1334892 (1) 玖、發明說明 【發明所屬之技術領域】 本發明爲關於混合使用聚胺基甲酸乙酯彈性纖維與其 他纖維的編織物及其製造方法。若更詳言之，爲關於由該 編織物所作成之製品於穿著使用中難經由重複伸長所產生 之坯布的「變形、孔移距、邊緣不齊」，由裁斷部抽出紗 之所謂的「脫線」，於組織發生的梯狀傷痕和不勻，即「 漏針、點線」、坯布爲彎曲狀態之「捲曲」及由裁斷、縫 製之製品的針跡部分僅抽出彈性纖維且令坯布的伸縮性部 分變無「滑入」等之平針織物、羅紋編織、雙反面組織等 之圓針織物和其他之緯針織物、集圈抽花組織、經平組織 編物、經絨組織、經編緞紋組織等之經針織物、織物等之 混用聚胺基甲酸乙酯彈性纖維之編織物以及其製造方法。 【先前技術】 使用混用聚胺基甲酸乙酯彈性纖維的緯針織物、經針 織物、織物等之彈性坯布的製品，因爲延伸度大，且由伸 長狀態之回復力和合適性良好，故廣被利用。但是，若將 混用聚胺基甲酸乙酯彈性纖維之坯布予以裁斷、縫製作成 的製品予以重複伸張、則引起變形成變成不均勻的坯布「 變形' 孔移距、邊緣不齊」'抽紗「脫線」、坯布組織發 生梯狀傷痕和不勻之「漏針、點線」、坯布彎曲之「捲曲 」等問題。又，經由重複伸長則於縫製部分亦引起聚胺基 甲酸乙酯彈性纖維由針跡抽出，所謂的「滑入」。發生此 -4 - (2) (2)1334892 滑入且彈性纖維抽出的坯布部分當然變成無收縮力，故於 坯布上發生密度斑，且具有無法穿著使用的問題。 此些現象，即使於使用聚胺基甲酸乙酯彈性纖維以外 之彈性纖維的編織物亦發生，且於伸縮性強的聚胺基甲酸 乙酯彈性纖維的情況爲特別顯著。 此些問題的對策迄今已有下列提案。 (1) 抑制聚胺基甲酸乙酯彈性纖維的收縮力。 (i )令聚胺基甲酸乙酯彈性纖維的伸長倍率不 會頗高。 (ii)提高編織物的加工溫度並抑制聚胺基甲酸 乙酯彈性纖維的收縮力。 (iii )選擇定型性高的彈性纖維。 (2) 經由提高定型溫度，令聚胺基甲酸乙酯彈性纖 維彼此間的交點相互熔點。 (3 )使用低熔點的聚胺基甲酸乙酯彈性纖維防止低 溫下熔黏。 (4)提高縫製時之針跡密度，抑制聚胺基甲酸乙酯 彈性纖維的滑動，且難引起滑入。 (5 )以包芯紗之形式使用時，提高捻數，作成雙包 覆形式。又，亦提案將包芯紗與其他紗予以噴氣交纏的方 法（參照特開平04 — 11036號公報）。 (6)將滑入和孔移距且難織者，予以編結（參照特 開2002 — 69804號公報、特開2002—13052號公報）。 但是’如（1 ) ( i)般減低聚胺基甲酸乙酯彈性纖維 -5- (5) (5)1334892 維彼此間或其與非彈性紗之交叉部，較佳爲高熔黏聚胺基 甲酸乙酯彈性纖維與非彈性紗之交叉部予以熱熔黏所構成 〇 〔Π〕如〔I〕之混用聚胺基甲酸乙酯彈性纖維之編 織物，其爲再含有具有200 °C以上熔點之高熔點聚胺基甲 酸乙酯彈性纖維，且令此高熔點聚胺基甲酸乙酯彈性纖維 與上述高熔黏聚胺基甲酸乙酯彈性纖維之交叉部予以熱熔 黏。 〔III〕一種混用聚胺基甲酸乙酯彈性纖維之編織物 的製造方法，其特徵爲使用於100%伸長狀態下之150°c ' 4 5秒鐘乾熱處理後之強力保持率爲5 0 %以上，且具有 1 80 °C以下熔點之高熔黏聚胺基甲酸乙酯彈性纖維、和至 少一種之非彈性紗形成編織物的針織物後，經由乾熱或濕 熱定型使得高熔黏聚胺基甲酸乙酯彈性纖維彼此間或其與 非彈性紗之交叉部，較佳爲高熔黏聚胺基甲酸乙酯彈性纖 維與非彈性紗之交叉部予以熱熔點》 〔IV〕如〔III〕之混用聚胺基甲酸乙酯彈性纖維之 編織物的製造方法，其爲再使用具有200°C以上熔點之高 熔點聚胺基甲酸乙酯彈性纖維，且令此高熔點聚胺基甲酸 乙酯彈性纖維與上述高熔黏聚胺基甲酸乙酯彈性纖維之交 叉部予以熱熔黏= 【實施方式】 用以實施發明之最佳形態 -8 - (6) (6)1334892 以下，更詳細說明本發明。 本發明所用之聚胺基甲酸乙酯彈性纖維，若爲低溫下 亦可輕易熔黏’且具有耐熱性的高熔黏聚胺基甲酸乙酯彈 性纖維即可，其組成、製造方法等並無特別限制，例如， 令多元醇與過剩莫耳量之二異氰酸酯反應，製造兩終端具 有異氰酸酯基之聚胺基甲酸乙酯中間聚合物，且令可與該 中間聚合物之異氰酸酯基容易反應之具有活性氫的低分子 量二胺和低分子量二醇於惰性有機溶劑中反應，製造聚胺 基甲酸乙酯溶液（聚合物溶液）後，除去溶劑成形爲紗條 的方法、和令多元醇與二異氛酸酯與低分子量二胺或低分 子量二醇反應之聚合物固化且溶解於溶劑後，除去溶劑成 形爲紗條的方法、令前述固化之聚合物未於溶劑中溶解且 經由加熱成形爲紗條的方法、令前述多元醇與二異氰酸酯 與低分子量二醇反應取得聚合物，且不令該聚合物固化並 且成形紗條之方法，以及，令上述各種方法所得之聚合物 或聚合物溶液混合後，由混合聚合物溶液中除去溶劑且成 形紗條的方法等。其中’特別以（A )令多元醇與二異氰 酸醋反應所得之兩終端異氰酸醋基預聚物（以下稱爲「兩 終端NCO基預聚物」）、和（B)令多元醇與二異氰酸酯 與低分子量二醇反應所得之兩終端羥基預聚物（以下稱爲 「兩終端0H基預聚物」）反應所得之聚合物未固化予以 熔融紡紗之方法’因爲於低溫下易熔黏’且取得具有耐熱 性之高熔黏聚胺基甲酸乙酯彈性纖維上爲佳’且不含有溶 劑之回收，故爲經濟的。 -9- (7) (7)1334892 此時，構成（A) ， （B)成分之預聚物的多元醇可 爲相同或相異，但以使用數平均分子量爲800~3,000左右 的聚合物二醇爲佳。 此類聚合物二醇可使用聚醚二元醇、聚酯二元醇、聚 碳酸酯二元醇等。 聚酸二元醇可例示例如氧化乙院、氧化丙院、四氫咲 喃等之環狀醚之開環聚合所得的聚醚二醇：乙二醇、丙二 醇、1’4 — 丁二醇、1，5_戊二醇、新戊二醇、1，6 —己 二醇、3 —甲基_1’ 5 —戊二醇等之二元醇之縮聚所得的 聚醚二元醇等。 聚酯二元醇可例示例如乙二醇、丙二醇、1，4 — 丁二 醇、1’ 5 —戊二醇 '新戊二醇、〗，6—己二醇、3 —甲基 一 1 ’ 5 —戊二醇等之二元醇類所選出之至少一種、與己二 酸' 癸二酸、壬二酸等之二元酸類所選出之至少一種的縮 聚所得的聚酯二元醇；e _己內酯、戊內酯等之內酯類之 開環聚合所得的聚酯二元醇等。 聚碳酸酯二元醇可例示例如碳酸二甲酯、碳酸二乙酯 等之碳酸二烷酯；碳酸伸乙酯、碳酸伸丙酯等之碳酸伸烷 酯；碳酸二苯酯、碳酸二蔡酯等之碳酸二芳酯等所選出之 至少一種碳酸酯、與乙二醇、丙二醇、1, 4_ 丁二醇、1 ’5 戊—醇、新戊—醇、1，6 —己二醇、3 —甲基一1，5 -戊二醇等所選出之至少一種脂族二醇之酯交換反應所得 的碳酸酯二元醇等。 上述例示之聚醚二元醇、聚酯二元醇、或聚碳酸酯二 -10- (8) 1334892 元醇可單獨使用一種或組合二種以上’爲了取得良 黏性、聚醚二醇成分相對於使用合計量之聚合物 5〇質量％以上，較佳爲60質量％以上’且聚醚二 爲100質量％亦可。還有，聚醚二醇成分特別以聚 醚二元醇爲適於使用。 構成（A) 、 （B)成分之預聚物的二異氰酸 用製造聚胺基甲酸乙酯時所通常使用之脂族系、脂 、芳香族系、芳香脂族系等之二異氰酸酯。 此類二異氰酸酯可列舉例如4，4'—二苯基甲 氰酸酯、2，4一伸甲苯二異氰酸酯、1，5-萘二異 、伸二甲苯二異氰酸酯、氫化二伸甲苯二異氰酸酯 爾酮二異氰酸酯、1，6—伸己基二異氰酸酯、對— 二異氰酸酯、4，4’_二環己基甲烷二異氰酸酯' 甲基二甲苯二異氰酸酯、對一四甲基二甲苯二異氰 ，其可單獨使用一種或組合使用，其中以4，4· 一 甲烷二異氰酸酯、4，4· 一二環己基甲烷二異氰酸 佳使用。 鏈延長劑之低分子量二醇和低分子量二胺以反 適當，且可提供適度耐熱性者爲佳，且可使用具有 與異氰酸酯反應之活性氫原子，且一般以分子量爲 下的低分子量化合物。 此類低分子量化合物可使用例如乙二醇、丙二 ，4 — 丁二醇、1，5_戊二醇、新戊二醇、1，6 — 、3 —甲基一 1，5_戊二醇等之脂族二醇類，且在 好的熔 二醇以 醇成分 伸丁基 酯可使 環式系 烷二異 氰酸酯 、異佛 伸苯基 間一四 酸酯等 二苯基 酯爲較 應速度 二個可 500以 :醇' 1 己二醇 不妨礙 -11 - (9) 1334892 紡紗性之範圍內亦可使用甘油等三官能二元醇類 單獨一種或組合使用二種以上，但由作業性和對 提供適度物性方面而言，以乙二醇、1，4 — 丁二 又’此類低分子量二胺可使用例如乙二胺、 丙二胺、己二胺、伸二甲苯二胺、4，4 —二胺基 烷' 肼等。 亦可倂用低分子量二醇和低分子量二胺，於 ’以低分子量二醇更佳使用做爲鏈延長劑。 又，亦可混合使用丁醇等之一官能性單醇和 二丁胺等之一官能性單胺做爲反應調整劑或聚合 〇 聚胺基甲酸乙酯聚合反應時、或使用做爲紡 情性溶劑可列舉N，N —二甲基甲醯胺、N，N -醯胺、Ν，Ν，Ν，，Ν’一四甲基脲、N —甲基吡咯 甲基亞碩等之極性溶劑。 於上述（A ) ， （ B )成分之預聚物中，爲 候性、耐熱氧化性、耐黃變性，亦可添加紫外線 抗氧化劑、光安定劑等之任意成分。 紫外線吸收劑可列舉例如2 —（ 3，5 —二— 一 2 —羥苯基）苯並三唑、2— （3_第三丁基一 5 2 —羥苯基）一 5 —氯基苯並三唑、2— (2_羥基 聯苯）苯並三唑等之苯並三唑系之紫外線吸收劑 抗氧化劑可列舉例如3，9 —雙（2 -（ 3 — 丁基—4_羥基_5—甲基苯基）丙醯氧基）一 1， 。彼等可 所得纖維 醇爲佳。 丁二胺、 二苯基甲 本發明中 二乙胺和 度調整劑 紗溶液的 二甲基乙 烷酮、二 了改善耐 吸收劑、 第三戊基 _甲基一 -3，5 -〇 (3 _第三 1 -二甲 -12- (12) (12)1334892 體反應則可取得。所得之兩終端〇H基預聚物可使用附有 套管之齒輪泵（例如，KAP — 1川崎重工業股份有限公司 製）注入聚胺基甲酸乙酯彈性纖維用反應機。 還有，此兩預聚物合成時，可添加用以改善耐候性、 耐熱氧化性、耐黃變性等之上述各種藥品類。 (III )之紡紗用聚合物之合成可令以一定比率送入 之（A ) 、 （ B )之預聚物、連續反應則可取得。此時， 反應機以通常之聚胺基甲酸乙酯彈性纖維之熔融紡紗法所 用者即可’且以具備令紡紗用聚合物於加熱、熔融狀態下 攪拌、反應，且再移送至紡紗頭之機構的反應機爲佳。反 應條件爲於160〜220 °C下1〜90分鐘，較佳於180〜120 °C下 3〜80分鐘》 本發明之聚胺基甲酸乙酯彈性纖維爲於所合成之紡紗 用聚合物未固化下移送至紡紗頭，並由管嘴吐出、紡紗則 可取得，但紡紗用聚合物於反應機內的平均滯留時間爲根 據反應機之種類而異，依據下式算出。 於反應機內之平均滯留時間=(反應機容積/紡紗用聚 合物吐出量）X紡紗用聚合物之比重 一般而言’使用圓筒形反應機之情況爲約〗小時，使 用雙螺桿擠壓機之情況爲5〜10分鐘。紡紗溫度爲 180〜2 3 0 t ，由管嘴連續擠出後，冷卻，且附著紡紗油劑 並捲取則可取得。 此處，兩終端NCO基預聚物與兩終端〇H基預聚物 之比率爲令立即紡紗後之紗中NC〇基爲以0.3M質量％ ’ -15- (13) (13)1334892 較佳爲0_35〜0.85質量％殘留般適當調整齒輪泵的迴轉比 率爲佳。若N C 0基含有過剩〇 3質量％以上，則亦可經由 紡紗後之鏈延長反應提高強伸度、耐熱性等之物性。但是 ，若N C 0基爲少於0.3質量％，則恐令所得之聚胺基甲酸 乙酯彈性纖維的耐熱強力保持率降低，又，若超過1質量 % ’則紡紗用聚合物的黏度變低，發生難以紡紗的情況。 還有，紡紗纖維中之N C Ο基含有率爲如下測定。 將紡紗的纖維（約1克）以二丁胺/二甲基甲醯胺/甲 苯溶液溶解後’令過剩之二丁胺與試料中的NCO基反應 ’且以鹽酸滴定殘餘的二丁胺，並算出NCO基的含量。 本發明所用之聚胺基甲酸乙酯彈性纖維爲如上述於主 原料爲使用聚醚二醇，且以熔融反應紡紗法所製造之聚胺 基甲酸乙酯彈性纖維爲特佳。 本發明所使用之聚胺基甲酸乙酯彈性纖維爲於1 00% 伸長狀態下以150 °C、45秒鐘乾熱處理後之強力保持率爲 50%以上，較佳爲55%以上。強力保持率若低於50%，則 熱定型後之製品伸縮性降低，故爲不佳。 還有，強力保持率之上限並無特別限制，通常爲90% 以下，特別爲80%以下。 又，聚胺基甲酸乙酯彈性纖維之熔點爲180 °C以下， 較佳爲175t以下。若高於180 °C，則熔黏用的熱處理溫 度過高，且對製品的觸感、染色堅牢度等造成不良影響， 故爲不佳。 還有，熔點之下限爲！50°C以上’特別爲155t以上 -16- (14) (14)1334892 ’因爲與高熔點聚胺基甲酸乙酯彈性纖維混合使用時的尺 寸安定性、和坯布的伸長回復力方面而言爲佳。 還有，強力保持率之測定方法爲如後述。 本發明之混用聚胺基甲酸乙酯彈性纖維之編織物爲使 用上述高熔黏聚胺基甲酸乙酯彈性纖維及非彈性紗，更且 ’亦可混用例如具有2 0 0 °C以上熔點之高熔點聚胺基甲酸 乙酯彈性纖維作成具有下列構造者。 (1)將含有高熔黏聚胺基甲酸乙酯彈性纖維與至少 一種非彈性紗之複合紗使用於經紗和/或緯紗的織物。組 織可爲平織、綾織、棱紋織等任一者，且織機亦可使用梭 式織機、劍桿織機、噴氣式織機等。更且，經紗及緯紗可 全部爲該複合紗，且亦可複合紗與非彈性紗以1 : 1、1 : 2或1 : 3等之繡密比率混合使用。 (2 )於針織機之相同的線圈橫列中混用高熔黏聚胺 基甲酸乙酯彈性纖維及至少一種以上之非彈性紗的緯針織 物。將高熔黏聚胺基甲酸乙酯彈性纖維及非彈性紗織入之 緯針織物的編組織爲平編、羅紋組織、雙反面組織、兩面 編、及其組合' 及其變化的組織等之任一種組織物可編成 。關於針織機亦可使用圓針織機、橫針織機、全成形平型 針織機、襪子針織機等之全部針織機。高熔黏聚碳酸酯彈 性纖維可插入或織入均可。又’亦可爲高熔黏聚胺基甲酸 乙酯彈性纖維與非彈性紗的添紗組織，且亦可使用高熔黏 聚胺基甲酸乙酯與非彈性紗的複合紗。與（1 )同樣地於 全線圏橫列中織入闻熔黏聚胺基甲酸乙醋彈性纖維亦可， -17- (15) (15)1334892 且亦可於隔開1個以上線圈橫列予以織入。高熔黏聚胺基 甲酸乙酯彈性纖維與非彈性紗交互、或以適當間隔織入亦 可。更且’亦可混用高熔點聚胺基甲酸乙酯彈性纖維。以 下示出其例，但並非限定於此。 (2 ) - 1 全線圈橫列之例： 第1 口 高溶黏紗及非彈性紗、或複合紗 第2 口 高熔黏紗及非彈性紗、或複合紗 第3 口 高熔黏紗及非彈性紗、或複合紗 第4 口 高熔黏紗及非彈性紗、或複合紗 (2)-2 隔開1個線圈橫列之例： 第1 口 高熔黏紗及非彈性紗、或複合紗 第2 口 非彈性紗 第3 口 高熔黏紗及非彈性紗、或複合紗 第4 口 非彈性紗 (2 ) - 3 高熔黏紗與高熔點紗以隔開1個線圈橫列使 用之例： 第1 口 高熔黏紗及非彈性紗、或複合紗 第2 口 高熔黏紗及非彈性紗、或複合紗 第3 口 高熔黏紗及非彈性紗、或複合紗 第4 口 高熔點紗及非彈性紗、或複合紗 (2)-4 交互之例 第1 口 商溶黏紗 第2 口 非彈性紗、或高熔黏紗及非彈性紗 -18- (16) (16)1334892 第3 口 高熔黏紗 第4 口 非彈性紗、或高熔黏紗及非彈性紗 (3 )混用高熔黏聚胺基甲酸乙酯彈性纖維及至少一 種以上之非彈性紗的經針織物。將高熔黏聚胺基甲酸乙酯 彈性纖維及非彈性紗織入之經針織物的編組織爲鏈式針織 、經平組織編織、經絨組織、經編緞紋組織、及其組合、 及其變化的組織等之任一種組織物可編成。關於針織機亦 可使用特里科經編機、拉舍爾經編機、米蘭尼斯經編機等 之全部針織機。與（1)同樣地於全面織入高熔融聚胺基 甲酸乙酯彈性纖維亦可，且以適當間隔織入亦可。又，高 熔黏聚胺基甲酸乙酯彈性纖維可爲插入或織入均可。更且 ，亦可混用高熔點聚胺基甲酸乙酯彈性纖維。以下示出其 例，但並非限定於此。 (3 ) - 1 鏈式組織的針織物 圖1及圖2爲示出花邊布等所常使用的鏈式組織。此 鏈式組織於缺口縫製後易具有漏針、鬆開等之缺點。其對 策雖已提案出防止漏針的組織，但防止漏針組織的痕跡乃 在坯布上骯髒殘留，殘有妨礙高級感之問題。於是，於圖 1及圖2中’若以a爲非彈性紗、b爲本發明之高熔黏聚 胺基甲酸乙酯彈性纖維、或高熔黏聚胺基甲酸乙酯與高熔 點聚胺基甲酸乙酯彈性纖維拉齊織入並且熱定型，則於圖 1所示之X部中’高熔黏聚胺基甲酸乙酯彈性纖維與非彈 -19- (17) (17)1334892 性紗、及高熔黏聚胺基甲酸乙酯彈性纖維與高溶@ s 甲酸乙酯彈性纖維爲接觸且熱熔黏，取得伸長回 ，並且防止漏針、鬆開等之缺點，並且審美性亦無任何受 損的針織物。 (3)-2 鏈式組織以外之針織物 鏈式組織以外之一般所使用的組織，若將本發明之高 熔黏聚胺基甲酸乙酯彈性纖維插入或織入使用，則亦可經 由與非彈性紗的熔黏、及聚胺基甲酸乙酯彈性纖維彼此間 的熔黏，而難引起邊緣不齊（彈性纖維的不勻、抽出、飛 出）等’可實質上特別提高坯布的耐久性。又，可令坯布 爲更安定，難引起捲曲，且亦可察見縫製時的費用下降。 例如’於圖3〜8所示之組織圖中，經由適當使用高融 黏聚胺基甲酸乙酯彈性纖維，則可取得難發生孔移距 '邊 緣不齊、脫線、漏針、點線、捲曲和滑入的針織物。 圖3中，L1及L2爲全面插入（All— in)，圖4中之 L1與L2、L3與L4爲隔一根插入（1 in— 1 out)，圖5~8 中之LI、L2、L3爲全面插入（All— in)。又，圖3~8之 a爲非彈性紗、b爲本發明之高熔黏聚胺基甲酸乙酯彈性 纖維單獨或與高熔點聚胺基甲酸乙酯彈性纖維拉齊使用， 且圖5及6之C爲使用二根本發明之高熔黏聚胺基甲酸乙 酯彈性纖維，或本發明之高熔黏聚胺基甲酸乙酯彈性纖維 與高熔點聚胺基甲酸乙酯彈性纖維各使用一根。 更且，根據使用用途，於無縫製切斷口而就其原樣使 -20- (18) (18)1334892 用時，以往爲因洗滌和穿著使用時的擦痕，而具有脫線等 之耐久性上的問題，但其亦可大爲改善。 此處，與高熔黏聚胺基甲酸乙酯彈性纖維混用的非彈 性紗並無特別限制，例如可使用木綿、麻、羊毛、絹等之 天然纖維、人造絲、銅氨纖維、波里諾西克（Polynosic ) 等之再生纖維、醋酸酯等之半再生纖維、尼龍、聚酯、丙 烯酸等之化學合成纖維等之纖維，而聚胺基甲酸乙酯彈性 纖維之混用比例以1 ~40%左右爲佳。 又，於本發明之混用聚胺基甲酸乙酯彈性纖維之編織 物中，經由混合使用二胺且進行鏈長反應之乾式紡紗法之 耐熱性、彈性回復性優良之具有2 0 0 °C以上，較佳爲2 1 0 °C以上熔點的高熔點聚胺基甲酸乙酯彈性纖維，則亦可取 得一邊保持熔黏性一邊具有良好彈性性能的編織物。此時 ’此高熔黏聚胺基甲酸乙酯彈性纖維之使用量爲2〜40%左 右爲佳。 此處，乾熱定型之方法爲使用如栓拉幅機般的定型機 ，且經由熱風予以熱固定則可進行。此時，定型溫度爲 14 0〜200°C ’特別爲170〜190 t：，定型時間爲10秒鐘〜3分 鐘、特別爲30秒鐘〜2分鐘。 另一方面，濕熱定型之方法爲將針織物以放入型板之 狀態下，經由指定壓力的飽和蒸氣予以熱固定則可進行。 此時，定型溫度爲100〜130 °C，特別爲105〜125 °C，定型 時間爲2〜6 0秒鐘，特別爲5〜3 0秒鐘。 若根據本發明，則可於低定型溫度下加工，且取得難 -21 - (19) 1334892 發生孔移距、邊緣不齊、脫線、漏針、捲曲、 距現象的混用聚胺基甲酸乙酯彈性纖維的編織 以下，示出實施例和比較例，具體說明本 發明不被限制於下述實施例。還有，於下列例 質量份。 〔實施例1〕 合成以下之兩終端NCO基預聚物與兩終 聚物，做爲聚胺基甲酸乙酯彈性纖維合成用的 兩終端0Η基預聚物之合成 將做爲二異氰酸酯之4，4·—二苯基甲烷 (以下稱爲MDI ) 25份裝入經氮氣密封之附； 套管的反應鍋，並將做爲聚合物二醇之數： 2,000的聚伸丁基醚二元醇（以下稱爲PTMG) 攪拌一邊注入。反應1小時後，再將做爲低分 1 ’ 4 — 丁二醇27.6份注入，合成兩終端〇Η基 兩終端NCO基預聚物之合成 於經氮氣密封之80t：的反應鍋中裝入做 酯的MDI 47.4份，並添加紫外線吸收劑（2 — 一第三戊基一 2—羥苯基）苯並三唑：20% ) (3，9 —雙（2- (3— (3 —第三丁基—4 —笑 基苯基）丙酿氧基）一1，1 一二甲基乙基）- 滑入和孔移 物。 發明，但本 中，份均爲 端OH基預 原料。 二異氰酸酯 穿80°C溫水 P均分子量 100份一邊 子量二醇的 預聚物。 爲二異氰酸 (3，5 -二 、抗氧化劑 i基一 5 —甲 -2，4，8， -22- (20) (20)1334892 10 —四哼螺（5，5) ~\--烷：50%)、光安定劑（雙（2 ，2，6，6_四甲基_4 一呢症基）癸二酸酯：30%)之混 合物2.2份，並一邊攪拌一邊注入做爲聚合物二醇之數平 均分子量2,000的PTMG100份，且繼續攪拌1小時，取 得兩終端NCO基預聚物》 所得之兩終端NCO基預聚物與兩終端〇H基預聚物 以1 : 0.475之質量比，連續供給至具有攪拌翼之容量 2,2 00毫升的聚胺基甲酸乙酯彈性纖維用圓筒形反應機。 供給速度爲兩終端NCO基預聚物2 8.9 3克/分鐘，兩終端 OH基預聚物13.74克/分鐘。於反應機內之平均滯留時間 爲約1小時、反應溫度爲約1 9 0 °C。 所得之聚合物未固化，且導入保持於192 °C溫度之8 管嘴紡紗頭2台中。紡紗用聚合物經由頭中所設置的齒輪 泵予以計量，加壓，且以濾紙過濾後，由直徑0.6 m m、1 孔之管嘴以2.67克/分鐘之速度下，於長度6m之紡紗筒 內吐出（由管嘴之吐出總量：42.67克/分鐘），—邊賦予 油劑一邊以600m/分鐘之速度捲取，取得44分特的聚胺 基甲酸乙酯彈性纖維。 立即吐出後之聚胺基甲酸乙酯彈性纖維的NCO基含 有率爲〇·42質量％。此聚胺基甲酸乙酯彈性纖維之物性以 下述方法予以測定’結果熔點爲1 6 8 t、耐熱強力保持率 爲65%。更且，使用此彈性纖維以下述方法作成針織物， 且測定熱定型後之針織物的解編張力。結果示於表1。 -23- (21) 1334892 $點之測定方法 測定裝置：TMA (熱機器測定裝置） 使用石英探針 握把長：2 0 m m 伸長：Ο . 5 % 溫度範圍：室溫〜2 5 0 °C 升溫速度：20°C /min 評價：將熱應力爲Omgf時之溫度定義爲溶點 耐熱強力保持率的測定方法 !長予以 1 5 0 °C 之 t之聚胺 [伸試驗 ^測定。 :相對於 將聚胺基甲酸乙酯彈性纖維以1 〇公分之握] 保持伸長至20公分。於伸長狀態下放入保持於 熱風乾燥機中45秒鐘，並進行熱處理。熱處理彳 基甲酸乙酯彈性纖維之強力，使用定伸長速度之彳 機，以握把長5公分、伸長速度5 00mm/分鐘予J 測定時的環境爲溫度20°C、相對濕度65%。表i 熱處理前纖維的耐熱強力保持率》 針織物之作成 根）的 絲 '對1334892 (1) Description of the Invention [Technical Field] The present invention relates to a knit fabric in which polyurethane-based elastic fibers and other fibers are used in combination, and a method for producing the same. More specifically, it is a so-called "deformation, hole shift, and edge irregularity" of a fabric produced by the woven fabric which is difficult to be repeatedly stretched during wearing. "Off-line", trapped flaws and unevenness in the tissue, that is, "leaked needles, dotted lines", "curl" in which the grey fabric is bent, and only the elastic fibers are extracted from the stitches of the cut and sewn products, and the fabric is made The stretchable portion is free of "slip-in" jersey, rib weave, double-back tissue, etc., and other weft knitted fabrics, tucked tissue, warp-knitted fabric, warp-knitted tissue, warp knitting A knitted fabric of a satin structure or the like, a knitted fabric of a woven fabric, a woven fabric, or the like, and a method for producing the same. [Prior Art] A product using an elastic fabric of a weft knitted fabric, a knitted fabric, a woven fabric or the like mixed with a polyurethane elastic fiber is widely used because of its large elongation and good restoring force and suitability in an extended state. use. However, when a product obtained by cutting and sewing a fabric of a polyurethane-based elastic fiber is repeatedly stretched, the fabric is deformed into a non-uniform "transformation" hole pitch and edge irregularity. "Line", the gray cloth, the "leakage, the dotted line" of the ladder-like scars and unevenness, and the "curl" of the bending of the grey cloth. Further, by repeating the elongation, the polyurethane elastic fibers are also drawn from the stitches in the sewn portion, so-called "slip in". Occurs this -4 - (2) (2) 1334892 The portion of the fabric that has been slid into the elastic fiber and of course has no shrinkage force, so that density spots occur on the fabric and there is a problem that it cannot be worn. These phenomena occur even in a knitted fabric of an elastic fiber other than the polyurethane elastic fiber, and are particularly remarkable in the case of a polyurethane elastic fiber having high stretchability. The countermeasures for these problems have so far been the following proposals. (1) The contraction force of the polyurethane elastic fiber is suppressed. (i) The elongation ratio of the polyurethane elastic fiber is not so high. (ii) increasing the processing temperature of the woven fabric and suppressing the shrinkage force of the polyurethane reinforced elastic fiber. (iii) Select elastic fibers with high stereotypes. (2) By increasing the setting temperature, the points of the polyurethane elastic fibers are mutually melted. (3) The use of a low melting point polyurethane elastic fiber prevents fusion at a low temperature. (4) Increasing the stitch density at the time of sewing, suppressing the sliding of the polyurethane-based elastic fiber, and making it difficult to cause slipping. (5) When used in the form of a core-spun yarn, the number of turns is increased to form a double-clad form. Further, a method of air-entanglement of a core yarn and other yarns has been proposed (refer to Japanese Laid-Open Patent Publication No. Hei 04-11036). (6) Those who have slipped in and moved in a hole and are difficult to weave are knitted (refer to Japanese Laid-Open Patent Publication No. 2002-69804 and JP-A-2002-13052). However, as in (1) (i), the polyethyl urethane elastic fibers - 5 - (5) (5) 1338892 are interdigitated with each other or at the intersection with the non-elastic yarn, preferably a high-melting polyamine. The intersection of the ethyl urethane elastic fiber and the non-elastic yarn is thermally fused to form a woven fabric of the polyurethane elastic fiber mixed with [I], which further contains 200 ° C or more. a high melting point polyethylene urethane elastic fiber having a melting point, and heat-melting the intersection of the high melting point polyurethane reinforced elastic fiber and the above high-melting urethane elastic fiber. [III] A method for producing a knitted fabric of a polyurethane-containing elastic fiber, which is characterized in that the strength retention rate after drying at 150 ° C '45 seconds in a 100% elongation state is 50%. Above, and having a high-melting polyurethane elastic fiber having a melting point of less than 1 80 ° C and at least one non-elastic yarn forming a knitted fabric, the high-melting polyamine is formed by dry heat or moist heat setting The ethyl urethane elastic fibers are at the intersection with each other or with the inelastic yarn, preferably at the intersection of the high-melting urethane elastic fibers and the non-elastic yarns. [IV] [III] A method for producing a knitted fabric of a polyurethane-based elastic fiber, which is a high-melting polyurethane elastic fiber having a melting point of 200 ° C or higher, and the high-melting point polyurethane The intersection of the elastic fiber and the above-mentioned high-melting adhesive polyurethane elastic fiber is thermally fused = [Embodiment] The best mode for carrying out the invention -8 - (6) (6) 1338892 is described in more detail below. this invention. The polyurethane elastic fiber used in the present invention may be a high-melting polyurethane elastic fiber which can be easily melted and has heat resistance at a low temperature, and its composition and manufacturing method are not It is particularly limited, for example, to react a polyol with an excess of molybdenum diisocyanate to produce a polyurethane-terminated intermediate polymer having an isocyanate group at both ends, and to have an easily reactable isocyanate group with the intermediate polymer. A method of reacting a low molecular weight diamine of an active hydrogen with a low molecular weight diol in an inert organic solvent to produce a polyurethane solution (polymer solution), removing the solvent into a sliver, and making the polyol and the dimer After the polymer reacted with the low molecular weight diamine or the low molecular weight diol is cured and dissolved in a solvent, the solvent is removed into a sliver, and the cured polymer is not dissolved in the solvent and is formed into a yarn by heating. a method of reacting the aforementioned polyol with a diisocyanate and a low molecular weight diol to obtain a polymer without curing the polymer and forming a sliver And a method of removing a solvent from a mixed polymer solution and forming a gauze by mixing the polymer or polymer solution obtained by the above various methods. The two terminal isocyanate-based prepolymers (hereinafter referred to as "two-terminal NCO-based prepolymers") obtained by reacting polyol with diisocyanate (A), and (B) A method in which a polymer obtained by reacting an alcohol with a di-isocyanate and a low molecular weight diol obtained by reacting a two-terminal hydroxyl prepolymer (hereinafter referred to as "two-terminal OH-based prepolymer") is uncured to melt-spinning 'because at a low temperature It is economical because it is easy to melt and adhere to high-melting polyurethane elastomer with heat resistance and does not contain solvent. -9- (7) (7)1334892 At this time, the polyols constituting the prepolymer of (A) and (B) may be the same or different, but a polymer having a number average molecular weight of about 800 to 3,000 is used. A diol is preferred. As the polymer diol, a polyether diol, a polyester diol, a polycarbonate diol or the like can be used. The polyacid diol may, for example, be a polyether diol obtained by ring-opening polymerization of a cyclic ether such as oxidized acetonitrile, oxidized propylene or tetrahydrofuran: ethylene glycol, propylene glycol, 1'4-butanediol, A polyether diol obtained by polycondensation of a diol such as 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol or 3-methyl-1' 5-pentanediol. The polyester diol can be exemplified by, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1' 5-pentanediol 'neopentyl glycol, 〗 6, 6-hexanediol, 3-methyl-1' a polyester diol obtained by polycondensation of at least one selected from the group consisting of diols such as pentanediol and at least one selected from the group consisting of dibasic acids such as adipic acid and sebacic acid; a polyester diol obtained by ring-opening polymerization of a lactone such as caprolactone or valerolactone. The polycarbonate diol may, for example, be a dialkyl carbonate such as dimethyl carbonate or diethyl carbonate; an alkylene carbonate such as ethyl carbonate or propyl carbonate; diphenyl carbonate or diceyl carbonate. And optionally selected at least one carbonate such as diaryl carbonate, and ethylene glycol, propylene glycol, 1,4-butanediol, 1 '5 pentane-alcohol, neopentyl alcohol, 1,6-hexanediol, 3 a carbonate diol obtained by transesterification of at least one selected aliphatic diol such as methyl-1,5-pentanediol or the like. The above-exemplified polyether diol, polyester diol, or polycarbonate di--10-(8) 1334892-valent alcohol may be used alone or in combination of two or more 'in order to obtain good viscosity, polyether diol component The polymer may be used in an amount of 5 〇 mass% or more, preferably 60% by mass or more, and the polyether 2 may be 100% by mass. Further, the polyether diol component is particularly preferably a polyether diol. Diisocyanate constituting the prepolymer of the components (A) and (B) is a diisocyanate such as an aliphatic, a fat, an aromatic or an aromatic aliphatic which is usually used in the production of polyurethane. Examples of such diisocyanates include 4,4'-diphenylcyanate, 2,4-methyl-toluene diisocyanate, 1,5-naphthalene diiso, xylene diisocyanate, hydrogenated di-tonylene diisocyanate 2 Isocyanate, 1,6-extended hexyl diisocyanate, p-diisocyanate, 4,4'-dicyclohexylmethane diisocyanate' methyl xylene diisocyanate, p-tetramethyl xylene diisocyanate, which can be used alone One or a combination of them is preferably used as 4,4·monomethane diisocyanate or 4,4· dicyclohexylmethane diisocyanate. The low molecular weight diol and the low molecular weight diamine of the chain extender are preferably as appropriate, and may provide moderate heat resistance, and a low molecular weight compound having an active hydrogen atom reactive with isocyanate and generally having a molecular weight may be used. As such a low molecular weight compound, for example, ethylene glycol, propylene di, 4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-, 3-methyl- 1,5-pentane can be used. An aliphatic diol such as an alcohol, and in a good molten diol, an butyl butyl ester can be used to form a diphenyl ester such as a cycloalkane diisocyanate or an isophorhenyl phthalate. The speed of two can be 500: alcohol '1 hexanediol does not hinder -11 - (9) 1334892 Within the range of spinning properties, trifunctional glycols such as glycerin may be used alone or in combination of two or more, but For workability and for providing moderate physical properties, such as ethylene glycol, 1,4-butane and 'such low molecular weight diamines can be used, for example, ethylenediamine, propylenediamine, hexamethylenediamine, xylenediamine, 4,4-diaminoalkane' 肼 and the like. It is also possible to use low molecular weight diols and low molecular weight diamines as a chain extender for better use of low molecular weight diols. Further, a functional monoamine such as a monool or a dibutylamine such as butanol may be used in combination as a reaction regulator or a polymerization poly(ethyl urethane), or may be used as a spinning property. The solvent may, for example, be a polar solvent such as N,N-dimethylformamide, N,N-decylamine, hydrazine, hydrazine, hydrazine, hydrazine-tetramethylurea or N-methylpyrrolemethyl phenyl. The prepolymer of the above components (A) and (B) may be added to any of the components such as ultraviolet antioxidants and photosetters for weather resistance, thermal oxidation resistance, and yellowing resistance. The ultraviolet absorber may, for example, be 2-(3,5-di- 2-hydroxyphenyl)benzotriazole, 2-(3_t-butyl-5/2-hydroxyphenyl)-5-chlorobenzene. The benzotriazole-based ultraviolet absorber antioxidant such as triazole or 2-(2-hydroxybiphenyl)benzotriazole may, for example, be 3,9-bis(2-(3-butyl-4-hydroxy) _5-methylphenyl)propenyloxy)-1. These available fiber alcohols are preferred. Butane diamine, diphenyl group The dimethyl ketone of the diethylamine and degree adjusting agent yarn solution of the invention, the second improvement of the absorption resistance, the third amyl group - methyl -3,5 - fluorene ( 3 _Third 1 -Dimethyl-12- (12) (12)1334892 The bulk reaction can be obtained. The obtained two terminal 〇H-based prepolymer can be used with a gear pump with a casing (for example, KAP-1 Kawasaki) Reactors of Heavy Industries, Ltd.) Injecting a polyurethane elastomer fiber into a reactor. Further, when the two prepolymers are synthesized, various chemicals mentioned above for improving weather resistance, heat oxidation resistance, yellowing resistance, and the like may be added. (III) The synthesis of the spinning polymer can be carried out by feeding a prepolymer of (A) and (B) at a certain ratio, and a continuous reaction can be obtained. In this case, the reactor is usually a polyamine group. The melt spinning method of the ethyl formate elastic fiber can be used as a reaction machine having a mechanism for stirring and reacting the spinning polymer in a heated state or in a molten state, and then transferring it to the spinning head. The condition is 1 to 90 minutes at 160 to 220 ° C, preferably 3 to 80 minutes at 180 to 120 ° C. The polyurethane elastic fiber of the present invention is obtained by transferring the synthesized spinning fiber to the spinning head without being solidified, and discharging it by the nozzle and spinning, but the spinning polymer reacts. The average residence time in the machine varies depending on the type of the reactor, and is calculated according to the following formula: Average residence time in the reactor = (reactor volume / amount of polymer discharge for spinning) X proportion of polymer for spinning In general, the case of using a cylindrical reactor is about hr, and the case of using a twin-screw extruder is 5 to 10 minutes. The spinning temperature is 180 to 2 30 ton, after continuous extrusion from the nozzle, Cooling, and attaching the spinning oil and winding it can be obtained. Here, the ratio of the two terminal NCO-based prepolymer to the two-terminal 〇H-based prepolymer is such that the NC enthalpy in the yarn after the immediate spinning is 0.3M mass% ' -15- (13) (13) 1338892 Preferably, the rotation ratio of the gear pump is appropriately adjusted as 0 to 35 to 0.85 mass% residual. If the NC 0 group contains excess 〇 3% by mass or more, The chain extension reaction after spinning increases the physical properties such as strength and heat resistance. When the NC 0 group is less than 0.3% by mass, the heat-resistant strength retention rate of the obtained polyurethane-based elastic fiber is lowered, and if it exceeds 1% by mass, the viscosity of the spinning polymer becomes low. In the case where the spinning is difficult, the NC thiol content in the spun fiber is measured as follows. The spun fiber (about 1 g) is dissolved in dibutylamine/dimethylformamide/toluene solution. Thereafter, the excess dibutylamine is reacted with the NCO group in the sample, and the residual dibutylamine is titrated with hydrochloric acid, and the content of the NCO group is calculated. The polyurethane-based elastic fiber used in the present invention is as described above. The raw material is a polyether diol, and the polyurethane elastic fiber produced by the melt reaction spinning method is particularly preferable. The polyurethane-based elastic fiber used in the present invention has a strength retention ratio of 50% or more, preferably 55% or more after dry heat treatment at 150 ° C for 45 seconds in an elongation state of 100%. If the strength retention ratio is less than 50%, the stretchability of the product after heat setting is lowered, which is not preferable. Further, the upper limit of the strong retention ratio is not particularly limited, and is usually 90% or less, particularly 80% or less. Further, the polyethylene urethane elastic fiber has a melting point of 180 ° C or less, preferably 175 t or less. If it is higher than 180 °C, the heat treatment temperature for fusion bonding is too high, and it is adversely affected by the touch and dyeing fastness of the product, which is not preferable. Also, the lower limit of the melting point is! Above 50 °C 'especially 155t or more -16- (14) (14)1334892 'Because of the dimensional stability when mixed with high-melting polyurethane elastomeric fibers, and the elongation recovery of the grey fabric good. In addition, the measuring method of the strong retention rate is as follows. The woven fabric of the polyurethane reinforced elastic fiber of the present invention is a high-melting urethane elastic fiber and a non-elastic yarn, and can also be mixed, for example, having a melting point of 200 ° C or higher. The high melting point polyurethane polyurethane elastic fiber was formed to have the following constitution. (1) A composite yarn comprising a high-melt polyurethane elastic fiber and at least one non-elastic yarn is used for a warp and/or weft fabric. The tissue may be any of plain weave, woven weave, rib weave, and the weaving machine may also use a shuttle loom, a rapier loom, a jet loom, or the like. Further, the warp yarn and the weft yarn may all be the composite yarn, and the composite yarn and the non-elastic yarn may be mixed at a sewing ratio of 1:1, 1:2 or 1:3. (2) A high-melt polyurethane elastic fiber and a weft knitted fabric of at least one type of non-elastic yarn are mixed in the same course of the knitting machine. The weaving of high-melt urethane elastic fibers and non-elastic yarns into weft knitted fabrics, such as flat knitting, ribbing, double-backed tissue, two-sided knitting, and combinations thereof, and their changing tissues, etc. A tissue can be compiled. As the knitting machine, all knitting machines such as a circular knitting machine, a cross knitting machine, a full-form flat knitting machine, and a sock knitting machine can be used. High-melting polycarbonate elastic fibers can be inserted or woven. Further, it may be a yarn-bonding structure of a high-melt adhesive polyurethane elastic fiber and a non-elastic yarn, and a composite yarn of a high-melt adhesive polyurethane and a non-elastic yarn may also be used. Similarly, in the same manner as (1), weaving the fused-melt urethane elastic fiber in the full-line 圏 course, -17- (15) (15) 1338892 and may be separated by more than one course. Weaving it. The high-melt polyurethane elastic fibers may be interwoven with the non-elastic yarns or woven at appropriate intervals. Further, it is also possible to mix a high-melting point polyurethane elastic fiber. Examples thereof are shown below, but are not limited thereto. (2) - 1 Example of full coil course: 1st high-viscosity yarn and non-elastic yarn, or composite yarn 2nd high-melt yarn and non-elastic yarn, or composite yarn 3rd high-melt yarn and Examples of non-elastic yarns, or composite yarns, 4th high-melt yarns and non-elastic yarns, or composite yarns (2)-2, separated by 1 course: 1st high-melt yarn and non-elastic yarn, or Composite yarn 2nd non-elastic yarn 3rd high-melt yarn and non-elastic yarn, or composite yarn 4th non-elastic yarn (2) - 3 High-melt yarn and high-melting yarn are separated by 1 course Examples of use: 1st high-melt yarn and non-elastic yarn, or composite yarn 2nd high-melt yarn and non-elastic yarn, or composite yarn 3rd high-melt yarn and non-elastic yarn, or composite yarn 4 high-melting yarns and non-elastic yarns, or composite yarns (2)-4 Examples of interactions 1st commercial melt-bonded yarn 2nd non-elastic yarn, or high-melt yarn and non-elastic yarn -18- (16) (16)1334892 The third high-melt yarn, the fourth non-elastic yarn, or the high-melt yarn and the non-elastic yarn (3) mixed with high-melting polyurethane elastic fiber and at least one The non-elastic yarns warp knitted fabric. The knitted fabric of the high-melt urethane elastic fiber and the non-elastic yarn is knitted into a chain knitting, a warp-knitted fabric, a warp-knitted structure, a warp-knitted satin weave, and combinations thereof, and Any kind of tissue, such as a changed organization, can be compiled. As for the knitting machine, all knitting machines such as a tricot warp knitting machine, a raschel warp knitting machine, and a Milanese warp knitting machine can be used. In the same manner as in (1), the high-melting polyurethane-based elastic fibers may be woven in a comprehensive manner, and may be woven at appropriate intervals. Further, the high-melt adhesive polyurethane elastic fiber may be either inserted or woven. Further, a high melting point polyurethane elastic fiber may be mixed. The examples are shown below, but are not limited thereto. (3) - 1 Knitted fabric of chain structure Fig. 1 and Fig. 2 show a chain structure which is often used for a lace cloth or the like. This chain structure tends to have the disadvantages of missing needles, loosening, etc. after the gap is sewn. Although the countermeasures have been proposed to prevent the needle from leaking, the traces of the leak-proof tissue are left dirty on the fabric, and there is a problem that hinders the sense of quality. Therefore, in Fig. 1 and Fig. 2, if a is a non-elastic yarn, b is a high-melting polyurethane elastic fiber of the present invention, or a high-melting polyurethane and a high melting point polyamine. The ethyl urethane elastic fiber is woven and heat-set, and it is in the X part shown in Fig. 1 'high-melting urethane elastic fiber and non-elastic-19-(17) (17)1334892 Yarn, and high-melt urethane elastic fiber are in contact with high-soluble @ s ethyl formate elastic fiber, which is hot-melt, obtains elongation, and prevents the defects such as missing needles and loosening, and aesthetics There are no damaged knitted fabrics. (3)-2 The tissue generally used other than the chain structure other than the chain structure, if the high-melt polyurethane reinforced elastic fiber of the present invention is inserted or woven, it can also be used. The fusion of the inelastic yarn and the polyurethane elastic fiber are fused to each other, and it is difficult to cause edge irregularities (unevenness, extraction, and flying out of the elastic fiber), etc., which can substantially improve the durability of the fabric. Sex. Moreover, the fabric can be made more stable, it is difficult to cause curling, and the cost at the time of sewing can be observed. For example, in the organization diagrams shown in Figs. 3 to 8, by appropriately using the high-melting polyurethane elastic fiber, it is possible to obtain a hole-to-edge misalignment, an off-line, a missing needle, and a dotted line. , curled and slipped into the knit. In Fig. 3, L1 and L2 are full-insertion (All-in), and L1 and L2, L3 and L4 in Fig. 4 are inserted one by one (1 in-1 out), and LI1 and L2 in Figs. 5-8. L3 is a full-in (All-in). Further, a of FIGS. 3 to 8 is a non-elastic yarn, and b is a high-melting polyurethane elastic fiber of the present invention, which is used alone or in combination with a high-melting polyurethane elastic fiber, and FIG. 5 and 6C is a high-melting polyurethane elastic fiber using the two fundamental inventions, or a high-melting polyurethane elastic fiber of the present invention and a high-melting polyurethane elastic fiber. root. In addition, -20-(18) (18)1334892 is used as it is in the seamless cutting port, and it is conventionally used for durability such as off-line due to scratches during washing and wearing. The problem, but it can be greatly improved. Here, the non-elastic yarn mixed with the high-melt adhesive polyurethane elastic fiber is not particularly limited, and for example, natural fibers such as kapok, hemp, wool, and enamel, rayon, cuprammonium, and bolinose can be used. Recycled fibers such as Polynosic, semi-recycled fibers such as acetate, chemically synthesized fibers such as nylon, polyester, and acrylic, and the blending ratio of polyurethane-based elastic fibers is about 1 to 40%. It is better. Further, in the woven fabric of the polyurethane urethane elastic fiber of the present invention, the dry spinning method in which the diamine is mixed and the chain length reaction is carried out has excellent heat resistance and elastic recovery property of 200 ° C. In the above, a high-melting point polyurethane elastic fiber having a melting point of preferably more than 20 ° C can obtain a knitted fabric having good elastic properties while maintaining the meltability. At this time, the use amount of the high-melt adhesive polyurethane fiber is preferably from 2 to 40%. Here, the dry heat setting method can be carried out by using a setting machine such as a pin tenter and heat-fixing it by hot air. At this time, the setting temperature is 14 0 to 200 ° C ', particularly 170 to 190 t:, and the setting time is 10 seconds to 3 minutes, particularly 30 seconds to 2 minutes. On the other hand, the wet heat setting method can be carried out by heat-fixing the knitted fabric in a state where it is placed in a mold and saturated steam of a predetermined pressure. At this time, the setting temperature is 100 to 130 ° C, particularly 105 to 125 ° C, and the setting time is 2 to 60 seconds, particularly 5 to 30 seconds. According to the present invention, it can be processed at a low setting temperature, and it is difficult to obtain a mixture of polyamidoformate B - (19) 1334892 with a hole shift, edge irregularity, off-line, missing needle, curl, and distance phenomenon. Weaving of Ester Elastic Fibers Hereinafter, examples and comparative examples are shown, and the present invention is not limited to the following examples. Also, in the following examples, parts by mass. [Example 1] The following two terminal NCO-based prepolymers and two final polymers were synthesized, and the synthesis of the two terminal oxime-based prepolymers for the synthesis of polyurethane reinforced elastic fibers was used as the diisocyanate 4 , 4·-diphenylmethane (hereinafter referred to as MDI) 25 parts charged with nitrogen sealed attached; casing reaction pot, and will be used as polymer diol number: 2,000 polybutylene ether binary The alcohol (hereinafter referred to as PTMG) is injected while stirring. After reacting for 1 hour, 27.6 parts of low-component 1 '4-butanediol was injected, and the synthesis of the two terminal thiol-terminated NCO-based prepolymers was carried out in a nitrogen-sealed 80t: reaction vessel. 47.4 parts of the MDI of the ester, and added UV absorber (2 - a third amyl-2-hydroxyphenyl) benzotriazole: 20%) (3,9 - bis (2- (3 - (3 - Third butyl-4-pyridylphenyl)propenyloxy)-1,1-dimethylol)-sliding and pore-shifting. Invention, but in the present, the parts are all terminal OH-based pre-feedstocks. Diisocyanate penetrates 80 ° C warm water P average molecular weight 100 parts of one side diol prepolymer. It is diisocyanate (3,5 - two, antioxidant i base a 5- 2,4,4,8 , -22- (20) (20)1334892 10 — Four snails (5,5) ~\--alkane: 50%), light stabilizer (double (2,2,6,6_tetramethyl-4) A mixture of a sebacate: 30%), 2.2 parts, and 100 parts of PTMG as a polymer diol having an average molecular weight of 2,000, and stirring was continued for 1 hour to obtain a two-terminal NCO-based pretreatment. Two-terminal NCO-based prepolymerization obtained from the polymer And a two-terminal 〇H-based prepolymer was continuously supplied to a cylindrical reactor having a capacity of 2,200 ml of a polyurethane elastomer having a stirring wing at a mass ratio of 1:0.475. The supply speed was two. The terminal NCO-based prepolymer 2 was 8.9 3 g/min, and the two terminal OH-based prepolymer was 13.74 g/min. The average residence time in the reactor was about 1 hour, and the reaction temperature was about 19 0 ° C. The polymer was uncured and introduced into two 8-nozzle spinning heads maintained at a temperature of 192 ° C. The spinning polymer was metered by a gear pump provided in the head, pressurized, and filtered by filter paper, by diameter The nozzle of 0.6 mm and 1 hole was spouted at a speed of 2.67 g/min in a spinning cylinder of 6 m length (total discharge by nozzle: 42.67 g/min), while the side of the oil agent was given 600 m/ At a speed of minute, the polyethylene terephthalate elastic fiber of 44 dtex was obtained. The NCO group content of the polyurethane elastic fiber immediately after the spout was 〇·42% by mass. The physical properties of the ester elastic fiber were determined by the following method. The result melting point was 168 t The heat-resistant strength retention rate was 65%. Further, a knitted fabric was produced by the following method using the elastic fiber, and the untwisting tension of the knitted fabric after heat setting was measured. The results are shown in Table 1. -23- (21) 1334892 $ point Measuring method Measuring device: TMA (thermal machine measuring device) Using quartz probe grip length: 20 mm Elongation: Ο . 5 % Temperature range: room temperature ~ 2 5 0 °C Heating rate: 20 ° C / min Evaluation : The temperature at which the thermal stress is Omgf is defined as the method for determining the heat retention rate of the melting point of the melting point. The length of the polyamine at a temperature of 150 ° C is measured by a tensile test. : The elongation was maintained to 20 cm with respect to the grip of the polyurethane elastic fiber at 1 〇. It was placed in a hot air dryer for 45 seconds in an extended state, and heat-treated. The heat of the thioformate elastic fiber was heat-treated, and the temperature was 20 ° C and the relative humidity was 65% in the case where the length of the grip was 5 cm and the elongation rate was 5000 mm/min. Table i Heat-resistance retention rate of fiber before heat treatment" Silk of the knitted fabric"
對連褲襪針織機（Ronaty公司製，針數400 給紗口 2、4 口分別給紗6-尼龍長絲1 3分特7 I 1、3 口給紗聚胺基甲酸乙酯彈性纖維並且進行交I 熱定型 -24 - (24)1334892 表1 來自針織物的解編張力（cN) 解舒纖維 尼龍系 聚胺基甲酸乙酯彈性纖維 定型溫度 1 60°C 1 8 0°c 1 60°C 1 80°C 實施例1 1.0 6.3 1.5 3.2 寳施例2 0.5 1.1 0.5 1.1 比較例1 0.1 0.5 0.0 0.4 比較例2 1.1 因爲針織物內之 聚胺基甲酸乙酯 彈性纖維斷紗故 不能測定 1.6 因爲針織物內之 聚胺基甲酸乙酯 彈性纖維斷紗故 不能測定 實施例1、2因爲熔黏而令解編張力高，且於實施例 1之使用聚醚二醇的聚胺基甲酸乙酯彈性纖維之情況特別 爲解編張力高。又，實施例1、2均即使於180 °C熱定型 亦不會令針織物中的彈性纖維斷紗。比較例1之與高熔點 聚胺基甲酸乙酯彈性纖維之組合下雖難發生熔黏，且比較 例2爲以1 6 0 °C熱定型使得解編張力高’但經由1 8 0 °C熱 定型令針織物中之聚胺基甲酸乙酯發生斷紗。 〔實施例3〕 使用實施例1所得之聚胺基甲酸乙酯彈性纖維，且以 下述方法所作成之針織物予以熱定型後’進行洗滌試驗， 且目視觀察針織物的脫線、滑入、針織物面。結果示於表 -27- (25) (25)1334892 針織物之作成 對連褲襪針織機（Ron at y公司製、針數400根）的 給紗口 1，3 口給紗6 -尼龍假捻加工紗z捻3 3分特1〇 長紗、對2 ’ 4 口給紗6 —尼龍假捻加工紗s捻3 3分特1 〇 長紗’並再對全部4 口給紗聚胺基甲酸乙酯彈性纖維，並 以添紗編織作成針織物。織入倍率爲設定在2 · 5倍。 熱定型 將作成的針織物於保持在180 °C之乾燥機中乾熱處理 1分鐘。 洗滌試驗 由定型後之針織物作成15x20公分的切片試料’並使 用Suga試驗機（股）LM - 160洗滌試驗機重複進行20回 洗滌。 液量：1 50毫升 使用1 0個鋼球 溫度：5〇r 時間：1循環3 〇分鐘 評價方法 脫線：觀察於針織物之線圈橫列方向平行切割之針織 -28- (26) (26)1334892 物邊緣。 滑入：觀察於針織物浮線方向上切割之針織物邊緣， 並以彈性纖維爲由針織物端滑入5 mm以上的根數比率（％ )予以評價。 孔移距：觀察針織物之平滑程度。 捲曲：觀察針織物邊緣。 〔實施例4〕 使用實施例3同樣的針織物，並對1、3 口給紗實施 例1之聚胺基甲酸乙酯彈性纖維，對2、4 口給紗比較例 1之彈性纖維，且同實施例3作成針織物，並進行與實施 例3同樣之試驗。結果示於表2。 〔比較例3〕 僅使用比較例1之彈性纖維，且同實施例3作成針織 物，並進行同樣之試驗。結果示於表2。 〔比較例4〕 僅使用比較例2之彈性纖維，且同實施例3作成針織 物，並進行同樣之試驗。結果示於表2。 -29- (27) (27)1334892 表2 針織物觀察結果 脫線 滑入（％) 孔移距 捲曲 實 施 例 3 Μ V «'、 0 平滑 te 實 施 例 4 Μ /»w 5 平滑 Λτττ jjLU. / (w 比 較 例 3 有脫線 55 有凹凸 有弱捲曲 比 較 例 4 Μ /ι\\ 0 有凹凸 Μ 〆《、、 比較例4爲於針織物中發生聚胺基甲酸乙酯彈性纖維 斷紗。 〔實施例5〕 以實施例1相同方法取得1 5 6分特的聚胺基甲酸乙酯 彈性纖維。同實施例1測定物性之結果，此聚胺基甲酸乙 酯彈性纖維之熔點爲1 7 0 °C、耐熱強力保持率爲6 8 %。更 且’使用此彈性纖維且以下述方法作成經針織物，並測定 由熱定型後之針織物抽出聚胺基甲酸乙酯彈性纖維的阻力 値。結果示於表3。 針織物之作成 使用拉舍爾經編機（Carl Myer公司製，28針），並 對圖9之L1的a及L3的c使用6 —尼龍長紗56分特17 長紗’且於L2的b使用聚胺基甲酸乙酯彈性纖維，作成 經針織物。 -30- (28) (28)1334892 熱定型 將上述針織物於保持在190 °C之乾燥機中乾熱處理1 分鐘。 牽伸阻力値的測定 由上述針織物’採取如圖10所示之緯方向（寬） 25mmx經方向（長度）100mm的試驗片。此時，令聚胺基 甲酸乙酯彈性纖維之牽伸方向爲開始針織方向及針織終了 方向般，各採取5枚合計10枚的試驗片。 接著，如圖10作成試驗片。由該試驗片下端（D- D’ )於40mm之位置（B — B·)，將經方向插入之聚胺基甲 酸乙酯彈性纖維1以殘留1根之狀態切取試驗片。其次， 將殘留該聚胺基甲酸乙酯彈性纖維由朝向上方揪起二方向 上取出5mm部分（E— F)試驗片。更且，於該聚胺基甲 酸乙酯彈性纖維之延長線上，且由試驗片上端30mm之位 置，於寬度方向上加以寬3mm的切口 3。 以拉伸試驗機測定牽伸阻力値時，將拉伸試驗機的揪 起間隔調整至40mm，其次，以25mm (由A— A·上方）將 試驗片上方握住代替該試驗片之二個上方揪起，並對該聚 胺基甲酸乙酯彈性纖維加以0.1 cN初荷重，且以35mm ( 由C-C·下方）將握住該聚胺基甲酸乙酯彈性纖維代替4 下方之揪起，且以拉伸速度100mm/min拉伸，並且測定 直到該聚胺基甲酸乙酯彈性纖維被牽伸爲止的最大牽伸荷 -31 - (29) (29)1334892 重。其對開始針織及完全針織方向均各實施5回合計10 回，並計算其平均値且求出牽伸阻力値。 〔比較例5〕 除了使用PTMG做爲聚合物二醇，使用二胺做爲鏈延 長劑之156分特的聚胺基甲酸乙酯彈性纖維（Mobilon P 型日淸紡績（股）製，熔點2 1 7 °C、耐熱強力保持率 93% )於圖9之L2之b中做爲插入紗以外，同實施例5 作成經針織物。熱定型後，同實施例5測定L2之b紗的 牽伸阻力値。結果示於表3。 〔實施例6〕 使用與實施例5同樣的針織機，並於圖3之L1之a 使用6-尼龍長紗56分特17長紗，於L2之b使用實施 例5之聚胺基甲酸乙酯彈性纖維並作成經針織物，且進行 與實施例5同樣之試驗。結果示於表3。 〔比較例6〕 除了於圖3之L2之b使用與比較例5同樣之彈性纖 維以外，同實施例6作成針織物，並進行同樣之試驗。結 果示於表3。 〔實施例7〕 使用與實施例5同樣的針織機，並於圖4之L1及L2 -32- (30) 1334892 之a使用6—尼龍長紗56分特17長紗，於L3及L4之b 使用實施例5之聚胺基甲酸乙酯彈性纖維並作成經針織物 ，且進行與實施例5同樣之試驗。結果示於表3。 〔比較例7〕 除了於圖4之L3及L4之b使用比較例5之彈性纖 維以外，同實施例7作成針織物，並進行同樣之試驗。結 果示於表3。 表3 牽伸阻力値測定結果 牽伸阻力値（cN ) 實施例5 5 6.8 比較例5 20.5 實施例6 不能牽伸 比較例6 29.8 實施例7 52.5 比較例7 17.8 實施例5 ' 7因熔黏而令牽伸阻力値變高，實施例6 爲以未牽伸程度中熔黏，取得難發生孔移距、邊緣不齊的 坯布。比較例5、6 ' 7之與高熔點聚胺基甲酸乙酯彈性纖 維之組合下難發生熔黏’且牽伸阻力値亦低，並發生孔移 距、邊緣不齊。 -33- (31) (31)1334892 〔實施例8〕 以下述方法作成針織物、熱定型後，測定針織物之解 編張力和確認聚胺基甲酸乙酯彈性纖維彼此間之熔黏狀況 、及以目視評價洗滌試驗所造成的針織物損傷（洗滌耐久 性）。結果不於表4。 針織物之作成 使用拉舍爾針織機（Carl Myer公司製，28針），作 成圖5所示之組織圖的針織物。於圖5中，於L1之a使 用6 -尼龍長紗5 6分特1 7長紗 '於L2之c使用與比較 例5相同的彈性纖維，於L3之c使用實施例1之聚胺基 甲酸乙酯彈性纖維並編成經針織物做爲主針織物°更且， 於主針織物之間使用尼龍長紗1 1 〇分特24長紗做爲分離 橫列線並作成經針織物。 熱定型 將上述針織物於保持在190 °C之乾燥機乾熱處理1小 時。 解編張力之測定 測定分離橫列線之尼龍紗的解編張力。解編速度爲 10 0mm/分鐘，並測定1分鐘的解編張力，計算最高點5 處的平均値。 -34- (32) (32)1334892 熔黏狀況之確認 將主針織物之尼龍紗溶解於20%稀鹽酸，並觀察聚胺 基甲酸乙酯彈性纖維彼此間之接觸部的熔融狀況。 針織物損傷評價中的試料作成 對於熱定型之針織物編織方向切出縱3.3公分、橫2 4.0公分的短長方狀試料，且由橫方向之裁斷面對編織方 向以40度之角度加入切口，分成「開始編織側」和「完 成編織側」，且合倂縱方向的裁斷部並以超三角度機予以 縫製作成環狀試料。 針織物損傷評價中的試料洗滌 將作成之試料於下述條件中連續進行300分鐘之洗滌 〇 洗滌機：家庭用二槽式洗滌機 洗劑量：調整至1·3克/公升（使用弱鹼洗劑） 水量：3 0公升 負荷布：綿、混用聚胺基甲酸乙酯彈性纖維拜氏原棉 布針織物，1. 〇公斤。 針織物之損傷評價 觀察「開始編織側」' 「完成編織側」之裁斷部的損 傷程度，並以下述四階段評價。 -35- (33) 1334892 ◎:未察見損傷 〇：稍微察見損傷 △:察見損傷 X :損傷激烈 其中，△和X爲猶豫做爲衣料穿用程度的損傷，◎和 〇爲洗滌耐久性方面佳。For pantyhose knitting machine (Ronaty company, needle number 400, yarn feeder 2, 4 mouth respectively, yarn 6-nylon filament, 1 3 dtex, 7 I 1, 3, yarn, polyurethane elastic fiber and Carrying out I heat setting -24 - (24)1334892 Table 1 De-knit tension from knitted fabrics (cN) Unlocking fiber nylon-based polyurethane elastic fiber setting temperature 1 60 ° C 1 8 0 ° c 1 60 °C 1 80 °C Example 1 1.0 6.3 1.5 3.2 Baoji Example 2 0.5 1.1 0.5 1.1 Comparative Example 1 0.1 0.5 0.0 0.4 Comparative Example 2 1.1 Cannot be determined because the polyurethane-based elastic fiber in the knitted fabric is broken. 1.6 Since the polyurethane-based elastic fibers in the knitted fabric were broken, it was not possible to determine the polyamidocarboxylic acid of the polyether diol which was used in Example 1 because of the melt-adhesion and the high debonding tension. In the case of the ethyl ester elastic fiber, the debonding tension is particularly high. Further, in Examples 1 and 2, even if heat setting at 180 ° C, the elastic fibers in the knitted fabric are not broken. Comparative Example 1 and high melting point polyamine Although it is difficult to melt and bond under the combination of ethyl urethane elastic fibers, and Comparative Example 2 is heat setting at 160 ° C The unzipped tension was high, but the polyurethane was broken by heat setting at 180 ° C. [Example 3] Using the polyurethane elastic fiber obtained in Example 1, The knitted fabric obtained by the following method was heat-set and then subjected to a washing test, and the knitted fabric was visually observed for the off-line, slip-in, and knitted fabric surface. The results are shown in Table -27-(25) (25)1334892 Knitted fabric Paired pantyhose knitting machine (Ron at y company, 400 needles) yarn feeder 1, 3 mouth yarn 6 - nylon false twist processing yarn z捻 3 3 points special 1 long yarn, pair 2 '4 mouth yarn 6 - nylon false twist processing yarn s 捻 3 3 points special 1 〇 long yarn 'and then all the four yarns of polyurethane elastic fiber, and weaved into a knitted fabric. The magnification was set at 2 · 5 times. The heat-formed knitted fabric was dry-treated for 1 minute in a dryer maintained at 180 ° C. The washing test was carried out by setting the knitted fabric of 15×20 cm into a sample of the finished fabric and using Suga. The test machine (unit) LM-160 washing test machine repeats 20 washes. Liquid volume: 1 50 ml makes Use 10 steel balls Temperature: 5〇r Time: 1 cycle 3 〇 minutes Evaluation method Off-line: Observe the knitting of the knitted fabric in the direction of the course of the knitting -28- (26) (26)1334892 Edge. In: The edge of the knitted fabric cut in the direction of the float of the knitted fabric was observed, and the elastic fiber was used as the ratio (%) of the number of roots of the knitted fabric to slide 5 mm or more. Hole shift: Observe the smoothness of the knitted fabric. Curl: Observe the edge of the knit. [Example 4] Using the same knitted fabric of Example 3, the elastic polyurethane fibers of Example 1 were applied to the yarns of Examples 1 and 3, and the elastic fibers of Comparative Example 1 were applied to the yarns of 2 and 4, and A knitted fabric was produced in the same manner as in Example 3, and the same test as in Example 3 was carried out. The results are shown in Table 2. [Comparative Example 3] Only the elastic fiber of Comparative Example 1 was used, and a knitted fabric was produced in the same manner as in Example 3, and the same test was carried out. The results are shown in Table 2. [Comparative Example 4] Only the elastic fiber of Comparative Example 2 was used, and a knitted fabric was produced in the same manner as in Example 3, and the same test was carried out. The results are shown in Table 2. -29- (27) (27)1334892 Table 2 Knitted fabric observation results off-line slip-in (%) Hole shifting curl Example 3 Μ V «', 0 smoothing te Example 4 Μ /»w 5 Smooth Λτττ jjLU. / (w Comparative Example 3 has off-line 55. There are irregularities and weak curls. Comparative Example 4 Μ /ι\\ 0 has embossing Μ ",, and Comparative Example 4 is the occurrence of breakage of polyurethane soft fiber in knitted fabric. [Example 5] A polyurethane elastic fiber of 156 dtex was obtained in the same manner as in Example 1. As a result of measuring the physical properties of Example 1, the melting point of the polyurethane elastic fiber was 1 70 ° C, heat-resistant strength retention rate of 68%. Moreover, 'the elastic fiber was used and the knitted fabric was produced in the following manner, and the resistance of the polyurethane elastic fiber extracted from the heat-set knitted fabric was measured.结果. The results are shown in Table 3. The knitted fabric was made using a raschel warp knitting machine (28 needles manufactured by Carl Myer Co., Ltd.), and a 6-nylon long yarn 56 dtex was used for the a and L3 c of the L1 of Fig. 9. 17 long yarn 'and b is used in the b of L2 to make a knit fabric. -30 - (28) (28)1334892 Heat setting The above-mentioned knitted fabric was dry-treated for 1 minute in a dryer maintained at 190 ° C. The measurement of the draft resistance 値 was taken from the above-mentioned knitted fabric 'taken in the weft direction as shown in Fig. 10 ( The test piece of the direction of the direction of the direction of the knitting direction and the end of the knitting was carried out in the direction of the beginning of the knitting direction and the end of the knitting, and five test pieces of a total of ten pieces were taken. Next, a test piece was prepared as shown in Fig. 10. From the lower end (D-D') of the test piece at a position of 40 mm (B - B ·), the directionally inserted polyurethane elastic fiber 1 was left as one. The test piece was cut out in the state. Next, the residual polyurethane elastic fiber was taken out from the upward direction and the 5 mm portion (E-F) test piece was taken out. Further, the polyurethane elastic fiber was used. On the extension line, a slit 3 having a width of 3 mm was placed in the width direction from a position of 30 mm at the upper end of the test piece. When the draft resistance was measured by a tensile tester, the stretching interval of the tensile tester was adjusted to 40 mm, followed by To 25mm (by A-A·above) Hold the top of the test piece instead of the test piece, and apply a 0.1 cN initial load to the polyurethane elastic fiber, and hold the polyaminocarboxylic acid at 35 mm (from CC·below). The ethyl ester elastic fiber was replaced by the lower layer 4 and stretched at a stretching speed of 100 mm/min, and the maximum draft load until the stretch of the polyurethane elastic fiber was measured - 31 - (29) ( 29) 1338892 Heavy. For each of the starting knitting and the full knitting direction, five rounds were performed for five times, and the average enthalpy was calculated and the drafting resistance 値 was determined. [Comparative Example 5] In addition to the use of PTMG as a polymer diol, a 156 dtex polyurethane elastic fiber using a diamine as a chain extender (Mobilon P type Nippon Textile Co., Ltd., melting point 2) 1 7 ° C, heat-resistant strength retention rate 93%) A knitted fabric was produced in the same manner as in Example 5 except that it was inserted as an insert yarn in L2 of Fig. 9 . After heat setting, the draft resistance 値 of the yarn of L2 was measured in the same manner as in Example 5. The results are shown in Table 3. [Example 6] The same knitting machine as in Example 5 was used, and 6-nylon long yarn 56 dtex 17 long yarn was used in the L1 a of Fig. 3, and the polyaminocarbamic acid B of Example 5 was used in the L2 b. The ester elastic fiber was molded into a knitted fabric, and the same test as in Example 5 was carried out. The results are shown in Table 3. [Comparative Example 6] A knitted fabric was produced in the same manner as in Example 6 except that the elastic fiber similar to that of Comparative Example 5 was used in the case of L2 in Fig. 3, and the same test was carried out. The results are shown in Table 3. [Example 7] The same knitting machine as in Example 5 was used, and a 6-nylon long yarn 56 dtex 17 long yarn was used in the L1 and L2 - 32- (30) 1334892 of Fig. 4, and the L3 and L4 were used. b The polyurethane elastic fiber of Example 5 was used and a knitted fabric was produced, and the same test as in Example 5 was carried out. The results are shown in Table 3. [Comparative Example 7] A knitted fabric was produced in the same manner as in Example 7 except that the elastic fibers of Comparative Example 5 were used in the cases of L3 and L4 of Fig. 4, and the same test was carried out. The results are shown in Table 3. Table 3 Drafting resistance 値 Measurement result Drafting resistance 値 (cN) Example 5 5 6.8 Comparative Example 5 20.5 Example 6 Unable to draw Comparative Example 6 29.8 Example 7 52.5 Comparative Example 7 17.8 Example 5 '7 Due to fusion bonding On the other hand, in the case of the drafting resistance, the drafting resistance was increased, and in Example 6, it was melted at the undrawn degree, and a gray cloth in which the hole shifting distance and the edge were difficult to occur was obtained. In the combination of Comparative Example 5, 6'7 and the high-melting point polyurethane elastic fiber, the melt-adhesion was hard to occur, and the drafting resistance was also low, and the hole shift and edge irregularity occurred. -33- (31) (31) 1338892 [Example 8] After the knitted fabric was formed and heat-set, the untwisting tension of the knitted fabric was measured, and the state of fusion of the polyurethane fibers was confirmed. And the knitted fabric damage (washing durability) caused by the washing test was visually evaluated. The results are not shown in Table 4. Knitting fabric production A knit fabric having a texture shown in Fig. 5 was produced using a Raschel knitting machine (28 needles manufactured by Carl Myer Co., Ltd.). In Fig. 5, the same elastic fiber as in Comparative Example 5 was used for the L1 a 6 6-nylon long yarn 5 6 dtex 1 7 long yarn ', and the polyamino group of Example 1 was used for the L3 c. The ethyl formate elastic fiber is knitted into a knitted fabric as a main knitted fabric. Further, a nylon long yarn of 1 1 〇 特 24 long yarn is used as a separate row line between the main knitted fabrics and made into a knitted fabric. Heat setting The above knitted fabric was heat-treated in a dryer maintained at 190 ° C for 1 hour. Detachment Tension Measurement The de-knit tension of the nylon yarn separating the course lines was measured. The de-scission speed was 10 0 mm/min, and the untwisting tension of 1 minute was measured, and the average 値 at the highest point of 5 was calculated. -32- (32) (32)1334892 Confirmation of the state of fusion and adhesion The nylon yarn of the main knitted fabric was dissolved in 20% dilute hydrochloric acid, and the molten state of the contact portion between the polyurethane fibers was observed. The sample in the evaluation of the damage of the knitted fabric was cut into a short rectangular sample having a length of 3.3 cm and a width of 2 4.0 cm for the knitting direction of the heat-set knitted fabric, and the slit was added to the knitting direction at an angle of 40 degrees from the transverse direction. It is divided into "starting weaving side" and "finishing weaving side", and the cutting part in the longitudinal direction is stitched into a ring-shaped sample by a super three-angle machine. Sample washing in the evaluation of knitted fabric damage The prepared sample was washed continuously for 300 minutes under the following conditions: washing machine for household use: two-tank washing machine: adjusted to 1.3 g/liter (using weak alkali washing) The amount of water: 30 liters of load cloth: cotton, mixed with polyurethane elastic fiber, Bayer cotton fabric, 1. 〇 kg. Evaluation of the damage of the knitted fabric The degree of damage of the cutting portion of the "starting knitting side" and "completed knitting side" was observed and evaluated in the following four stages. -35- (33) 1334892 ◎: No damage detected 〇: Slightly observed damage △: Inspected damage X: Intensive damage Among them, △ and X are hesitant as damage to the wear of clothing, ◎ and 〇 are washable and durable Good in terms of sex.
〔比較例8〕 除了將比較例1之彈性纖維使用於圖5之L 3之c以 外，同實施例8作成經針織物。熱定型後，測定分離橫列 線的解編張力，確認聚胺基甲酸乙酯彈性纖維的熔黏狀況 ，且進行與實施例8同樣之試驗。結果示於表4。 〔實施例9〕[Comparative Example 8] A knitted fabric was produced in the same manner as in Example 8 except that the elastic fiber of Comparative Example 1 was used in the case of L 3 of Fig. 5 . After heat setting, the untwisting tension of the separated course was measured, and the state of fusion of the polyurethane elastic fiber was confirmed, and the same test as in Example 8 was carried out. The results are shown in Table 4. [Example 9]
使用與實施例8同樣之針織機’並於圖6之L1之a 使用6 _尼龍長紗56分特1 7長紗，於L2之c使用比較 例1之聚胺基甲酸乙酯彈性纖維，於L3之c使用實施例 1之聚胺基甲酸乙酯且作成經針織物，並進行與實施例8 同樣之試驗。結果示於表4。 〔比較例9〕 除了將比較例1之彈性纖維使用於圖6之L3之c以 外，同實施例9作成經針織物，並進行同樣之試驗。結果 示於表4。 -36- (34) 1334892 〔實施例1 Ο〕 使用與實施例8同樣之針織機，並於圖7之L1之a 使用6 —尼龍長紗5 6分特1 7長紗，於L 2之b使用實施 例1之聚胺基甲酸乙酯彈性纖維，且未使用分離橫列線作 成經針織物，且進行與實施例8同樣之試驗。結果示於表Using the same knitting machine as in Example 8 and using 6 _ nylon long yarn 56 dtex 17 yarn in the L1 a of Fig. 6, and using the polyurethane elastic fiber of Comparative Example 1 in L2 c, The polyurethane of Example 1 was used as the knitted fabric in L3, and the same test as in Example 8 was carried out. The results are shown in Table 4. [Comparative Example 9] A knitted fabric was produced in the same manner as in Example 9 except that the elastic fiber of Comparative Example 1 was used in the case of L3 of Fig. 6, and the same test was carried out. The results are shown in Table 4. -36- (34) 1334892 [Example 1 Ο] Using the same knitting machine as in Example 8, and using a 6-nylon long yarn of 5 6 dtex and 1 7 long yarn in L1 of Fig. 7, in L 2 b The polyurethane elastic fiber of Example 1 was used, and a knitted fabric was not used as the separated yarn, and the same test as in Example 8 was carried out. The results are shown in the table
〔比較例1 〇〕 除了將比較例1之彈性纖維使用於圖7之L2之b以 外，同實施例1 〇作成經針織物，並進行同樣之試驗。結 果示於表4。 〔實施例1 1〕[Comparative Example 1 〇] A knitted fabric was produced in the same manner as in Example 1 except that the elastic fiber of Comparative Example 1 was used in the case of L2 of Fig. 7, and the same test was carried out. The results are shown in Table 4. [Example 1 1]
使用與實施例8同樣之針織機，並於圖8之L1之a 使用6—尼龍長紗56分特17長紗，於L2之b使用實施 例1之聚胺基甲酸乙酯彈性纖維，且未使用分離橫列線作 成經針織物，且進行與實施例8同樣之試驗。結果示於表 4 〇 〔比較例11〕 除了將比較例1之彈性纖維使用於圖8之L2之b以 外，同實施例Π作成經針織物，並進行同樣之試驗。結 果示於表4。 -37- (35)1334892 表4 解編張力和彈性纖維彼此之熔點狀態評價，及裁斷部之損 傷評價結果 解編張 彈性纖維相互之熔黏狀況 裁斷部之損傷 •脫線評價 力(CN) 開始編織側 完成編織側 實施例8 18.6 不能剝離熔黏性大 〇 〇 比較例8 7.2 可剝離熔黏性小 X X 實施例9 12.0 不能剝離熔黏性大 〇 〇 比較例9 4.8 可剝離熔黏性小 Δ Δ 實施例1 0 一 不能剝離熔黏性大 〇 〇 比較例1 0 一 可剝離熔黏性小 X X 實施例1 1 — 不能剝離熔黏性大 ◎ 〇 比較例1 1 — 可剝離熔黏性小 Δ △ 實施例8、9爲分離橫列線的解編張力高，顯示分離 橫列線與熱熔黏聚胺基甲酸乙酯彈性纖維爲強力熔黏。比 較例8、9爲分離橫列線的解編張力低，顯示難發生與高 熔點聚胺基甲酸乙酯彈性纖維的熔黏。又，關於聚胺基甲 酸乙酯彈性纖維彼此的熔黏狀況，亦於實施例8、9爲高 熔黏聚胺基甲酸乙酯彈性纖維與高熔點聚胺基甲酸乙酯彈 性纖維爲完全熔黏，即使將接觸部拉伸亦無法剝離。比較 例8、9之高熔點聚胺基甲酸乙酯彈性纖維彼此爲熔黏弱 ，若將接觸部拉伸則接觸部分離。又，實施例1 0、1 1爲 -38-Using the same knitting machine as in Example 8, and using 6-nylon long yarn 56 dtex 17 long yarn in L1 a, and polyurethane polyurethane elastic fiber of Example 1 in L2 b, and The knitted fabric was not used in the separated course line, and the same test as in Example 8 was carried out. The results are shown in Table 4 比较 [Comparative Example 11] A knitted fabric was produced in the same manner as in Example 8 except that the elastic fiber of Comparative Example 1 was used in the case of L2 of Fig. 8 and the same test was carried out. The results are shown in Table 4. -37- (35)1334892 Table 4 Evaluation of the debonding tension and the melting point state of the elastic fibers, and the damage evaluation results of the cutting part. De-straining of the elastic portion of the elastic fiber and the damage of the cutting part • Off-line evaluation force (CN) Starting the braided side to complete the braided side Example 8 18.6 Can not peel off the melt adhesiveness 〇〇 Comparative Example 8 7.2 Peelable melt viscosity small XX Example 9 12.0 Can not peel off the melt adhesiveness 〇〇 Comparative Example 9 4.8 Strippable melt viscosity Small Δ Δ Example 1 0 Can not be peeled off and melted. Comparative Example 1 0 One peelable melt viscosity is small XX Example 1 1 - Can not be peeled off and melted ◎ 〇 Comparative Example 1 1 - Strippable melt adhesion Smallness Δ Δ In Examples 8 and 9, the de-knit tension of the separated course line was high, and the separation course line and the hot-melt adhesive polyurethane fiber were strongly melted. Comparative Examples 8 and 9 have a low unwinding tension for the separated course line, indicating that it is difficult to melt and adhere to the high melting point polyurethane elastomer. Further, regarding the fusion state of the polyurethane elastic fibers, the high-melting polyurethane elastic fibers and the high-melting polyurethane elastic fibers are completely melted in Examples 8 and 9. Sticky, even if the contact portion is stretched, it cannot be peeled off. The high-melting-point polyurethane elastomer fibers of Comparative Examples 8 and 9 were weakly fused to each other, and the contact portions were separated if the contact portion was stretched. Further, Embodiment 10, 1 1 is -38-