling agent is used in combination, it provides poorer heat resistance and elastic restoring force than when Ηβ is used alone. This diol type chain coupling agent Representative examples include ethylene glycol, 1,2-3-butanediol, propylene glycol, 1,6-hexanediol, and 3-methyl-1,5-pentanediol. Preferably, the prepolymer and H20 is added by the equivalent ratio represented by the following formula 2: (Please read the precautions on the back before filling in this page) Packing -------- Order --------- Line · Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 1 2 14 3 This paper size applies the Chinese National Standard (CNS) A4 Regulations (210 X 297 mm) 483905 Printed by the Employees ’Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 BZ__15. Description of the invention ( \)) For example, if the equivalent ratio of H20 is less than 1.8, the equivalent of the amine produced will exceed the equivalent of the remaining NCO, so a high molecular weight prepolymer cannot be obtained. On the other hand, if the equivalent ratio exceeds 2.2, the equivalent of the remaining NCO is greater than the equivalent of the amine produced, so that many cross-links related to the carbamate or dicondensate are lost, and the thermoplastic properties are lost. Experimental data show that when the equivalent ratio of NCO equivalent to H20 equivalent is 2.0, the longest high molecular weight straight chain can be obtained. The polymer generation process can be performed in a continuous or batch mode. In a batch type procedure, the prepolymer and a certain amount of H20 are added with stirring. This stirring was not stopped until C02 did not break. When the bubbles are removed and the reaction viscosity increases, the reaction is aged on a small plate in a hot air oven. The hot air oven is preferably heated at 120-17 ° C. The oven preferably uses heated nitrogen rather than oxygen-containing air. Oxygen easily causes the prepolymer to turn yellow during aging. The aging prepolymer breaks into The pellets were then extruded into an pellet II. In a continuous mode procedure, the prepolymer was immediately mixed with H20 at a high-speed mixing stage, and reacted in a screw-mounted multi-axis reaction extruder. In order to produce carbon dioxide and a product containing urea bond, the carbon dioxide is continuously removed through a vacuum exhaust hole, and the product is extruded into a small ball. (A) Prepolymer formation reaction

2 OCN-D-NCO + HO-A-OH 一 OCN-D-NH-C(0)-0-A-0-(〇)c、 NH-D-NCO 二異氰酸酯聚醇預聚物 , 15 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ^--------^--------- 483905 A7 B7 五、發明說明（外） (B)胺化 0CN-D-NH-C(0)-0-A-0-(0)C-NH-D-NC0 + H20 0CN-D-NH-C(0)-0-A-0-(0)C-NH-D-NHC00H —0CN-D-NH-C(0)-〇_A-〇-(0)C_NH-D_NH2 + co2 ⑴ (c)尿素官能基生成 0CN-D-NH-C(0)-0-A-0-(0)C-NH-D-NH2 — 0CN-D-NH-C(0)-0-A-0-(0)C-NH-D-NH-C(0)-NH-D-NH- C(0)"*0~A-0-(0)C-NH-D-NH2 (D)聚合 n/2 0CN-D-NH-C(0)-0-A-0-(0)C-NH-D-NH-C(0)-NH-D-NH- C(0)-0-A-0-(0)C-NH-D-NH2 -> [A-0-(〇)C-NH-D-NH-C(0)-NH-D- NH-C(0)-0]n 首先，一雙官能芳香族有機異氰酸酯與一雙官能有機聚醇(莫耳比2:1)反應得到每一相反端均具有一 NCO基之預聚物。每兩當量該預聚物之NCO加入一當量之水，以使該預聚物之兩末端NCO之任一轉化成一胺基。兩分子之於一端具有一胺基而於另一端具有一 NCO基之預聚物彼此反應，以製得一透過一尿素聯結相接合之加成物。換言之，一預聚物之胺基與另一預聚物之NCO基反應，以形成一尿素聯結，其線性連結兩個芳香族有機異氰酸酯。因此合成高分子量之直聚胺基甲酸酯尿素樹脂，其具有高抗熱性與彈性回復力。根據本發明方法所製備之聚胺基甲酸酯尿素樹脂具有 5-30克/10分鐘之融熔率(MI)，140-160°C之軟化點，280- 16 $張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) 訂---------線丨經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（α) 4〇〇 kg/m2之張力強度，92-94°/。之300%立即彈力回復，以及9卜93%之500%立即彈力回復。這些物理性質測量如下：融熔率(MI):於120°C真空烘箱中乾燥5小時之後，於26(TC5,000克之負載下測量一樣品之MI。軟化點：將兩個依如下所示之方式所製備之試樣切成^ 10mm X 10mm之尺寸，並於送入軟化點測里機益則先f了堆疊起來。具有1，〇〇〇克負載之針穿入樣品中達1毫米深度之處，測量其溫度而得該樣品之軟化點。張力強度，延展率，300%立即彈力回復，以及500% 立即彈力回復：以一 ASTM D412模切割與軟化點所用者相同之樣品，以一通用測試機(UTM)測量物理性質。利用熱壓製備測量物理性質所用之試樣。過去使用熱壓之製備技術非常差，因此所得之試樣在品質上無法進行物性測試。現在，塗佈鐵氟龍之織布技術使得該熱壓可用以製備合標準的試樣。該熱壓對於在短時間內從少量材料製得試樣而言非常方便。常用的熱壓經設計以可加熱與冷卻。試樣製備之準備工作包括調整加熱板的溫度至220-240°C之範圍內，並稱重材料至180克。提供三層鐵板結構。在底部置放一塊以鐵氟龍片覆蓋的板子，接著放一尺寸爲250mm X 250mm X 2mm之試樣框於該鐵氟龍片上。其次，將該稱重後的材料倒入框中，均句分佈於其上，之後，把一覆有鐵氟龍片之板子像一個蓋子般放在該框上。將所得之構造插於加熱板間，然後於10噸壓力下加壓1分鐘，， 17 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） (請先閱讀背面之注意事項再填寫本頁) ^--------^---------^ » 經濟部智慧財產局員工消費合作社印製 483905 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明（ιΟ 以及3 0噸壓力下加壓2分鐘。將該構進移至一冷卻板上，在冷卻的同時於30噸壓力下加壓2分鐘。在打開蓋子後，拆解該結構，以得到一重量約160克且2·ι毫米厚度之試樣。所得之試樣於l2〇°C下老化I2小時，以適合於物性測試之用。因爲根據本發明所製備之聚合物具熱塑性，故其可以一擠製齊模製。決定一個材料之壓縮可模製性之因素之一爲获材料在濟製時可恒疋進給的能力。怪定進給材料之平穩操作意謂著該材料具有足以確保均勻融熔態與恆定輸出率之熱塑性。該壓縮可模製性可藉由繪製一擠製器之Tq 隨日寸間的變化而測定。根據本發明之熱塑性聚胺基甲酸酯尿素樹脂之壓縮可模製性評估可利用一擠製器爲之，如 Brabender所販售之稱爲”Piastic〇der，，者，顯示的結果爲在 RPM 爲 50 與 Barrel 溫度爲 230-250-260-240°C 之條件下，2 OCN-D-NCO + HO-A-OH-OCN-D-NH-C (0) -0-A-0- (〇) c, NH-D-NCO diisocyanate polyol prepolymer, 15 pcs Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ^ -------- ^ --------- 483905 A7 B7 V. Description of the invention (outside) (B) Amination 0CN-D-NH-C (0) -0-A-0- (0) C-NH-D-NC0 + H20 0CN-D-NH- C (0) -0-A-0- (0) C-NH-D-NHC00H —0CN-D-NH-C (0) -〇_A-〇- (0) C_NH-D_NH2 + co2 ⑴ (c ) The urea functional group generates 0CN-D-NH-C (0) -0-A-0- (0) C-NH-D-NH2 — 0CN-D-NH-C (0) -0-A-0- (0) C-NH-D-NH-C (0) -NH-D-NH- C (0) " * 0 ~ A-0- (0) C-NH-D-NH2 (D) polymerization n / 2 0CN-D-NH-C (0) -0-A-0- (0) C-NH-D-NH-C (0) -NH-D-NH- C (0) -0-A- 0- (0) C-NH-D-NH2-> [A-0- (〇) C-NH-D-NH-C (0) -NH-D- NH-C (0) -0] n First, a bifunctional aromatic organic isocyanate is reacted with a bifunctional organic polyol (Molar ratio 2: 1) to obtain a prepolymer having an NCO group at each opposite end. One equivalent of water is added for every two equivalents of NCO of the prepolymer to convert any of the two terminal NCOs of the prepolymer into an amine group. The two molecules have a prepolymer having an amine group at one end and an NCO group at the other end to react with each other to produce an adduct that is bonded through a urea linkage. In other words, the amine group of one prepolymer reacts with the NCO group of another prepolymer to form a urea linkage that linearly connects two aromatic organic isocyanates. Therefore, a high molecular weight straight polyurethane urethane resin is synthesized, which has high heat resistance and elastic recovery. The polyurethane urea resin prepared according to the method of the present invention has a melting rate (MI) of 5-30 g / 10 minutes, a softening point of 140-160 ° C, and a scale of 280- 16 $ Zhang applies to Chinese national standards (CNS) A4 specification (210 X 297 mm) (Please read the notes on the back before filling out this page) Order --------- Line 丨 Printed by the Intellectual Property Bureau Staff Consumer Cooperative of the Ministry of Economic Affairs 483905 A7 B7 5. Description of the invention (α) Tensile strength of 400 kg / m2, 92-94 ° /. 300% of the elastic recovery immediately, and 93% of 500% of the elastic recovery immediately. These physical properties are measured as follows: Melt rate (MI): After drying in a 120 ° C vacuum oven for 5 hours, measure the MI of a sample under a load of 26 (TC5,000 g. Softening point: place two as shown below The sample prepared in this way was cut into a size of ^ 10mm X 10mm, and it was stacked before being fed into the softening point measuring machine. A needle with a load of 1,000 grams penetrated the sample to 1 mm. At the depth, measure the temperature to obtain the softening point of the sample. Tensile strength, elongation, 300% immediate elastic recovery, and 500% immediate elastic recovery: Use an ASTM D412 die to cut the same sample as the softening point. A universal testing machine (UTM) measures physical properties. The samples used for measuring physical properties are prepared by hot pressing. In the past, the preparation technology using hot pressing was very poor, so the obtained samples could not be tested for physical properties in terms of quality. Now, coating Teflon's weaving technology allows the hot pressing to be used to prepare standard samples. The hot pressing is very convenient for preparing samples from a small amount of material in a short time. The common hot pressing is designed to heat and cool down. The preparation of the sample preparation includes adjusting the temperature of the heating plate to the range of 220-240 ° C and weighing the material to 180 grams. A three-layer iron plate structure is provided. A Teflon-covered plate is placed at the bottom. Then place a sample frame with a size of 250mm X 250mm X 2mm on the Teflon sheet. Secondly, pour the weighed material into the frame, and evenly distribute it on it. Then, cover one with Teflon. The plate of the dragon piece is placed on the frame like a lid. The obtained structure is inserted between the heating plates, and then pressurized for 1 minute at a pressure of 10 tons. 17 This paper size applies the Chinese National Standard (CNS) A4 specification ( 210 X 297 mm) (Please read the notes on the back before filling out this page) ^ -------- ^ --------- ^ »Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 B7 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (ιΟ and 30 minutes of pressure for 2 minutes. Move the structure to a cooling plate, and add 30 tons of pressure while cooling. Press for 2 minutes. After opening the lid, disassemble the structure to get a weight of about 160 grams and 2 · Samples with a thickness of 1 mm. The obtained samples were aged at 120 ° C for 2 hours to be suitable for physical property testing. Since the polymer prepared according to the present invention is thermoplastic, it can be extruded and molded uniformly . One of the factors that determines the compression moldability of a material is the ability to obtain a constant feed of the material when it is being saved. The smooth operation of a given feed material means that the material has enough to ensure a uniform melt state and Constant output thermoplasticity. The compression moldability can be determined by plotting the Tq of an extruder over time. The compression moldability of the thermoplastic polyurethane urea resin according to the present invention An extruder can be used for the evaluation, such as "Piastic〇der" sold by Brabender. The results are shown at a RPM of 50 and a Barrel temperature of 230-250-260-240 ° C. ,

Tq維持在35-40。固定擠製出該樹脂。經一模具擠製出之桿形產物之外觀觀察可知，該產物具有一無膠質的澄淨表面。本發明可藉由以下所進行說明之實例而得一較佳之了解，但其並非用以限制本發明。Tq remains at 35-40. The resin was fixedly extruded. Observation of the appearance of the rod-shaped product extruded through a die shows that the product has a clear surface without colloid. The present invention can be better understood through the examples described below, but it is not intended to limit the present invention.

實例I 亞丁基亞弓基己二酸酯（PBHA，Mw==1，〇〇〇)，一種聚醇，於UOt：真空烘箱下乾燥5小時，至一丨5〇 ppm或更少水含量之程度，以得到一預聚物之起始物。甲烷二苯 18 本紙張尺度過用肀國國家標準（CNS)A4 ^¥721〇" 297公釐） I------------ 裝--------訂---------線· (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483905 A7 B7 五、發明說明（基_4,4，-二異氰酸酯(MDI)於45°C烘箱中熔化。將該二異氰酸酯與該聚醇混合物(當量比，二異氰酸酯 :聚醇= 1.80:1.00)進給至一配有可控制攪拌器之圓底筒形反應器中，其設立於一維持在90°C下之油浴中。它們在 100 ppm有機錫催化劑(如T-10)存在下反應5分鐘或以上，同時以1，000 rpm攪拌，以製得一預聚物。該預聚物之反應過程可利用監視攪拌器馬達所負載之電流變化而加以偵測，發現在攪拌後2分鐘達最高點。爲了提供胺官能基予該預聚物，在攪拌下加入〇·8〇當量之Η20。此反應爲放熱反應，並產生C02。當攪拌持續時，除去氣泡，並造成異常的黏度增加。當合成之聚合物纏在攪拌器周圍時，將該聚合物攤平在一覆有可釋片之盤上。於一 l2〇°C之熱空氣烘箱中老化5小時。如上述般利用熱壓將該老化之聚合物製成物性測試用之試樣。所測試之物性見於下表1中。實例Π 使用 1.80丄0:0.80 之 MDI:PBHA-1500:H20 當量比重覆實例I之步驟。依此製得之聚合物物性見於下表1中。Example I Butylidene adipate (PBHA, Mw == 1, 000), a polyalcohol, dried in a UOt: vacuum oven for 5 hours to a water content of 50 ppm or less Degree to obtain the starting material of a prepolymer. Methane dibenzene 18 This paper has been used in the national standard (CNS) A4 ^ ¥ 721〇 " 297 mm) I ------------ Packing -------- Order --------- Line · (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 B7 V. Description of the invention (Base_4,4, -2 The isocyanate (MDI) was melted in an oven at 45 ° C. The diisocyanate and the polyol mixture (equivalent ratio, diisocyanate: polyol = 1.80: 1.00) were fed to a round-bottomed cylinder with a controllable stirrer The reactor was set up in an oil bath maintained at 90 ° C. They reacted for 5 minutes or more in the presence of a 100 ppm organotin catalyst (such as T-10), while stirring at 1,000 rpm to produce A prepolymer is obtained. The reaction process of the prepolymer can be monitored by monitoring the change in the current carried by the stirrer motor, and it is found that the highest point is reached 2 minutes after stirring. In order to provide an amine functional group to the prepolymer, Add 0.80 equivalents of Η20 under stirring. This reaction is an exothermic reaction and produces C02. When stirring is continued, bubbles are removed and cause abnormal viscosity Increase. When the synthesized polymer is wrapped around the mixer, flatten the polymer on a plate covered with releasable tablets. Age in a hot air oven at 120 ° C for 5 hours. Use as above The aged polymer was made into a sample for physical property testing by hot pressing. The physical properties tested are shown in Table 1 below. Example Π The MDI: PBHA-1500: H20 equivalent ratio of 1.80 丄 0: 0.80 was used to repeat the procedure of Example I. The physical properties of the polymers thus prepared are shown in Table 1 below.

實例III 重覆實例I之相同步驟，但使用聚四亞甲基醚二醇 (PTMG，Mw=l，000)作爲聚醇，且使用 ι·8〇:ι·〇:〇·8〇之 MDI:PTMG-1000:H20之當量比。製得之聚合物物性見於下 19 本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公爱） -------------^-----------------線 t (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 483905 Α7 Β7 五、發明說明（θ) 表1中。Example III The same procedure as in Example I was repeated, but using polytetramethylene ether glycol (PTMG, Mw = 1,000) as the polyhydric alcohol, and using MDI of ι · 80: ι · 〇: 〇.80 : PTMG-1000: H20 equivalent ratio. The physical properties of the polymer obtained are shown in the following 19 paper standards applicable to China National Standard (CNS) A4 specifications (210 X 297 public love) ------------- ^ -------- --------- Line t (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 Α7 Β7 V. Description of the invention (θ) Table 1.

實例IV 重覆實例I之相同步驟，但使用聚四亞甲基醚二醇 (PTMG，Mw=l，500)作爲聚醇，且使用 2,00:1.00:1.00 之 MDI:PTMG-1500:H20之當量比。製得之聚合物物性見於下表1中。Example IV The same procedure as in Example I was repeated, but using polytetramethylene ether glycol (PTMG, Mw = 1,500) as the polyalcohol, and using MDI: PTMG-1500: H20 of 2,00: 1.00: 1.00 Equivalence ratio. The physical properties of the obtained polymer are shown in Table 1 below.

比較例I 於攪拌下將〇·8〇當量之丁二醇(BD)加入以與實例I相同之方式製得之預聚物中作爲一鏈偶合劑。當合成之聚合物纏在高速攪拌器周圍時’將該聚合物攤平在一覆有可釋片之盤上。於一 120°C之熱空氣烘箱中老化5小時。如上述般利用熱壓將該老化之聚合物製成物性測試用之試樣。該聚合物之物性見於下表1中。比較例Π 使用 2·00:1·00:1·00 之 ΜΠΟΙ:ΡΒΗΑ-1500:Βϋ 當量比重Comparative Example I 0.80 equivalent of butanediol (BD) was added to the prepolymer prepared in the same manner as in Example I under stirring as a one-chain coupling agent. When the synthesized polymer is wrapped around a high-speed stirrer, the polymer is flattened on a disc covered with releasable tablets. Aging in a hot air oven at 120 ° C for 5 hours. As described above, the aged polymer was made into a test sample for physical properties by hot pressing. The physical properties of the polymer are shown in Table 1 below. Comparative Example Π Use of ΜΠΟΙ: ΡΒΗΑ-1500: Βϋ equivalent weight of 2.00: 1.00: 1.00

覆比較例I之步驟。依此製得之聚合物物性見於下表1中比較例III 重覆比較例I之相同步驟，但使用聚四亞甲基醚二醇 (PTMG，Mw=l，〇〇〇)作爲聚醇，.且使用 1·80:1·0··0·80 之 20 本紙張尺度適用中國國家標準（CNS)A4規格（210 χ 297公釐） I------------ 、哀-------丨訂---------線t (請先閱讀背面之注意事項再填寫本頁) 483905 Α7 Β7 五、發明說明（) MDLPTMG-lOOOiBD之當量比。製得之聚合物物性見於下表1中。The procedure of Comparative Example I was repeated. The physical properties of the polymer obtained in this way are shown in Comparative Example III in Table 1 below, repeating the same steps of Comparative Example I, but using polytetramethylene ether glycol (PTMG, Mw = 1, 00) as the polyalcohol, .And use 1 · 80: 1 · 0 ·· 0 · 80 of this paper size to apply Chinese National Standard (CNS) A4 specification (210 χ 297 mm) I ------------ 、 Lay ------- 丨 Order --------- Line t (Please read the notes on the back before filling this page) 483905 Α7 Β7 V. Description of the invention () MDLPTMG-1000iBD equivalent ratio. The physical properties of the obtained polymer are shown in Table 1 below.

比較例IV 重覆比較例I之相同步驟，但使用聚四亞甲基醚二醇 (PTMG，Mw=l，500)作爲聚醇，且使用 2_00:1·00:1·00 之 ΝΠ)Ι:ΡΤΜΟ-1500:Η2Ο之當量比。製得之聚合物物性見於下表1中。表 1 實例硬度 (Shore A) 張力強度 (Kg/cm2) 300% 延展率彈力回 (%) 復 (%) 500% 彈力回軟化點復 ΓΟ C%) I 80 340 750 93.5 91.5 145 II 79 330 780 94.1 92.1 143 III 79 300 740 93.6 91.6 141 IV 78 290 750 94.0 92.3 140 C. I 82 320 710 85.2 72.5 72 C. II 80 310 750 84.6 73.2 75 C. III 78 280 720 84.5 74.3 68 C. IV 77 260 740 83.7 73.5 70 表I中之數據證明根據本發明方法所製得之聚胺基甲酸酯尿素樹脂在抗熱性與彈性回復上遠較傳統方法所製得者優異。這些本發明之聚胺基甲酸酯尿素樹脂可進行融熔本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐） -------------k i — (請先閱讀背面之注意事項再填寫本頁) 訂——.------亨經濟部智慧財產局員工消費合作社印製 483905 A7 B7___ 五、發明說明（/ ) 紡紗，以製造有用之彈性纖維。本發明已以舉例說明之方式加以說明，應了解所用之技術本質上係用以說明而非限制。本發明之諸多修飾與變 •化在以上的揭示下均屬可能。因此，應了解者爲在如附請求保護之申請專利範圍內，可以該特定說明以外之方式實施本發明。 R------------^--------訂---------線- (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製本紙張尺度適用中國國家標準（CNS)A4規格（210 X 297公釐）Comparative Example IV The same steps as in Comparative Example I were repeated, but using polytetramethylene ether glycol (PTMG, Mw = 1,500) as the polyhydric alcohol, and 2_00: 1 · 00: 1 · 00 (NΠ) 1 Equivalent ratio of: ΡΤΜΟ-1500: Η2Ο. The physical properties of the obtained polymer are shown in Table 1 below. Table 1 Example Hardness (Shore A) Tensile strength (Kg / cm2) 300% Elongation Elastic return (%) Complex (%) 500% Elastic return to softening point Complex ΓΟ C%) I 80 340 750 93.5 91.5 145 II 79 330 780 94.1 92.1 143 III 79 300 740 93.6 91.6 141 IV 78 290 750 94.0 92.3 140 C. I 82 320 710 85.2 72.5 72 C. II 80 310 750 84.6 73.2 75 C. III 78 280 720 84.5 74.3 68 C. IV 77 260 740 83.7 73.5 70 The data in Table I prove that the polyurethane urea resin prepared according to the method of the present invention has far better heat resistance and elastic recovery than those made by traditional methods. These polyurethane urea resins of the present invention can be melted. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) ------------- ki — (Please read the precautions on the back before filling this page) Order ——.------ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 483905 A7 B7___ V. Description of the invention (/) Spinning to make useful Of elastic fibers. The invention has been described by way of illustration, and it should be understood that the techniques used are by way of illustration and not limitation. Many modifications and variations of the present invention are possible under the above disclosure. Therefore, it should be understood that the present invention may be implemented in a manner other than the specific description within the scope of the patent application as claimed. R ------------ ^ -------- Order --------- line- (Please read the precautions on the back before filling in this page) Ministry of Economy Wisdom The paper size printed by the Property Cooperative Consumer Cooperative is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm)

Claims

483905 .Announcement A8 B8 C8 D8

Scope of patent application1. A thermoplastic polyurethane urea resin for melt spinning, including the polymer represented by the following chemical formula I: (Please read the precautions on the back before writing this page) [A -0- (0) C-NH-D-NH-C (0) -NH-D-NH-C (0) -0] n [I] where A represents an organic polyalcohol residue having about 500 to Number average molecular weight of 5,000 and weight average molecular weight / number average molecular weight (Mw / Mn) of 1.5 to 2.5, and the number of functional groups in the range of 1.8 to 2.2, 0 represents an aromatic organic diisocyanate residue The number of functional groups is in the range of 1.8 to 2.2, and η represents the number of repeating units. 2. The thermoplastic polyurethane urea resin according to item 1 of the application, wherein the aromatic organic diisocyanate residue D has an average molecular weight of the number of aromatic diisocyanates of 500 or less. 3. The thermoplastic polyurethane urea resin according to the first patent application range, wherein the aromatic organic diisocyanate residue D is a methanediphenyl-4,4'-diisocyanate residue. 4. The thermoplastic polyurethane urea resin according to item 1 of the scope of the patent application, wherein the organic polyol residue A is selected from the group consisting of aliphatic polyester polyols, aliphatic polyether polyols, and aliphatics. Polycaprolactone polyols, aliphatic carbonate polyols, and aliphatic siloxane polyols. 5. The thermoplastic polyurethane urea resin according to item 4 of the application, wherein the organic polyalcohol A has a number average molecular weight of about 1,000 to 2,000 and L. 8 to .2 · The average weight of 2 is 1. The size of this paper is applicable to China National Standard (CNS) A4 (210 X 297 mm) 483905 λ8 Β8 C8 D8 ----------; ----- VI. Patent application range sub-quantity / number average molecular weight (Mw / Mn). 6. —Method for preparing thermoplastic polyurethane urea resin for melt spinning, the polyurethane urea resin has the following chemical formula I: [A-0- (0) C-NH-D -NH-C (0) -NH-D-NH-C (0) -0] n [I] where A represents an organic polyol residue, having a number average molecular weight of about 500 to 5,000, and 1.5 Weight average molecular weight / number average molecular weight (Mw / Mn) to 2.5, and the number of functional groups in the range of 1.8 to 2.2, D represents an aromatic organic diisocyanate residue, and the number of functional groups is in the range of 1.8 to 2.2, and n represents the number of repeating units, and includes the following steps: (A) reacting an organic polyol with an excess of an organic diisocyanate to obtain a prepolymer, the organic polyol having a number average molecular weight of about 500 to 5,000 and 1.5 to 2.5 Weight average molecular weight / number average molecular weight (Mw / Mn) and the number of functional groups in the range of 1.8 to 2.2, the number of functional groups of the aromatic organic diisocyanate in the range of 1.8 to 2.2; (B) making the prepolymer Part of the diisocyanate group is aminated; (C) between the residual isocyanate group and the newly obtained amine group Two molecules of the reaction, to produce a urea functional group, so that through this two linear molecules of the prepolymer of engagement; and (D) The urea-containing bis prepolymer. 7. The method according to item 6 of the scope of patent application, in which this step. ^ 2 A paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ......---------- ----------- V -------------- Order ---------------- line- (Please read the back first (Notes are reproduced on this page) 483905 A8B8C8D8 6. The scope of patent application (A) is based on the equivalent ratio of the aromatic organic diisocyanate to the polyol within the range of 1.5 to 2.5. (Please read the notes on the back before writing this page) 8. The method according to item 6 of the scope of patent application, wherein step (B) is based on the equivalent ratio of NCO group to H20 of the prepolymer ranging from 1.8 to 2.2 Within the range. 9. The method according to item 6 of the application, wherein the aromatic organic diisocyanate has an average molecular weight of the number of aromatic diisocyanates of 500 or less. 10. The method according to item 6 of the application, wherein the organic polyol is selected from the group consisting of aliphatic polyester polyols, aliphatic polyether polyols, aliphatic polycaprolactone polyols, and aliphatics. Carbonate polyols, and aliphatic siloxane polyols. Line Π. The method according to item 10 of the scope of patent application, wherein the organic polyol A has a number average molecular weight of about 1,000. To 2,000 and a weight average molecular weight / number average molecular weight (Mw / Mn) of 1.8 to 2.2. 3 This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)