1328055 玖、發明說明： 【發明所屬之技術領域】 本發明係有關於一種藉由熔紡二種不同結晶速度之半結 晶聚合物製造複合纖維之方法。 【先前技術】 複合纖維’特別是複合聚晞烴及複合聚酯纖維之許多實 例’及製造彼等之方法，已為本技藝所知。請閱，例如，「聚 口物科學及工程百科全書」（丁he Encycl〇pedia1328055 玖, INSTRUCTION DESCRIPTION OF THE INVENTION: FIELD OF THE INVENTION The present invention relates to a process for producing a composite fiber by melt spinning a semi-crystalline polymer of two different crystallization rates. [Prior Art] Many examples of composite fibers, particularly composite polyalkylene hydrocarbons and composite polyester fibers, and methods of making them, are known in the art. Please read, for example, "Encyclopedia Science and Engineering Encyclopedia" (Ding He Encycl〇pedia
Science and Engineering)，第 3版，第 11 卷，頁 43 3订。 荒永（Aranaga)等人在曰本公開案平成u_1 58733號中揭示 種具有潛捲縮性之聚對苯二酸乙二醇自旨/聚對苯二酸丙二 醇酉曰（PET/PPT)之複合纖維。在荒永及其他專利中都認定高 回復捲縮纖維具有製造高價值非織織物之潛能。 角本（Kakumoto)等人在日本公開案”⑽^““⑼號中揭 示一種自二種不同熔融黏度之ΡΕτ聚合物製造複合纖維之方 法，此法係在2,200至4,800米/分之速度下旋紡，然後在另 一階段旋纺拉伸並捲繞以製造具有潛捲縮性之複合纖維。 坪井（Tsuboi)等人在曰本公開案p2〇〇2_61〇29號中揭示一 種在3000米/分下旋紡以製造ρΕΤ/ρρτ複合纖維之方法。如 此製造的紗線經後拉伸步驟而實現捲縮。 旋纺複合纖維之技藝己相當完善。例如，美國專利第 3，671，379號揭不複合聚酯纖維之旋紡，完成旋紡之設備及 提供所欲產物所需之紡絲頭之設計。 【發明内容】 89682 1328055Science and Engineering), 3rd edition, Volume 11, page 43 3 set. Aranaga et al., in the disclosure of Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Composite fiber. High-return crimping fibers have been identified in Waste and other patents as having the potential to produce high value nonwoven fabrics. Kakumoto et al., Japanese Patent Publication (10)^"" (9) discloses a method for producing composite fibers from two different melt viscosity ΡΕτ polymers, which is at a speed of 2,200 to 4,800 m/min. Spinning, and then spinning and winding at another stage to produce a composite fiber having a latent crimping property. Tsubo (Tsuboi) et al. disclose a 3,000 m in the present disclosure p2〇〇2_61〇29 / Spinning spinning to produce a ρΕΤ/ρρτ composite fiber. The yarn thus produced is crimped by a post-drawing step. The technique of spinning a composite fiber is quite perfect. For example, U.S. Patent No. 3,671,379 The spinning of the non-composite polyester fiber, the spinning spinning equipment and the design of the spinning head required to provide the desired product. [Summary of the Invention] 89682 1328055
關於一種製造聚醋複合纖維之方法，此方法 下所組成：結合至少二種可結晶聚酯聚合物， 聚合物’及使該等溶融聚合物流動通過具有 之纺絲頭，該纺絲頭適合於製造複合纖維， —股0.5至6旦之纖維，該股係以最大收縮率 物在旋紡條件下之結 【實施方式】 <〇%之線速度旋紡，該二種可結晶聚酷聚合 下之結晶速度各不相同。 根據本發明自半結晶聚酯製造之複合纖維，其特徵為不 需要任何額外的加工步驟如拉伸步驟、退火步驟或本技藝 所教7F貫現具有高潛捲縮性之纖維所需之任何此等其他步 驟，初紡纖維即具有出乎意外高的潛收縮性及高度的潛捲 縮性。根據本發明製造之初紡纖維幾無捲縮，使其高度適 用於製造非織物及習知編織及針織紡織物。在製造步驟完 成之後，潛收縮性及捲縮性即可顯現而提供具有優異伸展 及回縮之高密度紡織物。 本技藝己熟知自不同結晶速度之聚合物製造複合纖維。 然而，本技藝並未教示或建議具有高潛收縮性及高潛捲縮 性之纖維可由二種在最大收縮率旋紡速度（maximum shrinkage spinning rate : MSSR)旋紡時結晶速度相互不同之 可結晶聚酯旋紡複合纖維而製造。理由是迄目前為止並未 得知在旋紡二種可結晶聚酯之複合纖維時有河“尺之存在。 為本發明之用，最大收縮率旋紡速度（mssr)係定義為如 此製造I纖維具有較在與MSSR相差至少± _丨〇%所製造之纖 89682 1328055 維為高之潛收縮性之旋紡速度。如以下所示，MS SR係局部 最大，使得在較MSSR為高及為低之旋紡速度下所製造的都 是低收縮性纖維。 本發明不受其方法之任何特別科學說明所限制。然而， 本發明人相信，從二種不同結晶速度之可結晶聚合物在旋 紡之條件下旋紡複合纖維時，MSSR之存在基本上端視該結 晶速度之差異而定。在旋紡速度低於MSSR 10%以下，尤其 是低於20%以下時，較不會結晶之聚合物會產生不足之定 向，不能在稍後加熱時提供顯著之收縮，因而很少產生捲 縮。在旋纺速度大於MSSR 10%以上，尤其是大於20%以上 時，二種聚合物都會產生充足之定向，致二種聚合物都會 發生結晶，而留下不大的結晶度差異。然後在稍後加熱時， 很少發生收縮，因而很少產生捲縮。然而，在MSSR附近， 二種聚合物都會進行定向，但定向之程度僅足以在一聚合 物引發顯著的結晶，而另一雖會定向但很少結晶。在低結 晶度聚合物之玻璃轉移溫度以上加熱時，低結晶度聚合物 會進行高收縮，而高結晶度聚合物則不會，因而產生高度 捲縮之纖維。 熟諳本技藝者將了解，許多變數的合併效果將決定MSSR 在任何既定特定條件下之特定值。在對MS SR之特定值以及 收縮率及捲縮率最大值有影響之變數當中，還包括二種聚 合物之結晶速度之比，較快結晶組份之結晶速度之絕對大 小，製造中纖維之厚度或旦數，旋紡溫度及加諸於移動纖 維線之急冷型式。從以下諸實例可看出，聚合物結晶速度 89682 丄以8055 之差異’在其他變數固定時’會造成MSSR有很大的差異。 根據本發明方法製造之複合纖維在剖面上係不對稱，不 疋並排複合纖維’便是皮芯複合纖維，其中皮及芯之縱向 轴並非-致。在一具體例中，二組份係以實質恒定之比存 在於纖絲剖面；而在另-具體例中，該二組份的剖面比不 同。在實行本發明時，二組份較佳係以恒定比存在於整個 纖維長度。組份聚合物較佳以並排關係存在於旋纺纖維中。 一在本發月之方n冑由本發明方法製造之複合纖維中 一種水酗又重里比係在3〇/7〇_7〇/3〇，較佳4〇/的-6_〇，更 佳45/55-55/45之範園内。 在本發明之較佳具體例中，本發明方法所用之二種聚酿 具有不同之組成。較佳組成包括PET/PPT、PET/聚（對笨二 酸丁二醇酯）（PBT)及ΡΡΤ/ΡΒτ，而以PET/pp 丁為最佳。二組 份《特性黏度較佳不同。適用於本發明之其他聚酿包括聚 (;，6-二莕二甲酸乙二醇酯)、聚(2,6_二莕二甲酸丙二醇酯)、 聚（聯苯甲酸丙二醇酯）、聚（對苯二酸環己基丨，4_乙二醇酯）、 聚（對苯二酸丨，3·環丁烷乙二醇酯）、及聚（聯苯甲酸1，3_環丁 烷乙二醇酿）。 諸聚合物有利的是特性黏度（intrinsic Visc0suy : IV)及組 成都不相同，例如，在較佳之pET及ρρτ組合中，ρΕτ之特 徵為具有1V等於或低於約0.80 dl/g，而ΡΡΤ之特徵為具有IV 等於或大於約0.85 dl/g。儘管如此，二種聚合物必須充分類 似始能相互黏附；否則複合纖維將分裂成為二纖維。 本發明方法所製造之初紡複合纖維無明顯的捲縮。「無明 89682 1328055 顯的捲縮」—詞係涵蓋一種情況，其中捲縮頻率（每單位長 度之捲縮數量）小於纖維捲縮後每吋捲縮總數量之1 〇%。初 纺複合纖維較佳無捲縮。捲縮可在㈣狀態下曝露於 …時發生--貫質鬆弛」一詞係意指可讓紗線在輕微張力下， 例如’在以下如何測定捲縮之說明中1.5克重量懸吊於紗線 束時。若纖維在過大張力下，捲縮展現及收縮都會受到約 束，而纖維很可能會熱定形，隨之而來的是潛捲縮性減少 或消失°最後捲縮展現可在乾熱或濕熱狀況下達成。 在MSSR之士-丨〇%範圍内之旋紡速度下所旋紡之纖維具有 同度所欲之初紡纖維幾無捲縮與可實現收縮率（其在較佳具 例中為等於或超過4〇%)之組合。根據本發明方法所製造 之纖維’在例如需要具有高潛捲縮性及良好回復性之低捲 縮纖維製造非織織物時，相當有用。 根據本發明製造之潛捲縮性纖維之好處之一係在捲縮已 發生後，纖維需經退火始能在該捲縮之纖維之非結晶部份 引發結晶’因而可穩定住捲縮及增強拉伸後之捲縮回復性。 為實行本發明之方法而結合之諸聚合物之選擇，有利的 疋由比較諸侯用聚合物之結晶速度來決定。一種便利於實 行本發明之結晶速度之測定方法，係利用ASTM D3418-82 所述差示掃描熱量法（DSC)之方法來測定每一候用材料在對 應於預期旋紡條件之相同溫度範圍内之等溫結晶速度曲 線。藉由選擇聚合物及處理溫度以強調結晶速度之差異， 本發明之益處即可實現。以下將提出測定等溫結晶速度之 方法之特定實例’及特定聚合物之比較。 89682 1328055 在本發月方法之一具體例中，係將二種組成上不同之聚 酉曰自’’方絲頌熔紡以形成複合纖維。根據美國專利案第 3’671’379號所揭#之方& ’不論是後凝集或前凝集（㈣卜 coalescence or pre_coalescence)紡絲頭皆可使用。 圖1顯示可用於本發明方法之橫流驟冷熔纺裝置之一具體 例。驟冷虱體1經過送氣室4，通過絞接擋板丨8並經過篩網5 進入紡絲頭正面3以下之區2内，產生實質層流氣體通過剛 自纺絲頭毛細管（未示出）纺出之仍㈣融之纖維6。播板Μ 係、”交接在頂部，且其位置可調整以改變驟冷氣體通過區2之 流量。紡絲頭正面3係以距離八嵌在區2頂部之凹口内，俾騾 冷氣體不致接觸剛旋纺之纖維，而在延遲至纖維由凹口側 面加熱之後才接觸。（在圖！裝置之_替代具體例中，㈣ 頭正面不在凹口内）。驟冷氣體（若有需要可加熱）繼續前進 通過纖維並進入圍繞裝置之空間中。唯有一小量的氣體會 被通過纖維出口 7離開區2之移動纖維帶走。在本發明方法 之-具體例中，整理劑係藉整理劑輕施塗於現為固體之纖 維。在自驟冷區2胃出及若有f要通過整理劑輥後，纖維即 可能經由-或多支導輥，如所示"及12，導至飼入輥13。 飼入輥之速度決定且實質等於旋纺之線速度。從辕Η，妙 線可能經由-或多支額外導輕(未示出)送至捲繞輕Μ。 當使用橫向、徑向或相似向氣體流時，根據本發明之方 法之抽拉速度係在約爆5，_米/分之範圍内。當使用順流 驟冷氣體流（未不出）時，根據本發明之方法之抽拉速度係在 約820-6,000米/分之範圍内。 89682 -10· 1328055 旋紡可用本技藝己知用於製造複人嬙 ,'士 - 设0纖維心任何方法完 成。美國專利案第3,6?1，379號之揭示内 古Μ 丁内各在這—方面特別 哥關。 在本發明方法之-具體例中，請閱圖2，二種聚酉旨溶 分別計量(用未示出之裝置），送至纺絲頭4背面3中標示為: 及2之二環之孔中。請閱圖3 ’密封構 、 傅仵（未不出）可避免二熔 月豆在紡絲頭4之背面3混合。仍請閱圖3，_ Μ 一熔體通過個別槽 道5及6至纺絲頭4之前面7,在此在彼等離開纺絲頭總成時 合併成為並排複合纖維。然後，經擠壓之紗線束即如圖丨所 示向下抽拉並驟冷及捲繞。 實例 測定以下特定具體例中所用聚合物之等溫結晶速度。每 一聚合物都在表丨所示溫度下獨立測定，然後將結果合併以 提供圖4所示圖解比較。 將6-8笔克之PET試樣放入藉内冷却器π控制之柏琴-愛瑪 (Perkin-Elmer : PE) DSC-7 (差示掃描熱量計）中，以 5〇0(：/分 速度由50°C加熱至285°C，保持在285°C 3分鐘，以2〇〇。〇/ 分冷却至表1所示介於150。〇與225它中間之結晶溫度之_。 將試樣保持在指定溫度1〇_6〇分鐘，直至結晶完成。將另一 6-8毫克之2GT試樣加熱至285t 3分鐘，然後在液態氮溫度 中冷却。將經驟冷之樣本轉移至在3(TC下靜置之^^ Dsc_7 中。然後’將樣本以200 °C /分速度加熱至表1所示介於 130°C與160°C中間之結晶溫度之一。將試樣保持在指定溫 度下40分鐘，直至結晶完成。在每一情形，結晶已進行一 89682 1328055 半所需之時間tl/2，係自數據決定。 將6-8毫克之PPT試樣放入PE DSC-7中，以50°C/分速度由 50°C加熱至260°C，保持3分鐘，及以200°C/分速度冷却至 表1所示介於100°C與200°C中間之結晶溫度之一。將試樣保 持在指定溫度下10-60分鐘，直至結晶完成。將另一 6-8毫克 之PPT試樣加熱至285°C並保持3分鐘，繼之與PET試樣一樣 在液態氮中冷却。然而，在將試樣移入液態氮中時特別小 心使用熱鑷子以避免與冷鑷子接觸所產生的可能部份驟 冷。利用冷鑷子將經驟冷之PPT樣本轉移至在5 °C下靜置之 P-E DSC-7中，然後以200°C/分速度加熱至表1所示介於 60°C與65°C中間之結晶溫度。 將6-8毫克之PBT試樣放入PE DSC-7中，以50°C/分速度由 50°C加熱至260°C，保持3分鐘，及以200°C/分速度冷却至 表1所示介於150°C與200°C中間之結晶溫度之一。將試樣保 持在指定溫度下10-60分鐘，直至結晶完成。將另一 6-8毫克 之PBT試樣在熱重量分析盤内加熱，並以鑷子接觸樣本冷却 至液態氮溫度。將經驟冷之PBT利用急冷之鑷子移至在 -10°C下靜置之P-E DSC-7中。將試樣以200°C/分速度加熱至 表1所示介於37°C與45°C中間之結晶溫度之一。將試樣保持 在指定溫度下40-60分鐘，直至結晶完成。 將結果圖解合併於圖4中以顯示三種聚合物之結晶行為之 極度差異。 89682 -12- 1328055 表1結晶半時 結晶溫度 PET PPT PBT 37〇C 4.42 分 40°C 0.55 45〇C 0.25 60°C 4_47 分 62〇C 2.78 63 °C 2.17 64〇C 1.15 100°C 0.60 120°C 1.32 130°C 5.93 分 140°C 3.97 1.47 150°C 2.18, 1.98 160°C 1.35, 1.17 1.33 170°C 0.98 1.33 0.40 175〇C 0.93 180°C 0.93 2.12 0.60 185〇C 1.15 190。。 6.20, 2.75 1.50 195 V 1.32 6.50 2.97 200°C 1.60 13.0 6.15 205〇C 1,90 210 V 3.08 215。。 4.47 220〇C 7.25 225〇C 11.95 89682 -13- 1328055 聚酯之特性黏戽（IV)係以Viscotek強制流動黏度計Υ-900 型在19°C下及根據ASTM D-4603-96但在0.4%濃度之50/50重 量％之三氟乙酸與二氣甲烷混合物中測量。然後將所測得黏 度與在60/40重量％酚/1,1，2,2-四氯乙烷中之標準黏度予以關 聯而得此處所提供之特性黏度。 初纺纖維發生捲縮並根據以下程序測量捲縮率。利用搖 絞紗機以張力約0.1 gpd (0.09 dN/德士）將每一纺紗形成為 5 00〇+/-5總旦數（55 50分德士）之絞紗。然後在70+/-2卞（2 1 +/-1°C)及65 +/-2%相對濕度下’將絞紗調控最少16小時。 將經調控之绞紗垂直懸吊於紗架上，絞紗底端附加5〇〇克重 量（100 mg/d; 90 mg/dtex)’並測量絞紗長度至精確度1毫米。 此一初紡長度之測量值在此即稱為「最初長度」。 然後將500克重量移走，並將樣本放入維持於1 6〇它之烘 箱中，並保持5分鐘使捲縮發生。然後，將絞紗移走並在7〇+/ -2 F (21 +/-1 C )及65 +/-2%相對濕度下調控最少μ小時。 將 1.5 mg/den (1.35 mg/dtex)重量（例如，555〇 dtex絞紗時 7 · 5克）掛在絞紗底部，令加重之絞紗達到平衡長度並測量絞 紗之長度至1毫米内並記錄為"cb"。在測試期間内，將丨35 mg/dtex重量留在絞紗上。接著，將5〇〇克重量（1〇〇mg/d; 9〇 mg/dtex)掛在絞紗底端，並測量絞紗之長度至i毫米内並記 錄為”Lb’^根據以下公式計算捲縮率值（％)(如以下所述在熱 定形前），”CCb” CCb-100 X (Lb-Cb)/Lb 將500克重量移走，然後將绞紗掛在紗架上並在烘箱中在 89682 -14 - 1328055 杓250 F(121 C )下，且1.3 5 mg/dtex重量仍在時熱定形5分鐘， 之後，自烘箱中取出紗架及絞紗，並如上調控2小時。 下述心序再度測量絞紗之長度並將其長度記錄為"Ca"。將 5 00克重量再懸吊於絞紗上，並如上測量絞紗長度並記綠為 "La”。根據以下公式計算熱定形後捲縮率值（％)，"cc ,, CCa=100 X (La-Ca)/La 表中有ccat記綠。 收縮率之定義為： 收縮率= i〇〇 X (最初長度-La)/最初長度。 根據本發明方法之較佳具體例製造之纖維，其特徵為CC 在30°/。以上，最佳在40%以上。 利用一對偉納及弗雷德勒（Werner & Pfleiderer)共轉動28 毫米雙螺旋擠壓機，將指定聚合物熔融及擦壓。PET擠壓機 中所達到的最高熔體溫度為，而ρρτ擠壓機中 的對應溫度則為約265-275 t。擠壓機將聚合物飼入齒輪泵 中計量以送至紡絲頭總成。 知在速度s 2500米/分旋紡之紗線捲繞於李索納（Less〇na) 959型捲繞機上。將在速度225〇〇米/分旋紡之紗線捲繞於巴 瑪（Barmag) SW6 2s 600捲繞機（德國Barmag公司）上，其最 高捲繞速度為6,000米/分。 紡絲頭係後凝集雙組份纺絲頭，有3 4對毛細管排成圓形， 每對毛細管間之内角為30，毛細管直徑為〇 64毫米及毛細 管長度為4.24米。纖維中二種聚合物之重量比為5〇/5〇。34 支纖絲紗之總旋纺重量為約33.4/分。紗線旦數係以旋紡速 89682 -15 - 1328055 度決定。 貫免12 ’ 實例1至7 Α·根據美國專利案第5，171，898號所揭示之方法，將丙烯 醛在酸性陽離子交換催化劑之存在下水合以形成3-羥基丙 醛’製造丨，3-丙二醇。將催化劑及未反應丙烯醛分離出，然 後根據美國專利案第3,536,763所揭示之方法，利用雷尼 (Raney)鎳催化劑，將3_羥基丙醛催化式氫化。將產物 丙二醇自含水溶液中回收並予以純化。 B·自1，3-丙二醇及二甲基對苯二甲酸酯（"dmt")在二容器 方法中，利用鈦酸四丙酯催化劑，TyZOr® TPT (杜邦公司註 冊商標），以60 ppm (以聚合物為準），製造聚（對苯二酸丙 二醇醋）。將熔融之DMT在1 85。(：下加至酯基轉移容器内之 1，3·丙二醇及催化劑中，並將溫度提高至21〇〇c，同時移除 甲醇。將所得中間產物移至縮聚合容器中，其中愿力降至^ 毫巴（10.2 g/cm )及溫度提高至255°C。當達到所欲熔體黏度 時，即提高壓力並將聚合物擠壓、冷却及切成粒錠。將粒 錠以固相在212。(：之轉籠烘乾機中進一步聚合至特性黏度為 1.04 dl/g。 C.將具特性黏度為0.54 dl/g之聚（對苯二酸乙二醇 酯）（Crystar® 4415 ’杜邦公司註冊商標）與以上步驟b所製 造之聚（對苯二酸丙二醇酯）自以上所述熔紡成為複合纖維。 將PET擠壓機設定於275°C，及PPT擠壓機設定於26〇°c。旋 纺頭保持於265°C。 纺絲頭溫度保持於約2 7 2 °C。纺絲頭凹進旋纺柱之頂部内 89682 •16- 1328055 0.75吋’俾驟冷$體在僅短暫延遲後即接觸剛紡成之纖維。 驟冷氣體係空氣，以室溫約2(TC供應。紡絲頭下方區域之 南度（圖1中之"2")為172 cm。驟冷空氣具以下流量分佈，此 係沿平均纖絲路徑距分配網5吋（12.7 cm)所測得。 表2 : 離紡絲頭距離(cm) 空氣速度(mpm) 15 8.5 30 9.4 46 9.4 61 11.0 76 11.0 91 11.3 107 11.6 122 16.5 137 34.1 152 39.6 168 29.6 使纖維通過一對在驟冷柱底部以2000米/分運轉之室溫輥 上並用李索納959型恆定張力捲繞機捲繞。 纖維中二種聚合物之重量比為50/50。34支纖絲紗之總旋 紡重量為約33.4克/分。 產物紗也以差示掃描熱量法（DSC)測試。裝置為T.A儀器 型2920MDSC，V2.5F，在-50與300。(：之間操作，以1〇度/分 89682 -17-A method for producing a polyester conjugated fiber, the method comprising: combining at least two crystallizable polyester polymers, a polymer, and flowing the molten polymer through a spinning head having a spinning head suitable for For the manufacture of composite fibers, which are fibers of 0.5 to 6 denier, which are knotted under the conditions of maximum shrinkage under spinning conditions [embodiment] < 〇% linear speed spinning, the two crystallizable poly cool The rate of crystallization under polymerization varies. A composite fiber made from a semi-crystalline polyester according to the invention, characterized in that it does not require any additional processing steps such as a stretching step, an annealing step or any of the art required to teach fibers having high latent crimp properties. In these other steps, the as-spun fiber has an unexpectedly high latent shrinkage and a high degree of latent shrinkage. The as-spun fibers produced in accordance with the present invention are not crimped, making them highly suitable for use in the manufacture of non-woven fabrics and conventional woven and knitted fabrics. After the manufacturing step is completed, the latent shrinkage and crimpability are visualized to provide a high-density textile having excellent stretch and retraction. It is well known in the art to make composite fibers from polymers of different crystallization rates. However, the art does not teach or suggest that fibers having high latent shrinkage and high latent shrinkage can be crystallized by two different crystallization rates at the maximum shrinkage spinning rate (MSSR) spinning. Manufactured from a polyester spin-spun composite fiber. The reason is that until now, it has not been known that there is a river "the ruler" when spinning the two kinds of crystallizable polyester composite fibers. For the purpose of the present invention, the maximum shrinkage spinning speed (mssr) is defined as such The fiber has a spinning speed higher than that of the fiber manufactured by the MSSR at least ± _ 丨〇 % of the fiber 89682 1328055. As shown below, the MS SR is locally maximal, making it higher than the MSSR and Low shrinkage fibers are produced at low spinning speeds. The invention is not limited by any particular scientific description of the method. However, the inventors believe that crystallizable polymers from two different crystallization rates are spinning. When spin-spun composite fibers are spun under spinning conditions, the presence of MSSR is basically determined by the difference in crystallization rate. When the spinning speed is lower than 10% of MSSR, especially below 20%, the polymerization is less crystalline. The material will produce insufficient orientation and will not provide significant shrinkage when heated later, so that shrinkage will rarely occur. When the spinning speed is greater than 10% of MSSR, especially above 20%, both polymers will produce sufficient It Both crystals are crystallized, leaving little difference in crystallinity. Then, when heated later, shrinkage rarely occurs and shrinkage is rarely produced. However, in the vicinity of MSSR, two polymers Orientation, but the degree of orientation is only sufficient to induce significant crystallization in one polymer, while the other is oriented but less crystalline. When heated above the glass transition temperature of a low crystallinity polymer, the low crystallinity polymer will High shrinkage is achieved, while high crystallinity polymers do not, resulting in highly crimped fibers. Those skilled in the art will appreciate that the combined effect of many variables will determine the specific value of the MSSR under any given specific conditions. The specific value of SR and the variable of the maximum shrinkage rate and the crimping rate also include the ratio of the crystallization speed of the two polymers, the absolute size of the crystallization rate of the faster crystalline component, and the thickness or denier of the fiber in the manufacturing process. The number, the spinning temperature and the quenching pattern applied to the moving fiber line. It can be seen from the following examples that the polymer crystallization rate of 89682 丄 is different from 8055' in other variations. When the number is fixed, the MSSR will be greatly different. The composite fiber produced by the method of the present invention is asymmetric in cross section, and the composite fiber which is not side by side is a sheath-core composite fiber, wherein the longitudinal axis of the sheath and the core is not - In one embodiment, the two components are present in the filament cross section at a substantially constant ratio; and in another embodiment, the cross-sectional ratio of the two components is different. In the practice of the present invention, the two components are Preferably, the polymer is present in a constant ratio over the entire length of the fiber. The component polymers are preferably present in the spin-spun fiber in a side-by-side relationship. One of the composite fibers produced by the method of the present invention in the present month is a leeches. It is in the range of 3〇/7〇_7〇/3〇, preferably 4〇/-6_〇, more preferably 45/55-55/45. In a preferred embodiment of the present invention, the present invention The two types of brewers used in the method have different compositions. Preferred compositions include PET/PPT, PET/poly(p-butylene phthalate) (PBT) and ΡΡΤ/ΡΒτ, with PET/pp butyl being preferred. The two components "the characteristic viscosity is better. Other polyls suitable for use in the present invention include poly(;,ethylene glycol dicarboxylate), poly(propylene glycol 2,6-dioxadicarboxylate), poly(propylene glycol dibenzoate), poly( Cyclohexyl phthalate, 4_ethylene glycol ester), poly(barium terephthalate, 3·cyclobutane ethylene glycol ester), and poly(dibenzoic acid 1,3_cyclobutane ethylene) Alcohol brewing). The polymers are advantageously intrinsic Visc0suy (IV) and composition are different. For example, in the preferred combination of pET and ρρτ, ρΕτ is characterized by having 1V equal to or lower than about 0.80 dl/g. Characterized by having an IV equal to or greater than about 0.85 dl/g. Nevertheless, the two polymers must be sufficiently similar to each other to adhere to each other; otherwise the composite fibers will split into two fibers. The as-spun composite fibers produced by the process of the present invention have no significant crimping. "Unknown 89682 1328055 significant curling" - the word system covers a situation in which the crimping frequency (the number of crimps per unit length) is less than 1% of the total number of crimps per crimp after crimping. The as-spun composite fiber is preferably not crimped. The term "permeabilization" occurs when exposed to (4) in the state of (4) means that the yarn can be allowed to hang under slight tension, for example, '1.5 g of weight is suspended in the yarn in the following description of how to measure the crimp. When wiring harness. If the fiber is under too much tension, the crimping and shrinkage will be constrained, and the fiber is likely to be heat-set, with consequent reduction or disappearance of the latent crimp. The final crimp can be displayed under dry heat or hot heat. Achieved. The spun-spun fibers at a spinning speed in the range of MSSR-丨〇% have a few curls of the same desired spinning fiber and can achieve shrinkage (which in the preferred case is equal to or exceeds 4〇%) combination. The fiber ' manufactured by the method of the present invention is quite useful when, for example, a low-retracted fiber having a high latent crimping property and a good recovery property is required to produce a nonwoven fabric. One of the benefits of the latently crimped fibers produced in accordance with the present invention is that after the crimping has taken place, the fibers need to be annealed to initiate crystallization in the amorphous portion of the crimped fibers, thereby stabilizing the crimp and enhancing The curl recovery after stretching. The choice of polymers to be combined for carrying out the process of the present invention is advantageously determined by comparing the rate of crystallization of the polymers of the princes. A method for determining the crystallization rate of the present invention by using the differential scanning calorimetry (DSC) method described in ASTM D3418-82 to determine each of the materials in the same temperature range corresponding to the expected spinning condition. Isothermal crystallization speed curve. The benefits of the present invention can be achieved by selecting the polymer and processing temperature to emphasize the difference in crystallization speed. A specific example of a method for determining the isothermal crystallization rate and a comparison of specific polymers will be presented below. 89682 1328055 In one embodiment of the method of the present month, two different compositions of poly-ply from the '' square wire are melt-spun to form a composite fiber. The spinneret can be used in accordance with the method disclosed in U.S. Patent No. 3'671'379, whether it is post-aggregation or pre-agglutination (coalescence or pre-coalescence). BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 shows a specific example of a cross-flow quench melt spinning apparatus which can be used in the process of the present invention. The quenching crucible 1 passes through the plenum 4, passes through the splicing baffle 8 and passes through the screen 5 into the zone 2 below the front face 3 of the spinning head, producing a substantially laminar gas passing through the spinneret capillary (not shown) ) Spinning still (four) melted fiber 6. The board is spliced at the top, and its position can be adjusted to change the flow rate of the quenching gas through zone 2. The front side of the spinneret 3 is embedded in the notch of the top of zone 2, and the cold gas is not in contact. The fiber that has just been spun, but only after the fiber is heated by the side of the notch. (In the figure, instead of the specific example, (4) the front of the head is not in the notch.) Quenching gas (heating if necessary) Moving on through the fibers and into the space surrounding the device. Only a small amount of gas will be carried away by the moving fibers exiting the zone 2 through the fiber outlet 7. In the method of the invention - in particular, the finishing agent is lighter by finishing agent Apply to fibers that are now solid. After the stomach is out of the quench zone 2 and if f is to pass through the finish roller, the fiber may be fed via a - or multiple guide rolls, as shown " and 12, Into the roller 13. The speed of the feeding roller is determined and is substantially equal to the linear speed of the spinning. From the 辕Η, the magic line may be sent to the winding tweezer via - or a plurality of additional light guides (not shown). Method according to the invention for radial or similar gas flow The drawing speed is in the range of about 5, _m/min. When a co-current quenching gas stream is used (not shown), the drawing speed according to the method of the present invention is about 820-6,000 m/min. 89682 -10· 1328055 Spinning can be used in the manufacture of retracement, which can be done by any method. The US Patent No. 3,6?1,379 reveals the internal Μ In the specific method of the method of the present invention, please refer to FIG. 2, two kinds of polypyrene are separately metered (using a device not shown), and sent to the back of the spinning head 4 3 is marked as: and 2 of the ring of the second ring. Please refer to Figure 3 'sealing structure, Fu Yan (not out) can avoid the second melting moon beans mixed on the back of the spinning head 3 3. Still see Figure 3 , _ Μ a melt through the individual channels 5 and 6 to the front face 7 of the spinneret 4 where they merge into a side-by-side composite fiber as they exit the spin pack assembly. The extruded yarn bundle is then Pull down and quench and wind as shown in Figure . Example The isothermal crystallization rate of the polymer used in the following specific examples was determined. The measurements were independently measured at the temperatures indicated, and the results were combined to provide a graphical comparison as shown in Figure 4. A 6-8 gram PET sample was placed in an internal cooler π controlled Perkin-Elmer (PE) In DSC-7 (differential scanning calorimeter), heat from 50 °C to 285 °C at 5 °0 (:/min, keep at 285 °C for 3 minutes, and cool to 2 〇〇. 1 is shown as 150. The crystallization temperature between 〇 and 225 is kept. The sample is kept at the specified temperature for 1 〇 6 minutes until the crystallization is completed. Another 6-8 mg of the 2GT sample is heated to 285t. After 3 minutes, it was then cooled in liquid nitrogen temperature. The quenched sample was transferred to ^^ Dsc_7 at 3 (TC). Then, the sample was heated at 200 ° C /min to one of the crystallization temperatures between 130 ° C and 160 ° C shown in Table 1. The sample was held at the specified temperature for 40 minutes until the crystallization was completed. In each case, crystallization has been carried out for a period of 89682 1328055, half required time tl/2, as determined by the data. 6-8 mg of PPT sample was placed in PE DSC-7, heated from 50 ° C to 260 ° C at 50 ° C / min, held for 3 minutes, and cooled at 200 ° C / min to Table 1 One of the crystallization temperatures between 100 ° C and 200 ° C is shown. The sample is held at the specified temperature for 10-60 minutes until the crystallization is complete. Another 6-8 mg of PPT sample was heated to 285 ° C for 3 minutes and then cooled in liquid nitrogen as in the PET sample. However, the use of hot tweezers is particularly careful when moving the sample into liquid nitrogen to avoid possible partial quenching due to contact with the cold tweezers. The quenched PPT sample was transferred to PE DSC-7, which was allowed to stand at 5 °C, using cold tweezers, and then heated at 200 ° C / min to the middle of 60 ° C and 65 ° C shown in Table 1. Crystallization temperature. 6-8 mg of PBT sample was placed in PE DSC-7, heated from 50 ° C to 260 ° C at 50 ° C / min, held for 3 minutes, and cooled at 200 ° C / min to Table 1 One of the crystallization temperatures between 150 ° C and 200 ° C is shown. The sample is held at the specified temperature for 10-60 minutes until the crystallization is complete. Another 6-8 mg of the PBT sample was heated in a thermogravimetric analysis disk and contacted with a forceps to cool to a liquid nitrogen temperature. The quenched PBT was transferred to a P-E DSC-7 which was allowed to stand at -10 °C using a quenched tweezers. The sample was heated at 200 ° C / min to one of the crystallization temperatures between 37 ° C and 45 ° C as shown in Table 1. The sample is held at the specified temperature for 40-60 minutes until the crystallization is complete. The results are graphically combined in Figure 4 to show the extreme differences in the crystallization behavior of the three polymers. 89682 -12- 1328055 Table 1 Crystallization half-time crystallization temperature PET PPT PBT 37〇C 4.42 points 40°C 0.55 45〇C 0.25 60°C 4_47 points 62〇C 2.78 63 °C 2.17 64〇C 1.15 100°C 0.60 120 °C 1.32 130°C 5.93 minutes 140°C 3.97 1.47 150°C 2.18, 1.98 160°C 1.35, 1.17 1.33 170°C 0.98 1.33 0.40 175〇C 0.93 180°C 0.93 2.12 0.60 185〇C 1.15 190. . 6.20, 2.75 1.50 195 V 1.32 6.50 2.97 200°C 1.60 13.0 6.15 205〇C 1,90 210 V 3.08 215. . 4.47 220〇C 7.25 225〇C 11.95 89682 -13- 1328055 The characteristic viscosity of polyester (IV) is based on Viscotek forced flow viscometer Υ-900 at 19 ° C and according to ASTM D-4603-96 but at 0.4 Measured in a mixture of 50% to 50% by weight of trifluoroacetic acid and digas methane. The measured viscosity is then correlated with the standard viscosity in 60/40% by weight of phenol/1,1,2,2-tetrachloroethane to provide the intrinsic viscosity provided herein. The as-spun fiber was crimped and the crimp ratio was measured according to the following procedure. Each of the spun yarns was formed into a skein of 500 +/- +/- 5 total denier (55 50 dtex) using a skein machine at a tension of about 0.1 gpd (0.09 dN/ton). The hank is then conditioned for a minimum of 16 hours at 70 +/- 2 Torr (2 1 +/- 1 ° C) and 65 +/- 2% relative humidity. The conditioned skein was suspended vertically on a creel with a weight of 5 gram (100 mg/d; 90 mg/dtex) attached to the bottom of the skein and the skein length was measured to an accuracy of 1 mm. The measured value of this initial spinning length is referred to herein as the "initial length". The 500 gram weight was then removed and the sample was placed in an oven maintained at 16 Torr and held for 5 minutes for crimping to occur. The hank was then removed and conditioned for a minimum of μ hours at 7 〇 + / -2 F (21 +/- 1 C) and 65 +/- 2% relative humidity. Hang 1.5 mg/den (1.35 mg/dtex) weight (for example, 7.5 gram of 555 〇 dtex skein) at the bottom of the skein, make the weighted skein reach the equilibrium length and measure the length of the skein to within 1 mm. And recorded as "cb". The 丨35 mg/dtex weight was left on the skein during the test period. Next, hang the weight of 5 gram (1 〇〇 mg / d; 9 〇 mg / dtex) at the bottom end of the hank, and measure the length of the skein to within i mm and record it as "Lb" ^ calculated according to the following formula Crimping rate value (%) (before heat setting as described below), "CCb" CCb-100 X (Lb-Cb)/Lb Remove 500 g of weight, then hang the skein on the creel and The oven was at 89682 -14 - 1328055 杓250 F (121 C ) and the weight of 1.3 5 mg/dtex was still set for 5 minutes while the creel and skein were removed from the oven and conditioned for 2 hours as above. The following sequence was used to measure the length of the skein and record its length as "Ca". Hang the 500 gram weight on the skein and measure the skein length as above and record the green as "La". The curling rate value (%) after heat setting is calculated according to the following formula, "cc ,, CCa=100 X (La-Ca)/La has ccat green. Shrinkage is defined as: Shrinkage = i〇〇 X (initial length - La) / initial length. A fiber produced in accordance with a preferred embodiment of the method of the invention is characterized by a CC of 30°/. Above, the best is above 40%. The specified polymer was melted and rubbed using a pair of Weiner & Pfleiderer rotating a 28 mm twin screw extruder. The highest melt temperature achieved in a PET extruder is, while the corresponding temperature in a ρρτ extruder is about 265-275 t. The extruder feeds the polymer into a gear pump for metering to the spin pack assembly. It is known that the yarn of the spinning speed of 2500 m/min is wound on a Less〇na 959 winder. The yarn at a speed of 225 mm/min was wound on a Barmag SW6 2s 600 winder (Barmag, Germany) with a maximum winding speed of 6,000 m/min. The spinneret was agglomerated into a two-component spinneret with 34 pairs of capillaries arranged in a circular shape with an internal angle of 30 between each pair of capillaries, a capillary diameter of 〇 64 mm and a capillary length of 4.24 m. The weight ratio of the two polymers in the fiber is 5〇/5〇. The total spinning weight of the 34 filament yarns was about 33.4 per minute. The yarn denier is determined by the spinning speed of 89682 -15 - 1328055 degrees. Example 1 to 7 Α Aromatic aldehyde is hydrated in the presence of an acidic cation exchange catalyst to form 3-hydroxypropionaldehyde's oxime, 3 according to the method disclosed in U.S. Patent No. 5,171,898. - Propylene glycol. The catalyst and unreacted acrolein are separated, and then 3-hydroxypropanal is catalytically hydrogenated using a Raney nickel catalyst according to the method disclosed in U.S. Patent No. 3,536,763. The product propylene glycol is recovered from the aqueous solution and purified. B. From 1,3-propanediol and dimethyl terephthalate ("dmt") In the two-tank method, using tetrapropyl titanate catalyst, TyZOr® TPT (registered trademark of DuPont), 60 Ppm (based on polymer) to produce poly(terephthalate propylene glycol vinegar). The molten DMT will be at 1 85. (: is added to the 1,3·propanediol and the catalyst in the transesterification vessel, and the temperature is raised to 21 ° C, while removing the methanol. The obtained intermediate product is transferred to a polycondensation vessel, wherein the force is lowered To ^ mbar (10.2 g/cm) and the temperature is increased to 255 ° C. When the desired melt viscosity is reached, the pressure is increased and the polymer is extruded, cooled and cut into pellets. Further polymerized to an intrinsic viscosity of 1.04 dl/g in a cage of 212. C. Poly(ethylene terephthalate) having an intrinsic viscosity of 0.54 dl/g (Crystar® 4415) 'DuPont registered trademarks' and the poly(trimethylene terephthalate) produced in the above step b are melt-spun into a composite fiber as described above. The PET extruder is set at 275 ° C, and the PPT extruder is set at 26〇°c. The spinning head is maintained at 265 ° C. The spinning head temperature is maintained at approximately 2 7 2 ° C. The spinning head is recessed into the top of the spinning column 89682 •16- 1328055 0.75吋'俾Quenching $ The body is contacted with the fiber that has just been spun after only a short delay. The air of the quenching system is about 2 at room temperature (TC supply. The area under the spinning head) The south degree ("2" in Figure 1) is 172 cm. The quenching air has the following flow distribution, which is measured along the average fibril path from the distribution network of 5 吋 (12.7 cm). Table 2: Spinning Wire head distance (cm) Air velocity (mpm) 15 8.5 30 9.4 46 9.4 61 11.0 76 11.0 91 11.3 107 11.6 122 16.5 137 34.1 152 39.6 168 29.6 Pass the fiber through a pair at the bottom of the quench column at 2000 m/min. The room temperature rolls were wound with a Leesona 959 constant tension winder. The weight ratio of the two polymers in the fiber was 50/50. The total spinning weight of the 34 filament yarns was about 33.4 g/min. The yarn is also tested by differential scanning calorimetry (DSC). The device is TA instrument type 2920MDSC, V2.5F, between -50 and 300. (: operation between 1 degree/min 89682 -17-