1286168 九、發明說明： 太屬之技術領域】 複合優ί心耐士性得到了改善的聚醋類 蘇時ίϊ的ΐ㈡ΓίϊΓ㈡g極其對-二及洗 本發明製造的伸縮性複合纖維，即使行一 =的沸水或幹熱處理等另外的染色或後加J理疋j 於然捲曲拉伸率和不低於7_自然彈 =敗復率，並且氣處理後的拉伸強度維持率大於 伸縮維持率大於等於80%，應用於後加工或洗滌時、， 製品的伸縮性、耐氣性和形態穩定性極其優異。 【先前技術】 關於聚酯類伸縮性纖維，在專利文獻丨中，公開了使 用2種有極限粘度差的聚對苯二甲酸乙二酯（ρΕΤ)的方 法。另外，專利文獻2和專利文獻3使利用一般的聚對苯 二甲酸乙二酯和高收縮性的共聚合聚對苯二甲酸乙二酯， 製造聚酯類有潛在捲曲性的纖維的方法成爲公知技術。此 外，在專利文獻4和專利文獻5中也提出了在聚對苯二甲 酸乙一知（PET)中’使用具有拉伸性的聚對苯二甲酸丙二醋 (PTT)或聚對苯二甲酸丁二酯（PBT)的方法。 但是’對於現有所述專利中記載的製造方法製造的聚 酯類伸縮性複合纖維’沒有特別提到沸水/幹熱處理前的捲 1286168 曲恢復特性和耐氣性。聚酯類伸縮性複合纖維的特徵在 於，其通常具有2成分的雙金屬結構，染色或後加工時， 彿水或幹熱處理過程中，通過該2成分的收縮率差導致的 不同收縮而呈現捲曲，表現捲曲特性。現在的情況是，一 般的聚酯類伸縮性複合纖維在無負荷或幾乎接近無負荷的 輕負荷下，沸水和幹熱處理後的捲曲拉伸率爲40%的水平 或高於該水平，彈性恢復率爲6〇%或高於6〇%，但是尚沒有 一種技術可以保證即使不進行所述熱處理加工，也能維持 伸縮特性，同時氣處理後也能維持拉伸強度和伸縮性。 對於作爲代表性的伸縮性纖維的聚氨酯纖維來說，在 通常的氣處理後，引起拉伸強度降低大於等於約3〇%並且 伸縮特性降低大於等於20%。另外，對於聚酯類纖維來說， 與聚氨酯纖維相比，其耐氣性優異，但是涉及即使不進行 沸水或幹熱處理，也具有一定水平以上的伸縮特性，並且 氣處理後能維持拉伸強度和伸縮特性的聚酯類伸縮性複合 纖維的技術還沒有保證。並且對此還存在發生製品加工或 洗滌時引起形態變形、或者使拉伸強度和伸縮性降低等問 題的危險。 另外，以前涉及伸縮性複合纖維的專利文獻基本上只 提出採用不同的聚酯類高分子製造複合紡絲，沒有提及構 成複合纖維的不同高分子聚合物本身的分子量分佈以及微 細結構對複合纖維物理性質的影響。專利文獻4中，提到 了聚對苯二甲酸乙二酯（PET)、聚對笨二甲酸丙二酯（ρττ) 以及改性的PET、PTT的粘度變化帶來的物理性質變化，但 6 1 1286168 疋’這篇專利也沒有提及構成複合纖維的不同高分子的分 子量分佈。當然，根據馬克-豪音庫等式（Mark_H〇uwink equation)，從粘度-分子量的關係可以推斷分子量，但是， 得不到有關分子量分佈的資訊。 對一般的聚酯類纖維來說，在耐化學性特別是耐氣性 上具有優秀的水平。但是對於聚對苯二甲酸乙二酯和聚對 苯二甲酸丙二酯的伸縮性複合纖維來說，本發明人等發現 因其化學結構的差異，僅調節紡絲工藝條件，將結晶度提 尚到一定水平以上是有困難的，因此，非結晶部區域在接 觸各種使用水、自來水和地下水而膨脹時，由於氣成分而 使聚酯類伸縮性複合纖維的拉伸強度和伸縮性降低。 於是，本發明人等在發現具有粘度差的2種不同聚酯 類聚合物的分子量、分子量分佈以及纖維的微細結構等是 影響纖維伸縮性、耐氣拉伸強度、耐氣伸縮性和形態穩定 性等的因素後’設計了最佳的2種聚合物分子量、分子量 分佈和纖維的微細結構。 專利文獻1特開平10 — 72732號公報 專利文獻2特開2000 — 328378號公報 專利文獻3特開平9-41234號公報 專利文獻4美國專利第3671379號公報 專利文獻5特開平1 1-189923號公報 1286168 【發明内容】 本發明的目的在於提供複合纖維及其製造方法，通過 設計複合纖維最適合的分子量、分子量分佈以及微細結 構，即使不進行另外的後加工處理，所提供的複合纖維也 食b顯現不低於30%的自然捲曲拉伸率和不低於7〇%的自然 彈性恢復率，並且氣處理後的拉伸強度維持率大於等於 85% ’伸縮維持率大於等於8〇%。 、本發明提供複合纖維，其由第1成分和第2成分構成， 並且截面形態爲並列,所❹i成分是聚對苯二曱酸乙φ 二酯，所述第2成分是聚對苯二甲酸丙二酯；所述複合纖 維伸縮性和耐氣性優異，#曲面變形係數冑1〇〜12，截 面變形度（a/b)爲1.2〜2· 5,第1成分聚對苯二甲酸乙二酯 邛刀的結晶度爲30%〜45%，，第2成分聚對苯二甲酸丙二 ，的結晶度爲35%〜5〇%,氣處理後的拉伸強度維持率大於 ^於85/。、伸縮維持率大於等於8〇%、自然捲曲拉伸率大於 等於30%、自然彈性恢復率大於等於7〇%。 s優選所述第1成分聚對苯二甲酸乙二醋的數均分子量鲁 疋上300() 18GGG，分子量分佈係數是i 8〜2· 2;第2成分聚 對本二甲酸丙二醋的數均分子量是30000〜50000，分子量 分佈係數是1.8〜2.4。 另外，本發明提供伸縮性和耐氣性優異的複合纖維的 襄造方法，其是包括工序(A)和⑻的方法，其中，在工序 A::」使兩種聚酯熔融成爲熔融物，其中一種聚合物是聚 、本-甲酸乙二酯’其數均分子量爲13〇〇〇〜18〇〇〇，分子 1286168 量分佈係數爲1.8〜2 2,另一種聚合物是聚對苯二曱酸丙 二醋，數均分子3刚0〜5()_，分子量分佈係數是 1 · 8 2. 4 ,在工序（B)中，使所述熔融物通過紡絲元件，其 在紡絲元件内的停留時間小於等於5分鐘，然後以 2000〜4000 米 / 分絲 μ & μA ^ 、 刀鐘的紡絲速度，使捲曲張力爲 〇·〇5〜0.10g/d的水平，獲得並列形態的複合絲後，進行拉 伸和熱較，以滿；^第i成分聚對苯二甲酸乙二輯部分的 結晶度爲3GL45%、第2成分聚對苯二甲酸丙二醋的結晶 度爲35%〜50%。 優選採用部分取向—拉伸/假撚工藝進行所述拉伸工 序。 另外，所述拉伸溫度優選爲85〜95ΐ，熱固定溫度優 選爲120〜180°C。 另外，優選所述拉伸時拉伸絲斷頭率小於等於1〇%。 另外，本發明提供用所述複合纖維製造的撚數（TM :撚 /米）爲15 0〜2 0 0 0的加工絲。 另外’本發明提供所述複合纖維與拉伸率大於等於 50°/。、沸水收縮率大於等於15%的高收縮性的原紗混紡的混 合纖維絲。 另外，本發明提供含有所述複合纖維的布帛。 根據本發明製造的耐氣性優異的伸縮性複合纖維，即 使處於不經過染色、後加工時的沸水或幹熱處理的狀態， 也可以保持自然捲曲拉伸率大於等於3〇%、自然彈性恢復 率大於等於70%的優異的伸縮性，而且氣處理後的拉伸強 1286168 度維持率大於等於85%、伸缩+ Μ# 製。f縮維持率大於等於80%,原紗和 匕的申縮性優異’同時利用工業用水、自來水、地下水 於由工和洗膝時，其形態穩定性極其優異。另外，對 於由本發明製造的伸縮性複a纏給 物&㈣n七 复σ纖維，紡絲時，減少了聚合 :=牛内的停留時間，從而將分子量的減少、原紗 物理性質和伸縮性的降低減到最小程度，並且，通 2形態μ並列型、曲面變形係摘爲l =形度定爲….5水平，而使曲絲(d〇 ^ =變：係數減到最小程度。另外，爲提高伸縮性、耐 氣ί和工藝性，設計各成分的分子量和分子量分佈，使聚 對苯了甲g|^乙二酯的數均分子量爲13刚]8刪，分 刀佈係數疋1·8〜2.2;聚對苯二甲酸丙二g旨的數均分子 爲30000〜5〇〇〇〇，合八7士 U刀子量分佈係數爲1·8〜2.4,並且紡絲時 爲;了將分子量的減少和分子量分佈賴大減到最小程度， 而設定纺絲元件内的停留時間小於等於5分鐘，從 絲和拉伸效率最大化，將第1成分聚對苯二甲酸乙二醋部 ^的結晶度維持在_〜、第2成分聚對苯二甲酸丙二 酉曰的結晶度維持在35%〜5〇%的水平。另外，爲提高拉伸工 藝性，將捲曲張力維持在0.05〜0· l〇g/d的水平，拉伸時絲 的斷頭率減到最小，其工藝性優異，同時，原紗的強拉伸 率、耐氣性和自然伸縮特性等優異’所以其能夠應用於 物、緯編、經編等多種用途。 實施方式 10 1286168 現狀是，現有的伸縮性複合纖維，後續工序時的布第 通常縮小大於等於10%。使用工業用水、自來水、地下水 專進行後加工和洗務時，受到水中含有的氣的侵害，原紗 的拉伸強度和伸縮性降低，所以製品加工時，其條件難以 設定，難以使縫製品的尺寸穩定，並且後加工和洗滌處理 時’存在伸縮恢復特性降低的問題。另外，對於一般的聚 醋類潛在捲曲絲來說，在染色或後加工時的沸水或幹熱處 理過程中，根據2成分的雙金屬原理，通過收縮率差導致 的不同收縮而表現捲曲特性，所以利用聚酯類伸縮性原紗 而不進行沸水或幹熱處理的方布製品等伸縮性聚酯製品的 用途開發還不充分。 本發明人等發現對於聚對苯二甲酸乙二酯和聚對苯二 甲酸丙一酯的伸縮性複合纖維來說，因其化學結構的差 異，僅調節紡絲工藝條件，將結晶度提高到一定水平以上 是有困難的，因此，非結晶部區域在接觸各種使用水、自 來水和地下水而膨脹時，由於氣成分而使聚酯類伸縮性複 合纖維的拉伸強度和伸縮性降低。即本發明人等發現了因 2種聚酯類高分子的結構差和分子量差而表現伸縮性，還 發現通過使各成分的分子量分佈係數、紡絲時元件内的停 留時間和拉伸條件達到最適合程度，而使結晶度和結晶完 全性（perfectness)最大化，從而能夠將接觸各種使用水、 自來水和地下水而膨脹時氣成分造成的侵害減到最小。因 此，可知進行後加工和洗務時，即使沒有進行沸水或幹熱 處理’也能表現自然捲曲拉伸率不低於30%、自然彈性恢 1286168 70%的優異的自然捲曲特性，同1286168 IX. Description of the invention: The technical field of the genus is too versatile. The eucalyptus of the eucalyptus is improved. (2) Γ ϊΓ ϊΓ 二 二 二 二 二 二 二 二 二 二 二 二 二 二 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗 洗Additional dyeing or post-additional heat treatment, such as boiling water or dry heat treatment, is not limited to 7_natural elastic = failure rate, and the tensile strength maintenance rate after gas treatment is greater than the expansion retention ratio is greater than Equivalent to 80%, when applied to post-processing or washing, the product is extremely excellent in stretchability, gas resistance and form stability. [Prior Art] In the polyester-based stretchable fiber, a method of using two kinds of polyethylene terephthalate (ρΕΤ) having an intrinsic viscosity difference is disclosed in the patent document. Further, Patent Document 2 and Patent Document 3 make a method of producing a polyester-based latent crimping fiber by using a general polyethylene terephthalate and a highly shrinkable copolymerized polyethylene terephthalate. Known technology. Further, in Patent Document 4 and Patent Document 5, it is also proposed to use a stretchable polytrimethylene terephthalate (PTT) or polyterephthalic acid in polyethylene terephthalate (PET). The method of butylene diester (PBT). However, the polyester-type stretchable composite fiber produced by the production method described in the above-mentioned patent does not specifically mention the roll recovery property and gas resistance before the boiling water/dry heat treatment. The polyester-based stretchable composite fiber is characterized in that it usually has a bicomponent structure of two components, and during the dyeing or post-processing, during the heat treatment of the water or dry heat, the two components are curled by different shrinkage caused by the difference in shrinkage ratio of the two components. , showing curl characteristics. The current situation is that the general polyester-based stretch composite fiber has a crimp elongation ratio of 40% or higher after boiling water and dry heat treatment under no load or near no load light load, and elastic recovery The rate is 6〇% or more than 6%, but there is no technique which can maintain the stretching property even without performing the heat treatment, and maintain the tensile strength and the stretchability after the gas treatment. For the polyurethane fiber as a representative stretchable fiber, after the usual gas treatment, the tensile strength is lowered by about 3% or more and the stretchability is lowered by 20% or more. In addition, the polyester fiber is superior in gas resistance to polyurethane fibers, but it has a stretching property of a certain level or more even without boiling water or dry heat treatment, and can maintain tensile strength after gas treatment. The technology of polyester-based stretchable composite fibers with stretch characteristics is not guaranteed. Further, there is a risk that the shape is deformed or the tensile strength and the stretchability are lowered when the product is processed or washed. In addition, the prior patent literature relating to stretchable composite fibers basically only proposes the use of different polyester polymers for the manufacture of composite spun yarns, and does not mention the molecular weight distribution of the different high molecular polymers constituting the composite fibers themselves and the fine structure of the composite fibers. The impact of physical properties. Patent Document 4 mentions changes in physical properties caused by changes in viscosity of polyethylene terephthalate (PET), polyparaxyl propylene dicarboxylate (ρττ), and modified PET and PTT, but 6 1 1286168 这篇 'This patent also does not mention the molecular weight distribution of different polymers constituting the composite fiber. Of course, according to the Mark_H〇uwink equation, the molecular weight can be inferred from the relationship of viscosity-molecular weight, but information on the molecular weight distribution is not obtained. For general polyester fibers, it has an excellent level of chemical resistance, particularly gas resistance. However, for the stretchable composite fiber of polyethylene terephthalate and polytrimethylene terephthalate, the inventors have found that only the spinning process conditions are adjusted due to the difference in chemical structure, and the crystallinity is raised. It is difficult to reach a certain level or more. Therefore, when the amorphous portion is inflated in contact with various water, tap water, and groundwater, the tensile strength and stretchability of the polyester-based stretchable composite fiber are lowered by the gas component. Then, the present inventors have found that the molecular weight, molecular weight distribution, and fine structure of fibers of two different polyester polymers having a difference in viscosity affect fiber stretchability, gas tensile strength, gas stretchability, and form stability. After the factors such as sex, 'the optimal two kinds of polymer molecular weight, molecular weight distribution and fine structure of the fiber were designed. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. 1286168 SUMMARY OF THE INVENTION An object of the present invention is to provide a composite fiber and a method for producing the same, by designing a molecular fiber, a molecular weight distribution, and a fine structure which are most suitable for a composite fiber, and providing a composite fiber even if no additional post-treatment is performed. The natural crimp elongation of not less than 30% and the natural elastic recovery rate of not less than 7% are exhibited, and the tensile strength maintenance ratio after the gas treatment is 85% or more and the stretch retention ratio is 8% or more. The present invention provides a composite fiber comprising a first component and a second component, and having a cross-sectional form in parallel, wherein the component is a polyethylene terephthalate, and the second component is polyterephthalic acid. Propylene ester; the composite fiber is excellent in stretchability and gas resistance, #面面 deformation coefficient 胄1〇~12, cross-sectional deformation degree (a/b) is 1.2~2·5, the first component polyethylene terephthalate The crystallinity of the diester boring knife is 30% to 45%, and the crystallinity of the second component polytrimethylene terephthalate is 35% to 5〇%, and the tensile strength maintenance rate after the gas treatment is greater than ^85. /. The expansion retention rate is greater than or equal to 8〇%, the natural crimp elongation is greater than or equal to 30%, and the natural elastic recovery rate is greater than or equal to 7〇%. s preferably, the number average molecular weight of the first component polyethylene terephthalate is 300 () 18 GGG, the molecular weight distribution coefficient is i 8 2 2 2; the second component is the number of polyparaben propylene glycol diacetate The average molecular weight is from 30,000 to 50,000, and the molecular weight distribution coefficient is from 1.8 to 2.4. Further, the present invention provides a method for producing a conjugate fiber excellent in stretchability and gas resistance, which is a process comprising the steps (A) and (8), wherein in the step A::", the two polyesters are melted into a melt, One of the polymers is poly(p-ethylene glycolate) whose number average molecular weight is 13〇〇〇18〇〇〇, the molecular weight distribution coefficient of 1286168 is 1.8~2 2, and the other polymer is polyparaphenylene difluoride. Acid propylene diacetate, number average molecule 3 just 0~5 () _, molecular weight distribution coefficient is 1 · 8 2. 4, in the process (B), the melt is passed through the spinning element, which is in the spinning element The residence time in the interior is less than or equal to 5 minutes, and then the warp speed is 〇·〇5 to 0.10 g/d at a spinning speed of 2000 to 4000 m/min, μ & μA ^ , and the knives are obtained in a side-by-side manner. After the composite yarn, the stretching and heat are compared to the full; the crystallinity of the i-component polyethylene terephthalate portion is 3GL45%, and the crystallinity of the second component polytrimethylene terephthalate is 35% to 50%. The stretching process is preferably carried out using a partial orientation-drawing/false twisting process. Further, the stretching temperature is preferably 85 to 95 Å, and the heat setting temperature is preferably 120 to 180 °C. Further, it is preferable that the tensile yarn breakage rate at the time of stretching is 1% or less. Further, the present invention provides a processed yarn having a number of turns (TM: 捻 / m) of 15 0 to 2 0 0 manufactured by the conjugate fiber. Further, the present invention provides the composite fiber and the elongation ratio of 50 ° / or more. A high-shrinkage raw yarn-blended mixed fiber yarn having a boiling water shrinkage ratio of 15% or more. Further, the present invention provides a fabric comprising the composite fiber. The stretchable conjugate fiber excellent in gas resistance produced by the present invention can maintain a natural crimp elongation of 3% or more and a natural elastic recovery rate even in a state of boiling water or dry heat treatment without dyeing or post-processing. Excellent stretchability of 70% or more, and the tensile strength after gas treatment is 1286168 degrees, the retention rate is 85% or more, and the expansion and contraction is +#. The shrinkage retention rate is 80% or more, and the original yarn and the yttrium have excellent shrinkage. When using industrial water, tap water, and ground water for work and knee washing, the shape stability is extremely excellent. In addition, with respect to the stretchable complex wrapper & (iv) n-seven complex sigma fiber produced by the present invention, when spinning, the polymerization time is reduced: = residence time in the cattle, thereby reducing the molecular weight, the physical properties of the raw yarn, and the stretchability. The reduction is minimized, and the pass form 2 is juxtaposed, the surface deformation is extracted as l = shape is set to ... 5 level, and the curve is changed (d〇^ = change: the coefficient is minimized. In order to improve the flexibility, gas resistance and processability, the molecular weight and molecular weight distribution of each component are designed, so that the number average molecular weight of poly(p-phenylene) g|^ ethylene diester is 13], and the distribution coefficient is 疋1·8~2.2; the number average molecular weight of poly(trimethylene terephthalate) is 30,000~5〇〇〇〇, and the distribution coefficient of U knives is 8.8~2.4, and is spinning; The molecular weight reduction and the molecular weight distribution are minimized, and the residence time in the spinning element is set to be less than or equal to 5 minutes, and the first component is polyethylene terephthalate. The crystallinity of the part is maintained at _~, and the crystallinity dimension of the second component poly(trimethylene terephthalate) In the level of 35%~5〇%. In addition, in order to improve the stretching processability, the crimping tension is maintained at a level of 0.05~0·l〇g/d, and the yarn breakage rate during stretching is minimized, and the process thereof is minimized. It is excellent in the strength, and the original yarn has excellent tensile strength, gas resistance, and natural stretch characteristics. Therefore, it can be applied to various applications such as weaving, weft knitting, warp knitting, etc. Embodiment 10 1286168 The current situation is that the existing stretchability In the case of composite fibers, the cloth in the subsequent process is usually reduced by 10% or more. When industrial water, tap water, and ground water are used for post-processing and washing, the tensile strength and stretchability of the original yarn are reduced by the gas contained in the water. Therefore, when the product is processed, the conditions are difficult to set, it is difficult to stabilize the size of the sewn product, and there is a problem that the stretch recovery property is lowered during the post-processing and the washing treatment. In addition, for the general polystyrene potential crimped yarn, In the boiling water or dry heat treatment during dyeing or post-processing, according to the bimetallic principle of the two components, the crimping property is exhibited by the different shrinkage caused by the difference in shrinkage ratio, so the polyester is utilized. The development of the use of a stretchable polyester product such as a stretch fabric having a stretchable raw yarn without boiling water or dry heat treatment is not sufficient. The present inventors have found that for polyethylene terephthalate and polytrimethylene terephthalate In the case of the ester-strainable composite fiber, it is difficult to adjust the crystallinity to a certain level or more due to the difference in chemical structure. Therefore, the amorphous portion is in contact with various waters, tap water, and When the groundwater is swelled, the tensile strength and the stretchability of the polyester-based stretchable conjugate fiber are lowered by the gas component. The present inventors have found that the polyester polyester polymer exhibits a structural difference and a molecular weight difference. It has also been found that by making the molecular weight distribution coefficient of each component, the residence time in the element during spinning, and the stretching conditions to the most suitable degree, the crystallinity and the crystal completeness are maximized, so that various uses can be contacted. Invasion caused by gas components when water, tap water and groundwater expand. Therefore, it is understood that the excellent natural curling property of the natural crimp elongation of not less than 30% and the natural elasticity of 1286168 70% can be exhibited even when the post-processing and the washing are performed without boiling water or dry heat treatment.
復率不低於 異，氣處理. 於是，補；®姻銘痛人处1 _The rate of recovery is not lower than the difference, the gas treatment. So, make up;
本發明巾對複合纖維的分子量、分子量分佈和微細結 構進行如下調節以製造具有優異的自㈣縮性和耐氣性的 聚酯類複合纖維。 本發明使用的2種聚合物優選第丨成分是數均分子量 爲13000〜18000，分子量分佈係數爲18〜2·2的聚對苯二 曱酸乙二酯；第2成分是數均分子量爲3〇〇〇〇〜5〇〇〇〇，分 子量分佈係數爲1· 8〜2· 4的聚對苯二曱酸丙二酯。 作爲本發明使用的聚合物，可以使用工業上使用的聚 酯類聚合物和它們的改性聚合物等。作爲具體的例子有以 聚對苯二甲酸乙二酯、聚對笨二甲酸丙二酯、聚對苯二甲 酸丁二酯等爲代表的聚酯；和用異戊酸、聚乙二醇等改性 的它們的共聚物等。 這些聚合物可以用一般所知的本體聚合、溶液聚合、 介面聚合等方法製造，本發明中，目的聚合物可以用其中 的任意一種方法製造，特別優選通過本體聚合法中的熔融 12 1286168 聚合或固體聚合製造的聚合物，這樣的聚合物在製造經費 方面是有利的。 本發明中，低分子量高分子的分子量最小值定爲 13000 ’高分子量高分子的分子量最大值定爲50000，其理 由如下。製造分子量不足13000的聚合物，對於聚合方法 本身並不難。但是，爲了利用這個聚合物進行纖維化，將 其製成片屑（或顆粒）狀的形態是有利的。而分子量不足 13000的話，製成片屑時，太容易破碎，所以難以製造具 有均勻形狀的片屑。另外，在氣處理時，相對容易受侵害。 分子量超過50000時，聚合時間過長，不僅在經濟方面不 利，而且由於必須過度提高紡絲溫度，熱分解導致分子量 減少、分子量分佈擴大，所以其作用不能體現。 另外，將聚對苯二甲酸乙二醋的分子量分佈係數限定 f U~2. 2,將聚對笨二甲酸丙二醋的分子量分佈係數限 疋在1.8 2. 4,延疋因爲，分子量分佈係數如果小於下限 分子量分佈太平均、低分子量物質的自增塑作用微 =微：工藝上容易發生問題；分子量分佈係數大於上限 值時刀子量分佈變大’表現爲多個聚合物混雜的效果， 所以伸縮性低下，並且隨著分子 方的數均分子量變低，相y 他刀于重 結晶的不充分之處分佈率變高，所以 難以使結晶度提高到一定二卜以：絲和拉伸工序上，變得 的問題。《水h上，還産生了耐氣性降低 本發明中 數均分子量t分子量分佈係數是將聚合物 1286168 /合解在，、氟異丙醇（HFIP)中，利用高溫用GPC設備（美國 aters a司），以聚苯乙烯作爲基準物質，測定數均分子 量（Μη)和重均分子量（Mw)，從下式⑴換算出分子量分佈係 數（PDI) 〇 [式⑴]The towel of the present invention adjusts the molecular weight, molecular weight distribution and fine structure of the composite fiber as follows to produce a polyester-based composite fiber having excellent self-reducing properties and gas resistance. The two polymers used in the present invention preferably have a second component of polyethylene terephthalate having a number average molecular weight of 13,000 to 18,000 and a molecular weight distribution coefficient of 18 to 2·2; and a second component having a number average molecular weight of 3; 〇〇〇〇~5〇〇〇〇, poly(p-phenylene terephthalate) having a molecular weight distribution coefficient of 1·8~2·4. As the polymer used in the present invention, commercially available polyester polymers, modified polymers thereof and the like can be used. Specific examples include polyesters represented by polyethylene terephthalate, poly(p-propylene succinate), polybutylene terephthalate, and the like; and isovaleric acid, polyethylene glycol, and the like. Modified copolymers thereof and the like. These polymers can be produced by a generally known method of bulk polymerization, solution polymerization, interface polymerization, etc., and in the present invention, the polymer of interest can be produced by any one of the methods, particularly preferably by melting 12 1286168 in bulk polymerization or Polymers produced by solid polymerization, such polymers are advantageous in terms of manufacturing costs. In the present invention, the molecular weight of the low molecular weight polymer is set to be 13,000 Å. The maximum molecular weight of the high molecular weight polymer is set to 50,000, and the reason is as follows. The production of a polymer having a molecular weight of less than 13,000 is not difficult for the polymerization method itself. However, in order to utilize this polymer for fibrillation, it is advantageous to form it into a chip (or granule) form. On the other hand, when the molecular weight is less than 13,000, when the chips are formed, the chips are too easily broken, so that it is difficult to produce chips having a uniform shape. In addition, it is relatively easy to be invaded during gas treatment. When the molecular weight exceeds 50,000, the polymerization time is too long, which is not only economically disadvantageous, but also because the spinning temperature is excessively increased, the molecular weight is reduced due to thermal decomposition, and the molecular weight distribution is enlarged, so that the effect cannot be exhibited. In addition, the molecular weight distribution coefficient of the polyethylene terephthalate is limited to f U~2. 2, and the molecular weight distribution coefficient of the poly(p-propylene dicarboxylate) is limited to 1.8 2. 4, because of the molecular weight distribution. If the coefficient is less than the lower limit, the molecular weight distribution is too average, and the self-plasticization effect of the low molecular weight substance is slightly micro: the process is prone to problems; when the molecular weight distribution coefficient is larger than the upper limit, the knife amount distribution becomes larger, which is manifested by the effect of multiple polymers. Therefore, the stretchability is low, and as the number average molecular weight of the molecular side becomes lower, the distribution rate of the phase y is insufficient in recrystallization, so it is difficult to increase the crystallinity to a certain level: silk and pull In the process of stretching, it becomes a problem. "Water h, also produced a decrease in gas resistance. The molecular weight distribution coefficient of the present invention is the molecular weight distribution coefficient of the polymer 1286168 /, in the fluoroisopropanol (HFIP), using high temperature GPC equipment (US aters As a reference material, the number average molecular weight (Μη) and the weight average molecular weight (Mw) are measured by using polystyrene as a reference material, and the molecular weight distribution coefficient (PDI) is converted from the following formula (1) 〇 [Formula (1)]
PDI = A 本發明中進行熔融紡絲時，聚合物的紡絲溫度設定爲 比各聚合物熔融溫度高2〇〜7(rc的溫度，聚合物的紡絲溫 度比聚合物熔融溫度高出的溫度小於2〇。匚時，會因熔融不 均勻而導致擠出機内的壓力變得過高，操作性降低，另外， 谷易産生製成的複合纖維的物理性質不均勻等問題，所以 不是優選的。另外，聚合物的紡絲溫度比聚合物的熔融溫 度咼出的溫度大於70。〇時，聚合物的流動性得到改善，但 聚合物發生熱分解等問題，所以不是優選的。 使吐出的各纖維狀聚合物在喷絲頭下結合，可以製造 出並列截面的複合纖維。 另外’在紡絲元件内被結合紡絲的偏心芯鞘型複合纖 維’因紡絲時的分子量差和粘度差而産生曲絲問題，解決 這個問題可以通過在噴絲頭的正下方進行結合，如圖i和 圖2那樣，控制原紗截面上聚合物之間的曲面變形係數爲 1· (M· 2，變形度爲1. 2〜2. 5。 另外，本發明人等發現分子量高的聚合物紡絲時，分 子量由於熱分解而大幅度降低，分子量分佈也變寬，所以 最大程度地減少紡絲元件内的聚合物熔融體的停留時間， 1286168 將其疋爲彳、於等於5分鐘，可以在極大程度上發揮所述特 徵帶來的物理性質、耐氯性和伸縮性。 ’ a i對於得到的複合纖維，可以採用通常的聚酯複合纖維 製每中利用的部分取向_拉伸/假撚工藝進行纖維化。 作爲本發明核心技術的構成要素，可以舉出將紡絲速 ^定爲2000〜4000米/分鐘。這是因爲，以小於2000米/ :刀的速度紡絲日寺’因低速紡絲導致聚合物熔融體的吐出量 減少，這不僅於經濟方面不利，而且拉伸時的拉伸比增加， 5熱收縮率上升，最終，對熱的形態敎性急劇下降。 般在低紡絲速度下以南倍率拉伸而形成的有結晶纖維 表現出對熱的高收縮率。另外，以大於4000米/分鐘的紡 絲速度紡絲時，2 _不同分子量的聚合物之間的熱特性、 物理特徵有很大不同’這導致紡絲性降低，進而紡絲工序 的穩定性下降，所以不是優選的。 另外，本發明的特徵之一爲，將卷取張力設定在 U5〜0. 1()g/d水平進行卷取。卷取張力小於Q5g/d時， 有因紡絲時絲的超餵（over feed)而使加工性降低的缺 點，卷取張力大於G.1()g/d時，紡絲時雖然不存在特別的 問題’但拉伸/假撚時，因捲曲的顯現和伸縮特性而使分絲 張力不穩定’增加絲的斷頭’存在加工性降低的缺點。 a作爲本發明的另一個技術核心的構成要f，它的特徵 是在採用部分取向-拉伸/假撚工藝製造時，錄伸溫度^ 爲85〜95t，熱固定溫度定爲12(M8(rc。對於拉伸溫^來 說’小於85。0：的溫度難以形，均句的拉伸，而大於阶的 1286168 溫度，熱量使增塑的程度增大，並且紡絲時的加工性、其 物理性質以及耐氣性變得不穩^，所以不是優選的。熱固 定溫度小於12(TC時，原紗及製品的結晶度、結晶的完全 性和非結晶區域的取向度減小，並且，熱收縮率增加，形 態穩定性和耐氯性下降；另外，熱㈣溫度大於18代時， 增塑程度變大，加工性和各項物理性質下降，所以不是優 選的。 作爲本發明最重要核心的技術構成要素，舉出是在複 合纖維拉伸絲中，第1成分聚對苯二甲酸乙二酯部分的結 晶度爲30%〜45%，第2成分聚對苯二甲酸丙二酯的結晶度 爲35%〜50%。本發明人等發現複合纖維的耐氣性與結晶度 有緊密相關的關係，通過將複合纖維的微細結構設計得更 加緻密，就可能改善複合纖維的耐氣性。 另外，根據本發明製造的複合纖維，通過紡絲時減小 聚合物在紡絲元件内的停留時間而使分子量的減少、原紗 物理性質和伸縮性的降低減到最小程度，並且，通過利用 在噴絲頭的正下方進行結合的工藝，如圖1和圏2那樣， 製成曲面變形係數爲1·〇〜1· 2、變形度爲ι·2〜2· 5水平的 並列型，與圖3那樣的現有的偏心芯鞘型原紗相比，纺絲 時的曲絲問題導致的加工性、功能性和物理性質的降低減 小到最小程度，另外，通過將卷取張力維持在 〇· 〇5〜0· 1 〇g/d的水平而使拉伸時的絲斷頭率減小到最小。 根據本發明的制絲條件製成的纖維的物理性質及功能 性示於表1。 1286168 實施例 以下，基於下述實施例，更詳細地說明本發明。下述 的實施例只是舉例說明本發明，並不限定本發明的範圍。 首先’說明根據本發明的方法製造的結合型複合纖維 的物理性質的評價基準和其測定方法。 ^ (1)數均分子量和分子量分佈的測定方法PDI = A In the melt spinning of the present invention, the spinning temperature of the polymer is set to be higher than the melting temperature of each polymer by 2 to 7 (the temperature of rc, and the spinning temperature of the polymer is higher than the melting temperature of the polymer). When the temperature is less than 2 Torr, the pressure in the extruder becomes too high due to uneven melting, and the workability is lowered. Further, the grain is liable to cause problems such as uneven physical properties of the produced conjugate fiber, which is not preferable. Further, the spinning temperature of the polymer is higher than the melting temperature of the polymer by more than 70. When enthalpy, the fluidity of the polymer is improved, but the polymer is thermally decomposed and the like, so that it is not preferable. Each of the fibrous polymers is bonded under the spinneret to produce a composite fiber of a side-by-side cross section. In addition, the molecular weight difference and viscosity of the eccentric core-sheath type composite fiber which is combined and spun in the spinning element due to spinning The problem of the curved wire is caused by the difference. The problem can be solved by combining directly under the spinneret. As shown in Fig. i and Fig. 2, the deformation coefficient of the surface between the polymers on the cross section of the original yarn is controlled as 1. (M. 2, the degree of deformation is 1. 2 to 2. 5. When the present inventors have found that the polymer having a high molecular weight is spun, the molecular weight is greatly reduced by thermal decomposition, and the molecular weight distribution is also widened. Minimize the residence time of the polymer melt in the spinning element, and 1286168 converts it to 彳, which is equal to 5 minutes, which can greatly exert the physical properties, chlorine resistance and flexibility of the characteristics. ' ai For the obtained conjugate fiber, it can be fiberized by the partial orientation _ stretching/false twisting process used in the usual polyester composite fiber. As a constituent element of the core technology of the present invention, spinning can be mentioned. The speed is set to 2000 to 4000 m/min. This is because the spinning of the Japanese temple at a speed of less than 2000 m/: knives reduces the amount of polymer melt discharged due to low-speed spinning, which is not only economically disadvantageous. Further, the stretching ratio at the time of stretching increases, and the heat shrinkage rate increases. Finally, the heat enthalpy is drastically lowered. The crystal fiber formed by stretching at a low spinning speed at a south spinning speed exhibits heat. high In addition, when spinning at a spinning speed of more than 4,000 m/min, thermal properties and physical characteristics between polymers of 2 _ different molecular weights are greatly different, which results in a decrease in spinnability and further a spinning process. Further, one of the features of the present invention is that the winding tension is set at a level of U5 to 0.1 (g/d), and the winding tension is less than Q5g/d. There is a disadvantage that the workability is lowered due to the over feed of the silk at the time of spinning. When the take-up tension is greater than G.1 () g/d, there is no particular problem in spinning, but the stretching/false In the case of enthalpy, the tension of the yarn is unstable due to the appearance of the curl and the expansion and contraction characteristics, and the breakage of the yarn is increased, which has the disadvantage of lowering the workability. a. The composition of another core of the present invention is f, which is characterized in that When manufactured by the partial orientation-stretching/false twisting process, the recording temperature ^ is 85 to 95 t, and the heat setting temperature is set to 12 (M8 (rc. For the tensile temperature ^, the temperature less than 85.0: is difficult to shape, the stretching of the sentence is uniform, and the temperature is greater than the order of 1286168. The heat increases the degree of plasticization, and the processability and physicality of spinning The nature and gas resistance become unstable, so it is not preferable. When the heat setting temperature is less than 12 (TC), the degree of crystallinity of the raw yarn and the product, the completeness of crystallization, and the degree of orientation of the amorphous region are reduced, and the heat shrinkage rate is increased, the form stability and the chlorine resistance are lowered; (4) When the temperature is greater than 18 generations, the degree of plasticization becomes large, and the workability and various physical properties are degraded, so that it is not preferable. As a technical component of the most important core of the present invention, it is mentioned that in the composite fiber drawn yarn, The crystallinity of the polyethylene terephthalate portion of the first component is 30% to 45%, and the crystallinity of the second component polytrimethylene terephthalate is 35% to 50%. The inventors have found that the composite fiber The gas resistance is closely related to the crystallinity, and by designing the fine structure of the composite fiber to be denser, it is possible to improve the gas resistance of the composite fiber. In addition, the composite fiber produced according to the present invention is reduced by spinning. The residence time of the polymer in the spinning element minimizes the decrease in molecular weight, the physical properties and the stretchability of the raw yarn, and the process of bonding by directly under the spinneret As shown in Fig. 1 and Fig. 2, a side-by-side type with a curved surface deformation coefficient of 1·〇~1·2, a degree of deformation of ι·2 to 2·5, and a conventional eccentric core-sheath type yarn of Fig. 3 are produced. In comparison, the reduction in workability, functionality, and physical properties caused by the problem of the filament at the time of spinning is minimized, and the winding tension is maintained at 〇· 〇5 to 0·1 〇g/d. The yarn breakage rate at the time of stretching was reduced to the minimum. The physical properties and functional properties of the fibers produced according to the spinning conditions of the present invention are shown in Table 1. 1286168 Examples Hereinafter, based on the following examples, The present invention is described in detail. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. First, the evaluation criteria of the physical properties of the bonded composite fibers produced by the method of the present invention and the method for measuring the same will be described. ^ (1) Method for determining number average molecular weight and molecular weight distribution
將聚合物溶解於六氟異丙醇（HFIP)，利用高溫用GPC 設備（美國Waters公司），以聚苯乙烯爲基準物質測定數均 分子量（Μη)和重均分子量（Mw),從下式（2)換算出分子量分 佈係數（PDI) [式⑵] (2)自然捲曲拉伸率和自然彈性恢復率的測定方法 爲了測定實施例中製造的可形成捲曲的複合纖維的作 爲其物理性質的自然捲曲拉伸率和自然彈性恢復率，按下 述進行操作。 以0· 05g/d的分絲張力從纖維束中卷取，獲得 800 1500丹尼爾後，放置2〇分鐘。將經過前面階段的樣 口口，在0· 002g/d負荷下，放置2分鐘以後，測定此時的長 度（Li)。在所述樣品上加〇· lg/d負荷，測定2分鐘後的長 度（L2)。然後’除去〇· lg/d負荷後，2分鐘後測定長度 用下述式⑻和式⑷算出自然捲曲拉伸率和自然:彈性恢復 率。The polymer was dissolved in hexafluoroisopropanol (HFIP), and the number average molecular weight (Μη) and the weight average molecular weight (Mw) were determined using a GPC apparatus (Waters, USA) at a high temperature using polystyrene as a reference substance. (2) Conversion of molecular weight distribution coefficient (PDI) [Formula (2)] (2) Method for measuring natural crimp elongation ratio and natural elastic recovery ratio In order to measure the physical properties of the crimpable composite fiber produced in the examples The natural crimp elongation and the natural elastic recovery rate were carried out as follows. The fiber bundle was taken up at a take-up tension of 0·05 g/d to obtain 800 1500 denier, and left for 2 minutes. The length (Li) at this time was measured after leaving the sample port of the previous stage and placing it under a load of 0·002 g/d for 2 minutes. A 〇· lg/d load was applied to the sample, and the length (L2) after 2 minutes was measured. Then, after the load of 〇· lg/d was removed, the length was measured after 2 minutes. The natural crimp elongation and the natural: elastic recovery ratio were calculated by the following formulas (8) and (4).
\)y 3 /V 自然捲曲拉伸率（％)==[(L2_Li)/L2]x1〇〇 17 1286168 自然彈性恢復率（％ ) = [(L2 — ⑷ 3；/CL2- Li)]xl〇〇 ⑶对氣性（拉伸強度維持率、伸縮維持率）的 利用次氣酸，在有效氣量爲⑽—爲?·： 將製造的複合纖維於3(rc_ 72小時4時 器以便有效氣不釋放到空氣中，處理72小時，然後^ 自然乾燥後，通過下述式（5M8)算出氣水處理的原紗的拉 伸強度維持率和伸縮維持率。 拉伸強度維持率（％) = S1/S()X100 (5) (S。：氣水處理前的拉伸強度，Si:氣水處理後的拉伸 強度） (此處’拉伸強度是基於KS κ 〇412測定的。） 伸縮維持率（％)=(捲曲拉伸維持率+彈性恢復維持 率)/2 (6) 牙 捲曲拉伸維持率（％) = (VCqx1〇〇 (?) (c。：氣水處理前的自然捲曲拉伸率，Ci ••氣水處理 的自然捲曲拉伸率） (此處，自然捲曲拉伸率（C()、Ci)的測定是基於上述（2) 的自然捲曲拉伸率的測定方法實施的） 彈性恢復維持率（％) = Ει/Ε〇χ1〇〇 ⑻ (E〇 .氣水處理前的自然彈性恢復率，:氣水處理後 的自然彈性恢復率） (此處’自然彈性恢復率（E。、E!)的測定是基於上述（2) 的自然彈性恢復率的測定方法實施的） 1286168 (4) 原紗截面的曲面變形係數和變形度的評價 如圖卜圖2和圖3所示，用掃描式電子顯微鏡（sem) 分析原紗的截面，然後，根據下述式（9)和式（1〇)進行計算。 曲面變形係數=c/d (9) 變形度=a/b (1〇) (5) 拉伸絲斷頭率的測定方法 以2kg的拉伸絲卷量對20〇根部分拉伸絲進行拉伸， 用百分率（％)表示絲斷頭的根數。 (6) 結晶度 根據X射線廣角衍射法測定拉伸和熱固定後的複合纖 維的結晶度，然後，根據Lorentzian分析法分離聚對苯二 甲酸乙二酯和聚對苯二甲酸丙二酯的結晶峰，再根據如下 式（11)測定各結晶度。 結晶度=(1 — Σ la/ Σ Ial〇〇)xl〇〇 (11) (此處，Ia=高分子的非結晶區域的散射強度，131。。=高 刀子的100%非結晶區域的散射強度） 實施例1 製造伸縮性複合纖維的過程中，設定紡絲溫度爲275 C、紡絲速度爲2800米/分鐘、捲曲張力爲〇· 〇9g/d、元 件内停留時間爲3分鐘，利用現有熔融複合紡絲設備，以 重量比5:5的比例，將數均分子量（Mn)爲ι4632、分子量 分佈係數（PDI)爲2.2的聚對苯二曱酸乙二酯和數均分子 量（Μη)爲32149、分子量分佈係數（{^。爲2· 4的聚對苯二 甲酸丙二酯，以圖l-(a)的並列截面，製造聚酯複合纖維。 1286168 置’對經所述纺絲/卷取而獲得的複合纖 維。實施扣拙± &單絲細度爲2·1丹尼爾的伸縮性複合纖 定溫产致ΐς。日、，拉伸比爲i·60、拉伸溫度爲85<t、熱固 耐〇C，結果示於表卜得到的纖維表現出優異的 、伸縮特性和拉伸加工性。 實施例2 〇 1 &伸縮性複合纖維的過程中H纺絲溫度爲280 彼纺絲速度爲2600米/分鐘、捲曲張力爲（K07g/d、元 内停留時間爲4分鐘，利用現有熔融複合紡絲設備，以 量比5:5的比例，將數均分子量（Μη)爲14632、分子量 刀佈係數（PDI)爲2.2的聚對苯二甲酸乙二g旨和數均分子 ^ (Μη)爲39334、分子分佈係數⑽爲）2.2的聚對苯二甲 -文丙一 g曰，以圖l—(a)的並列截面，製造聚酯複合纖維。 利用其他的拉伸裝置，對經所述紡絲/卷取而獲得的複合纖 維進行拉伸，製造單絲細度爲2·丨丹尼爾的伸縮性複合纖 維。實施拉伸時，拉伸比爲丨· 70、拉伸溫度爲90艽、熱固 定溫度爲160。(：，結果示於表卜得到的纖維表現出優異的 耐氣性、伸縮特性和拉伸加工性。 實施例3 製造伸縮性複合纖維的過程中，設定紡絲溫度爲283 °C、紡絲速度爲2400米/分鐘、捲曲張力爲〇. 〇8g/d、元 件内停留時間爲4分鐘，利用現有熔融複合紡絲設備，以 重量比5:5的比例，將數均分子量（Μη)爲16422、分子量 分佈係數（PDI)爲2.1的聚對苯二曱酸乙二酯和數均分子 !286168 (fn)爲45752、分子量分佈係數（[>1)1)爲2 〇的聚對苯二 :^丙一自曰’以圖[(a)的並列截面，製造聚酯複合纖維。 」用，他的拉伸裝置’對經所述紡絲/卷取而獲得的複合纖 給進行拉伸’製造單絲細度爲2· 1丹尼爾的伸縮性複合纖 〜實施拉伸時’拉伸比爲17Q、拉伸溫度爲9『c、熱固 =/皿度爲160 C ’結果示於们。得到的纖維表現出優異的 耐氣性、伸縮特性和拉伸加工性。 實施例4 。製化伸縮性複合纖維的過程中，設定紡絲溫度爲285 2、、方絲速度爲2100米/分鐘、捲曲張力爲0. 08g/d、元 内停留時間爲4分鐘，利用現有溶融複合紡絲設備，以 、量比6:4的比例’將數均分子量（Μη)爲16422、分子量 2係數爲2」的聚對苯二甲酸乙二s旨和數均分子 ，⑽爲细8、分子量分佈係數⑽）爲U㈣對苯二 :酸丙二醋’以圖卜⑻的並列截面，製造聚醋複合纖維。 维、n的拉伸裝置，對經所述纺絲/卷取而獲得的複合纖 ΓΓΓ，製造單絲細度爲2」丹尼爾的伸縮性複合纖 維。實施拉料，拉伸比爲164 定溫度爲170t，妹果干於矣…， 舄9〇C熱固 果不於表卜得到的纖維表現出優異的 耐氣性、伸縮特性和拉伸加工性。 比較例1 複合纖維的過程中’設定纺絲溫度爲270 、’…速又爲2800米/分鐘、捲曲張力 一 件内停留時間爲3分鐘，利】現有熔融複合紡絲設"備，： 1286168 重量比5:5的比例，將數均分子量(Mn)爲11683、分子量 刀佈係數（PDI)爲2.2的聚對苯二甲酸乙二醋和數均分子 量（Μη)爲14054、分子量分佈係數（pDI)爲2 3的聚對苯二 甲&丙一g日’以圖卜⑷並列截面，製造聚醋複合纖維。 利用其他的拉伸裝置，對經所述紡絲/卷取而獲得的複合纖 維進行拉伸，製造單絲細度爲21丹尼爾的伸縮性複合纖 維實施拉伸時’拉伸比爲16〇、拉伸溫度爲85^、熱固 定溫度爲15G°C ’結果示於表卜得到的纖維耐氣性和拉伸 加工性比較良好，而伸縮特性低下。 馨 比較例2 。製這伸縮性複合纖維的過程中，設定紡絲溫度爲270 C ’纺絲速度爲2600米/分鐘、捲曲張力爲〇· 15g/d、元 件内停留時間爲8分鐘，利用現有熔融複合紡絲設備，以 重量比5:5的比例，將數均分子量（Μη)爲11683、分子量 分佈係數（PDI)爲2.2的聚對苯二甲酸乙二g旨和數均分子 量（Mn)爲23744、分子量分佈係數（PDI)爲2· 8的聚對苯二 甲-文丙自曰以圖3的偏心芯勒型截面，製造聚酯複合纖 維。利用其他的拉伸裝置，對經所述紡絲/卷取而獲得的複 合纖維進行拉伸，製造單絲細度爲2.1丹尼爾的伸縮性複 。纖維。實施拉伸時，拉伸比爲：· 7〇、拉伸溫度爲8〇。〇、 熱固定溫度爲14〇°c，結果示於表卜得到的纖維耐氣性、 伸縮特性和拉伸加工性低下。 比較例3 製造伸縮性複合纖維的過程中，設定紡絲溫度爲28〇 22 1286168 t、紡絲速度爲1400米/分鐘、捲曲張力爲〇· i4g/d、元 件内停留時間爲8分鐘，利用現有熔融複合紡絲設備，以 重量比5 ·· 5的比例，將數均分子量（Mn)爲2〇422、分子量 分佈係數（PDI)爲2.4的聚對苯二甲酸乙二酯和數均分子 量（Μη)爲66450、分子量分佈係數（pDI；)爲2.7的聚對苯二 甲酸丙二酯，以圖1-(a)的並列截面，製造聚酯複合纖維。 利用其他的拉伸裝置，對經所述紡絲/卷取而獲得的複合纖 維進行拉伸，製造細度爲2· 1丹尼爾的伸縮性複合纖維。 實施拉伸時，拉伸比爲2· 90、拉伸溫度爲75t、熱固定溫 X爲145 C，結果示於表1。得到的纖維耐氣性、伸縮特性 和拉伸加工性低下。 23 1286168 表1 實施例 1 實施例 2 實施例 3 實施例 4 比較例 1 比較例 2 比較例 3 聚合物Α(Μη) PET2) (14632) PET (14632) PET (16422) PET (16422) PET (11683) PET (11683) PET (20422) 聚合物Β(Μη) ρττ3) (32149) PTT (39334) PTT (45752) PTT (49118) PTT (14054) PTT (23744) PTT (66450) PDKA/B) 2.2/2.4 2.2/2.2 2.1/2.0 2.1/1.9 2.2/2.3 2.2/2.8 2.4/2.7 元件內的停留 時間(分鐘） 3 4 4 4 3 8 8 紡絲溫度(°C) 275 280 283 285 270 270 280 紡絲速度 (米/分鐘） 2800 2600 2400 2100 2800 2600 1400 卷取張力(s/d) 0.09 0.07 0.08 0.08 0.09 0.15 0.14 截面形態υ S/S S/S S/S S/S S/S S/C S/S 曲面變形係數 (c/d) 1.15 1.10 1.10 1.15 1.10 1.45 1.20 變形度(a/b) 1.6 1.8 1.8 1.9 1.5 1.05 1.7 拉伸比 Γ 1.60 1.70 1.70 1.64 1.60 1.70 2.90 拉伸溫度(°C) 85 90 90 90 85 80 75 熱固定溫度(°C) 150 160 160 170 150 140 145 強度(s/d) 3.5 3.7 3.6 3.4 2.9 3.2 3.3 拉伸率(％) 34 36 32 31 37 39 38 PET結晶度 34 41 39 40 29 30 31 PTT結晶度 36 43 40 41 33 32 33 自然捲曲拉伸 率(％) 36 43 40 41 13 28 31 自然彈性恢復 率(％) 79 83 81 82 89 72 68 氯 處 理 刖 後 拉伸強度維 持率(％) 91 94 93 92 84 80 78 伸縮維持率 (%) 90 84 87 85 86 77 76 拉作 (%) 戸絲斷頭率 5.0 3.0 4.5 6.0 6.0 13.5 11.5 1) S/S :並列型、s/c ··偏心芯鞘型 2) PET :聚對苯二曱酸乙>酯 3)PTT:聚對苯二甲酸丙>酯 24 1286168 . 【圖式簡單說明】 圖1(a)〜（c)是根據本發明製造的耐氣性優異的聚酯 類複合纖維的截面圖，表示變形度。 圖2是表示根據本發明製造的耐氣性優異的並列型的 結合型聚酯類伸縮性複合纖維的曲面變形係數的圖。 圖3是表示偏芯鞘型聚酯類伸縮性複合纖維的曲面變 形係數的圖。 【主要元件符號說明】 a/b 變形度 # c/d 曲面變形係數\)y 3 /V Natural crimp elongation (%)==[(L2_Li)/L2]x1〇〇17 1286168 Natural elastic recovery rate (%) = [(L2 — (4) 3; /CL2- Li)]xl 〇〇(3) The use of sub-gas for gas (strength strength retention rate, expansion and retention rate), in the effective gas amount (10) - is ?:: The composite fiber to be produced is 3 (rc_ 72 hours 4 hours for effective gas) After the treatment was carried out for 72 hours, and then naturally dried, the tensile strength maintenance ratio and the stretch retention ratio of the gas-water-treated raw yarn were calculated by the following formula (5M8). Tensile strength maintenance ratio (%) = S1/S()X100 (5) (S.: tensile strength before gas-water treatment, Si: tensile strength after gas-water treatment) (here, 'tensile strength is measured based on KS κ 412.) Expansion retention rate (%) = (curl stretch retention rate + elastic recovery retention rate) / 2 (6) Dental curl tension retention rate (%) = (VCqx1 〇〇 (?) (c.: before gas water treatment Natural crimp elongation, Ci • • Natural crimp elongation of gas-water treatment) (here, the natural crimp elongation (C(), Ci) is determined based on the natural crimp elongation of (2) above. Measuring side Method of elastic recovery rate (%) = Ει/Ε〇χ1〇〇(8) (E〇. Natural elastic recovery rate before gas-water treatment: natural elastic recovery rate after gas-water treatment) (here 'natural The elastic recovery rate (E., E!) is measured based on the measurement method of the natural elastic recovery rate of (2) above. 1286168 (4) The evaluation of the surface deformation coefficient and deformation degree of the original yarn cross section is shown in Fig. 2 As shown in Fig. 3, the cross section of the original yarn is analyzed by a scanning electron microscope (sem), and then calculated according to the following formula (9) and formula (1〇). Surface deformation coefficient = c / d (9) Deformation =a/b (1〇) (5) Method for determining the breakage rate of the drawn yarn The 20-strand partially drawn yarn was stretched by the amount of drawn yarn of 2 kg, and the percentage of broken yarn was expressed by percentage (%). (6) Crystallinity The crystallinity of the composite fiber after stretching and heat setting was measured by X-ray wide-angle diffraction method, and then polyethylene terephthalate and polytrimethylene terephthalate were separated according to Lorentzian analysis. The crystallinity peak of the diester is measured according to the following formula (11). Crystallinity = (1 - Σ la / Σ Ial〇〇 Xl〇〇(11) (here, Ia = scattering intensity of the amorphous region of the polymer, 131. = scattering intensity of the 100% amorphous region of the high knife) Example 1 In the process of producing the stretchable composite fiber Set the spinning temperature to 275 C, the spinning speed to 2800 m/min, the crimping tension to 〇·〇9 g/d, and the residence time in the component to 3 minutes. Using the existing melt-spinning spinning equipment, the weight ratio is 5:5. The ratio of the number average molecular weight (Mn) was ι 4632, the polyethylene terephthalate having a molecular weight distribution coefficient (PDI) of 2.2, and the number average molecular weight (Μη) was 32,149, and the molecular weight distribution coefficient ({^. A polyester composite fiber was produced by using a parallel cross section of Fig. 1-(a) as a polyethylene terephthalate of 2.4. 1286168 is placed on the composite fiber obtained by the spinning/winding. The implementation of the buckled ± & monofilament fineness of 2·1 denier stretchable composite fiber to produce temperature. On the day, the draw ratio was i·60, the draw temperature was 85 < t, and the heat-resistant 〇C was obtained. As a result, the fiber obtained by the above showed excellent properties, stretchability, and stretch workability. Example 2 In the process of 〇1 & stretchable conjugate fiber, the H spinning temperature was 280, the spinning speed was 2,600 m/min, the crimping tension was (K07 g/d, the residence time in the element was 4 minutes, and the existing melt composite was utilized. Spinning equipment, with a ratio of 5:5, a number average molecular weight (?η) of 14632, a molecular weight knife coefficient (PDI) of 2.2, polyethylene terephthalate and a number average molecule ^ (Μη) A polyester conjugate fiber was produced by a parallel cross section of Fig. 1-(a), which is 39334 and a molecular distribution coefficient (10) of 2.2. The composite fiber obtained by the spinning/winding was stretched by another stretching device to produce a stretchable composite fiber having a monofilament fineness of 2·丨 denier. When the stretching was carried out, the stretching ratio was 丨·70, the stretching temperature was 90 Å, and the heat setting temperature was 160. (: The results show that the fibers obtained in the table exhibit excellent gas resistance, stretch characteristics, and stretch processability. Example 3 In the process of producing a stretchable composite fiber, the spinning temperature was set to 283 ° C, and spinning was performed. The speed is 2400 m / min, the crimping tension is 〇. 〇 8g / d, the residence time in the component is 4 minutes, and the number average molecular weight (Μη) is determined by the ratio of the weight ratio of 5:5 by the existing melt composite spinning equipment. 16422, polyethylene terephthalate with molecular weight distribution coefficient (PDI) of 2.1 and number average molecule! 286168 (fn) is 45752, molecular weight distribution coefficient ([>1)1) is 2 〇 polyparaphenylene Two: ^ Bingyi from the 曰 'to the parallel cross section of the figure [(a), the manufacture of polyester composite fiber. "Used, his stretching device 'stretches the composite fiber obtained by the spinning/winding" to produce a stretchable composite fiber having a monofilament fineness of 2.1 denier. The ratio is 17Q, the stretching temperature is 9『c, the thermoset=/the dish is 160 C'. The results are shown. The obtained fiber exhibited excellent gas resistance, stretchability and stretch processability. Example 4. In the process of producing the stretchable composite fiber, the spinning temperature is set to 285, the square wire speed is 2100 m/min, the crimping tension is 0. 08 g/d, and the residence time in the element is 4 minutes, and the existing molten composite spinning is utilized. The wire equipment, the ratio of the ratio of 6:4, the number average molecular weight (?η) is 16422, the molecular weight 2 coefficient is 2" of polyethylene terephthalate and the number average molecule, (10) is fine 8, molecular weight The distribution coefficient (10) is a parallel cross section of U(tetra)p-phenylene:acid propylene diacetate' to Figure (8) to produce a polyester composite fiber. A stretching device of dimensions and n was used to produce a stretchable composite fiber having a monofilament fineness of 2" denier for the composite fiber obtained by the spinning/winding. The pulling material is applied, the stretching ratio is 164, the temperature is 170t, the dry fruit is dried in the 矣..., and the 热9〇C heat-solid fruit does not exhibit excellent gas resistance, stretchability and stretchability. . Comparative Example 1 During the process of the composite fiber, the spinning temperature was set to 270, the speed of the cable was 2,800 m/min, and the residence time of the crimping tension was 3 minutes. The existing molten composite spinning set was prepared. 1286168 weight ratio of 5:5, the number average molecular weight (Mn) of 11683, molecular weight knife cloth coefficient (PDI) of 2.2 polyethylene terephthalate and number average molecular weight (Μη) is 14054, molecular weight distribution coefficient A polyacetate composite fiber was produced by a parallel cross section of (pDI) of 2 3 polyparaphenylene & The conjugate fiber obtained by the spinning/winding was stretched by another stretching device to produce a stretchable composite fiber having a monofilament fineness of 21 denier, and the stretching ratio was 16 Å. The stretching temperature was 85 ° and the heat setting temperature was 15 G ° C. The results show that the fibers obtained by the above-mentioned results have good gas resistance and tensile processability, and the stretch characteristics are low. Xin Comparative Example 2. In the process of producing the stretchable composite fiber, the spinning temperature is set to 270 C 'spinning speed is 2,600 m/min, the crimping tension is 〇·15 g/d, and the residence time in the element is 8 minutes, and the existing molten composite spinning is utilized. The device has a number average molecular weight (?η) of 11683, a molecular weight distribution coefficient (PDI) of 2.2, a polyethylene terephthalate and a number average molecular weight (Mn) of 23,744 in a weight ratio of 5:5. Polyethylene terephthalate having a distribution coefficient (PDI) of 2.8 was prepared from the eccentric core cross section of Fig. 3 to produce a polyester composite fiber. The composite fiber obtained by the spinning/winding was stretched by another stretching device to produce a stretchability of a monofilament fineness of 2.1 denier. fiber. When stretching is carried out, the stretching ratio is: 7 〇 and the stretching temperature is 8 Torr. The heat-fixing temperature was 14 〇 ° C, and the results showed that the fibers obtained in the table showed low gas resistance, stretch characteristics, and stretch workability. Comparative Example 3 In the process of producing the stretchable composite fiber, the spinning temperature was set to 28〇22 1286168 t, the spinning speed was 1400 m/min, the crimping tension was 〇·i4g/d, and the residence time in the element was 8 minutes. The existing molten composite spinning equipment has a number average molecular weight (Mn) of 2〇422, a molecular weight distribution coefficient (PDI) of 2.4 polyethylene terephthalate and a number average molecular weight at a weight ratio of 5··5. (Μη) was 66450, a polytrimethylene terephthalate having a molecular weight distribution coefficient (pDI;) of 2.7, and a polyester composite fiber was produced in the parallel cross section of Fig. 1-(a). The composite fiber obtained by the spinning/winding was stretched by another stretching device to produce a stretchable composite fiber having a fineness of 2.1 denier. When stretching was carried out, the draw ratio was 2.90, the stretching temperature was 75 t, and the heat setting temperature X was 145 C. The results are shown in Table 1. The obtained fiber was inferior in gas resistance, stretchability, and stretch workability. 23 1286168 Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Polymer Α (Μη) PET2) (14632) PET (14632) PET (16422) PET (16422) PET ( 11683) PET (11683) PET (20422) Polymer Β(Μη) ρττ3) (32149) PTT (39334) PTT (45752) PTT (49118) PTT (14054) PTT (23744) PTT (66450) PDKA/B) 2.2 /2.4 2.2/2.2 2.1/2.0 2.1/1.9 2.2/2.3 2.2/2.8 2.4/2.7 Residence time in the component (minutes) 3 4 4 4 3 8 8 Spinning temperature (°C) 275 280 283 285 270 270 280 Spinning Wire speed (m/min) 2800 2600 2400 2100 2800 2600 1400 Winding tension (s/d) 0.09 0.07 0.08 0.08 0.09 0.15 0.14 Section shape υ S/SS/SS/SS/SS/SS/CS/S Surface deformation factor (c/d) 1.15 1.10 1.10 1.15 1.10 1.45 1.20 Deformation (a/b) 1.6 1.8 1.8 1.9 1.5 1.05 1.7 Stretch ratio Γ 1.60 1.70 1.70 1.64 1.60 1.70 2.90 Stretching temperature (°C) 85 90 90 90 85 80 75 Heat setting temperature (°C) 150 160 160 170 150 140 145 Strength (s/d) 3.5 3.7 3.6 3.4 2.9 3.2 3.3 Tensile rate (%) 34 36 32 31 37 39 38 PET crystallinity 34 41 39 40 29 30 31 PTT Crystallinity 36 43 40 41 33 32 33 Natural crimp elongation (%) 36 43 40 41 13 28 31 Natural elastic recovery rate (%) 79 83 81 82 89 72 68 Tensile strength maintenance ratio after chlorine treatment (%) 91 94 93 92 84 80 78 Expansion and retention rate (%) 90 84 87 85 86 77 76 Pulling (%) Thread breaking rate 5.0 3.0 4.5 6.0 6.0 13.5 11.5 1) S/S: Parallel type, s/c · Eccentric core sheath type 2) PET: poly(p-benzoic acid ethyl ester) > ester 3) PTT: polytrimethylene terephthalate > ester 24 1286168. [Simplified illustration] Fig. 1(a)~(c) A cross-sectional view of a polyester-based composite fiber excellent in gas resistance produced according to the present invention, showing a degree of deformation. Fig. 2 is a view showing a curved surface deformation coefficient of a side-by-side type polyester-type stretchable conjugate fiber which is excellent in gas resistance and which is produced according to the present invention. Fig. 3 is a view showing a curved surface deformation coefficient of a eccentric sheath type polyester-based stretch composite fiber. [Main component symbol description] a/b deformation degree # c/d surface deformation coefficient
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