4 6 7 9 2 2 案號88120335_年 月 日 修正 _ 五、發明說明（1) 發明背景 . 1 ·發明範圍. 本發明有關一種方法，用以備製吸水性優越可與棉、 毛同等之聚酯纖維。 2 .先前技術說明 . 通常，聚酯纖維主要是甩對苯二甲酸或芳族二幾酸（ 諸如2, 6 -奈二甲酸’）或其酯衍生物，及乙二醇經由聚縮而 .備製。 聚酯纖維具有優越的機械性質與抗熱性，但與天然纖 維（諸如再生纖維素）比較時，吸水性不良，因為聚酯纖 維之結構為高結晶性，且其分子中少有諸如親水基之水親 和性族群。本文中使用"吸水性n —詞係表示纖維物質，.諸 .如單纖絲、纖維縷：、紡織品、針織品、不織布等的吸水程 度。.在需要吸水性之處使用聚酯纖維時.，可能會造成問題 〇 因此，已有人積極研究以發展吸水性極隹同時保有其 物理性質之聚酯纖維。 例如美國專刺No. 3, 3 2 9, 5 5 7與英國·專利No. 9 5 6, 8 3 3 之揭示中，聚酯在紡綵前即先攙入親水性聚烷乙二醇。.然 而，如此所得到的聚酯纖維除了不能達到令人滿意.的吸水 性外，其物理性質亦顯現相當之劣化。 韓國專利公告No. 9 3 - 6 7 7 9揭示的聚酯纖維添加一種 含有聚亞烴或聚胺之有機化合物作為主鏈。韓國專利公告 . · . · .N 〇. 8 6 - 3 9 7揭示的聚酯於添加溶離劑R 0 S 0 3 Μ (其中，R是 包含卜30個碳原子之烷基或包含7-40個碳原子之院基芳香-4 6 7 9 2 2 Case No. 88120335_ Year, Month, and Day Amendment_ V. Description of the invention (1) Background of the invention. 1 · Scope of the invention. The present invention relates to a method for preparing water-absorbent materials that are equivalent to cotton and wool. Polyester. 2. Prior technical description. Generally, polyester fibers are mainly terephthalic acid or aromatic diacid (such as 2, 6-neodicarboxylic acid ') or its ester derivatives, and ethylene glycol is obtained through polycondensation. Prepared. Polyester fiber has superior mechanical properties and heat resistance, but it has poor water absorption when compared with natural fibers (such as regenerated cellulose), because the structure of polyester fiber is highly crystalline and there are few molecules such as hydrophilic groups in its molecule. Water affinity ethnic group. The term "water absorption n" is used herein to indicate the degree of water absorption of fibrous substances, such as monofilaments, fiber strands, textiles, knitwear, nonwovens, and the like. The use of polyester fibers where water absorption is required may cause problems. Therefore, there have been active studies to develop polyester fibers that are extremely absorbent and retain their physical properties. For example, in the disclosures of U.S.A. No. 3, 3 2 9, 5 5 7 and U.K. · Patent No. 9 5 6, 8 3 3, the polyester is first incorporated with a hydrophilic polyethylene glycol before spinning. However, in addition to the unsatisfactory water absorption of the polyester fibers thus obtained, their physical properties also show considerable deterioration. The polyester fiber disclosed in Korean Patent Publication No. 9 3-6 7 7 9 adds an organic compound containing polyalkylene or polyamine as a main chain. Korean Patent Announcement.... .6. 6-3 9 7 The polyester disclosed by adding a dissolving agent R 0 S 0 3 M (where R is an alkyl group containing 30 carbon atoms or 7-40 Courtyard-based aromatic
467922 __案號88120335_年 月 日. 修正 _ 五、發明說明（2) 基，Μ是驗性金屬或驗土金屬）.後再進行纺絲，並使用一 種含水鹼性溶液作溶離處理，使纖維成多孔性。這些聚醋 纖維之吸水性顯著改進，但面臨價格昂貴之重大缺點。其 添加物價格高，而且其增加的處理製程也造成高製造成本 〇 提供聚酯纖維親水性的另一習知方法是添加膠狀二氧 化矽微粒。此法同樣造成製造成本增加。 發明概要. 因此，本發明目的之一在於克服先前技術中遭遇的上 述問題，並提供一種方法，用以備製顯示優異吸水性與物 理性質之聚酯纖維。 本發明另一目的在於提供一種方法，用以備製聚醋纖 維而不顯著增加其生產成本。· ' 在本發明一實施例中，提供一種高吸水性聚酿纖維之 備製方法，其中在聚酯聚合到紡絲前階段間的某一適當添 力口時間，以纖谁總重為基礎，添加重量比為0 . 0 1 - 5 0 %之無 機微粒。在此實施例之一層面中，此添加時間係從聚酯聚 合之階段、聚酯於壓力下流至嘖絲頭之階段、及聚酯熔態 擠壓成薄片之_階段中選出。在此實施例另一層面中，.無機 微粒係從氧化鈣微粒、氧化.鎂微粒.、.氧化錳微粒.、及此等 成份之混合物構成之群組中選出，且其尺寸範圍從0. 0 1到 5 0 μ«ι 發明詳細說明 通常，聚酯纖維是用聚羧酸及多元醇備製而成.的。至於本 發明之聚酯纖維，則使用芳族二羧酸或其酯衍生物。在本467922 __Case No. 88120335_Year Month. Amendment _ V. Description of the invention (2), M is a test metal or soil test metal). After spinning, and using an aqueous alkaline solution for dissolution treatment, Make the fibers porous. These polyester fibers have significantly improved water absorption, but face the significant disadvantage of being expensive. Its additives are expensive, and its increased processing process also results in high manufacturing costs. Another conventional way to provide hydrophilicity for polyester fibers is to add colloidal silica particles. This method also causes increased manufacturing costs. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to overcome the above-mentioned problems encountered in the prior art and to provide a method for preparing a polyester fiber exhibiting excellent water absorption and physical properties. Another object of the present invention is to provide a method for preparing a polyester fiber without significantly increasing its production cost. · 'In an embodiment of the present invention, a method for preparing a super absorbent polymerized fiber is provided, in which a certain time for adding force is applied between the polymerization of polyester and the pre-spinning stage, based on the total weight of the fiber , Adding inorganic fine particles with a weight ratio of 0.01 to 50%. In one aspect of this embodiment, this addition time is selected from the stage of polymerizing the polyester, the stage where the polyester flows under pressure to the reel head, and the stage where the polyester is extruded into a sheet in the molten state. In another aspect of this embodiment, the inorganic particles are selected from the group consisting of calcium oxide particles, oxidized magnesium particles, manganese oxide particles, and mixtures of these ingredients, and their size ranges from 0. 0 1 to 50 0 «Detailed description of the invention In general, polyester fibers are prepared from polycarboxylic acids and polyols. As for the polyester fiber of the present invention, an aromatic dicarboxylic acid or an ester derivative thereof is used. In this
第5頁 467322 _案號88120335_年月 日 修正 ._ 五、發明說明（3) 發明十有用之芳族二羧酸例子包括間苯二曱酸 '對苯二甲 酸、2，6 -奈二甲酸、苯二甲酸、己二酸、癸二酸、.及以上 各項之混合物。關於多元醇，主要是使用乙二醇，配合小 量的其他醇類，例如1，2 -丙二醇、丁二醇、i , 4 -環己二 醇、及2，2 -二甲基丙二醇。 必要時，.備製聚酯纖維十，可使用諸如熱安定劑、防 阻塞劑、抗氧化劑、抗靜電劑、U V吸收劑等之添加劑。 根據本發明，在備製聚酯纖維中.使用無機微粒是為了 賦予聚酯纖維高親水性。無機微粒係從氧化鈣微粒、氧化 鎂微粒、氧化錳微粒、及此等成份之混合物構成之群組中 選出。 . 至於備製聚醋纖維期間的無機微粒添加時間，可從聚 .酯聚合之.階段、聚酯於壓力下流至喷絲頭之階段、及聚酯 熔態擠壓成薄片之階段中選出。 在聚酯聚合階段中，無機微粒之添加時間最好恰在酯 化步驟完成後，或在聚縮步驟之時。就此點而言，添加的 無機微粒不可包含水份，以免抑制反應。 經由聚縮而被聚合後，聚酯在壓力下被傳送至一喷絲 .頭，以便紡成聚酯纖維。在此傳送過程中，可添加氧化鈣 微粒、氧化鎂微粒、氧化錳微粒、或此等成份之混合物。 關於此點，有些聚合物會被吸出傳送管，添加無機微粒， 再送回管内其餘的聚合物中。 當聚合後的聚酯被傳送到一擠壓機以生產聚酯薄片時 ，將無機微粒直接饋入。在本發明中，含有無機微粒之聚 酯薄片可單獨使用或與其他聚酯薄片混合使用。Page 5 467322 _Case No. 88120335_ Year, month, day, date .__ V. Description of the invention (3) Examples of ten useful aromatic dicarboxylic acids include isophthalic acid 'terephthalic acid, 2,6-naphthalene Formic acid, phthalic acid, adipic acid, sebacic acid, and mixtures of the above. As for the polyhydric alcohol, ethylene glycol is mainly used in combination with a small amount of other alcohols such as 1,2-propylene glycol, butanediol, i, 4-cyclohexanediol, and 2,2-dimethylpropylene glycol. When necessary, prepare polyester fibers. Additives such as heat stabilizers, anti-blocking agents, antioxidants, antistatic agents, UV absorbers, etc. can be used. According to the present invention, the inorganic fine particles are used in the prepared polyester fiber in order to impart high hydrophilicity to the polyester fiber. The inorganic fine particles are selected from the group consisting of calcium oxide fine particles, magnesium oxide fine particles, manganese oxide fine particles, and a mixture of these components. As for the adding time of the inorganic particles during the preparation of the polyester fiber, it can be selected from the stage of polymerizing the polyester, the stage of the polyester flowing under pressure to the spinneret, and the stage of extruding the polyester into a sheet in a molten state. In the polyester polymerization stage, the addition time of the inorganic fine particles is preferably just after the completion of the esterification step or at the time of the polycondensation step. In this regard, the added inorganic fine particles must not contain water, so as not to inhibit the reaction. After being polymerized by polycondensation, the polyester is conveyed under pressure to a spinneret for spinning into polyester fibers. During this transfer, calcium oxide particles, magnesium oxide particles, manganese oxide particles, or a mixture of these components may be added. In this regard, some polymers are sucked out of the transfer tube, inorganic particles are added, and returned to the remaining polymer in the tube. When the polymerized polyester is transferred to an extruder to produce polyester flakes, inorganic particles are fed directly. In the present invention, the polyester flakes containing inorganic fine particles can be used alone or in combination with other polyester flakes.
第6頁 4 6 7 922 案號 88120335 修正 五、發明說明（4) 通常，氧化鈣微 酸鈣礦石粉碎成小片 ，以分離氧化鈣與碳 容易且因製造過程簡 立刻轉變成氫氧化約 親水性使聚酯纖維可 亦有此種改進吸水性 無機微粒之大小 如_，.使用大小小於_0 水性的重大_改進。另 紡絲過程或後處理過 使用量，以聚酯重量 。_例如__，用量小於重 極微，而用量大於童 性質。. 如上所述，無.機 可紡性與後處理過程 無機微粒是磨損聚醋 能使用高純度的無機 根據以下範.例可 例僅係舉例之用，而 範例I _ _ 在一反應器中放 比45份之乙二醇，然 使之酿化。依重.量比 粒可從碳酸鈣礦石取得。首先，將碳 並在爐中以大約1, 〇 〇 〇 °c之溫度烘烤 氧化物。碳酸鈣微粒的好處在於取得 單:所以價格低廉。氧化#5遇到水時， (Ca(0H)2 )。因此，氧化鈣此楂高 以有極佳之吸水性。氧化鎂與氧化錳 的機制。_ 範圍較佳是在0 . 0 1至5 0 μπι之間。例 .0 1 μηι 的無機微粒時，並不產生吸 一方_面大於之.無機微粒於 程中容易造成纖維切斷。無機微粒的 為基礎，最好在重量比0. 1-50%左右 量.比0 . 1 %時，.對於吸水性的改進貢獻 '量比5 0 %時，會不良影響聚酯之物理 微粒不可含有水份或雜質，否則t在 中發現劣化。此外，由於聚酯中存在 物理性質的直接因素，所以最好儘可 微粒。 對本發明有更佳的理解，不過這些範 非用以限制本發明。 置重量比1 0 0份之對苯二甲酸與重量 後將之加熱至1 4 0 - 2 3 0 °C並加授動， 每份乙二醇溱加重量比0. 0 4份之三氧Page 6 4 6 7 922 Case No. 88120335 Amendment V. Description of the Invention (4) Generally, calcium oxide micro-calcium acid ore is pulverized into small pieces to separate calcium oxide from carbon easily, and due to the simple manufacturing process, it is immediately converted to hydroxide and hydrophilic. The polyester fiber can also have such improved water absorbent inorganic particles, such as _ ,. Use a size of less than _ 0 great improvement in water. Another spinning process or post-treatment has been used in terms of polyester weight. _For example, __, the amount is less than the extremely small amount, and the amount is greater than the child. As mentioned above, the non-mechanical spinnability and post-treatment inorganic particles are abrasive polyacetate. High-purity inorganic can be used according to the following examples. Examples can only be used for example, and example I _ _ in a reactor Put 45 parts of ethylene glycol, then make it brew. Weight-to-weight ratio granules can be obtained from calcium carbonate ore. First, the carbon is baked in an oven at a temperature of about 1,000 ° C. The advantage of calcium carbonate particles is to get the order: so the price is low. When oxidation # 5 encounters water, (Ca (0H) 2). Therefore, calcium oxide has a high water absorption. The mechanism of magnesium oxide and manganese oxide. _ The range is preferably between 0.01 and 50 μm. For example, when the inorganic fine particles of 0 μm are not produced, the absorption side is larger than that. The inorganic fine particles are liable to cause fiber cutting in the process. Based on inorganic fine particles, it is best to have an amount of about 0.1-50% by weight. When the ratio is 0.1%, the contribution to the improvement of water absorption will be adversely affected when the amount of polyester particles is 50%. Do not contain water or impurities, otherwise t will be found to be degraded. In addition, since there is a direct factor in the physical properties of the polyester, it is best to keep the particles as small as possible. The present invention is better understood, but these examples are not intended to limit the present invention. The weight ratio of 100 parts by weight of terephthalic acid and the weight is heated to 1 40-2 3 0 ° C and added, each part of ethylene glycol 溱 add weight ratio of 0. 4 parts of three oxygen
4 6 792 2 ^ 月 曰 修正 五、發明說明(5) 化1與015份之碌酸後，讓酿化之混合物在真空 及2 3 0 -2 8 5 C之溫度不聚縮4小時以。/ 使用液態氮固化聚輯！，並將之粉二成粉末。隨， f 3二二份ί此種粉末與重量比20份之氧化妈微粒^質 ，而其平均大小為〇. 4叫。门mn之間 真空及2 4 〇 - 2 9 0。(：溫度下摔/同貝合，通過在. 生聚酿Π。 下操作之雙螺桿炼態撥壓機’以產 ，二操份之聚醋1與重量比10份之聚醋Η，用 Ϊ二ί Ϊ :, 時’通過操作溫度為2 9 0 °C之溶態 擠壓機熔解，並經由一喷絲頭妨絲s以產生75/24聚醋纖 維。. 範例I I 以類.似範例I的方法備.製7 5 / 2 4聚酯纖維 比9 5份之聚酯I與重量比5份之聚酷I I。 比較範例Ϊ - - · 在反應器中放置重量比1 00份之對苯二甲酸與重量比 4 5份之乙二醇然後將之加熱至ϊ 4 〇 - 2 3 0 °C並加攪動，使 之酯化。依重量比每份乙二醇添加重量比〇 . 〇 4 .份之三.氧化 .錄與重量比0. 0 1 5份之磷酸後，讓酯化之混合物在真空及 2 3 0 - 2 8 5 °C之溫度下聚縮4小時以產生聚酯ϊ 。 使用液態氮固化聚酯I ，並將之粉碎成粉末。隨後， 將重量比8 0份之此種粉末與重量比2 〇份之膠狀二氧化矽微 粒同質混合3 0分鐘。膠狀二氧化石夕微粒之平均大小為〇 . 3 接著允許該同質混合物通過在真空及2 4 0 - 2 9 0 °C溫度 但使雨重量 μπι4 6 792 2 ^ Month Name Amendment V. Description of the invention (5) After the 1 and 015 parts of chloroacid are made, the brewed mixture is not polymerized and condensed under vacuum at a temperature of 2 30-2 8 5 C for 4 hours. / Curing the collection with liquid nitrogen! And powder it into powder. With this, f 3 22 parts of this powder and 20 parts by weight of oxidized mother particles ^ quality, and its average size is 0.4 called. The vacuum between the gates mn and 2 4 0-2 9 0. (: At the temperature, the temperature is the same as that of the shellfish, and it is produced by using a twin-screw refining pressure dial operating machine under the condition of raw juice production. The two parts of polyacetate 1 and the weight ratio of 10 parts of polyacetate are used. Ϊ 二 ί Ϊ :, '' is melted by a molten extruder with an operating temperature of 2 90 ° C and passed through a spinneret to produce 75/24 polyester fiber. Example II is similar. Method I of Example I. Preparation of 7 5/2 4 polyester fiber ratio of 95 parts of polyester I and 5 parts by weight of Polyco II. Comparative Example Ϊ--· Place in a reactor a weight ratio of 100 parts Terephthalic acid and 45 parts by weight of ethylene glycol are then heated to ϊ 4 0-230 ° C and agitated to make it esterified. Per weight of ethylene glycol is added in a weight ratio of 0. 〇3. Three parts. Oxidation. Recording weight ratio of 0.01 to 15 parts of phosphoric acid, the esterified mixture was polycondensed under vacuum and at a temperature of 2 3 0-2 8 5 ° C for 4 hours to produce poly Ester ϊ. Polyester I was cured with liquid nitrogen and pulverized into powder. Subsequently, 80 parts by weight of this powder and 20 parts by weight of colloidal silica particles were mixed homogeneously for 30 minutes. Gum Dioxide Stone The average size of the particles is 0.3. The homogeneous mixture is then allowed to pass under vacuum at a temperature of 2 0-2 0 0 ° C but the rain weight μπι
第8頁 4 6 7 922 _ 案號88120335_年 月 曰 修正 五、發明說明（6) 下操作之雙螺桿熔態擠壓機，以產生聚酯I I I。 攙和重量比9 0份之聚酯I與重量比1 0份之聚.醋I I I ，用 熱空氣在1 6 0 °C乾燥6小時，通過操作溫度為2 9 0 °C之熔態. 擠壓機溶解，並經由一喷絲頭纺絲，以產.生7 5 / 2 4聚酯纖 維。：Page 8 4 6 7 922 _ Case No. 88120335_ Year Month Revision V. Description of the Invention A twin-screw melt extruder operating under (6) to produce polyester I I I.搀 and 90 parts by weight of polyester I and 10 parts by weight of polymer. Vinegar III, dried with hot air at 160 ° C for 6 hours, through the molten state of the operating temperature of 29 ° C. Extrusion The press dissolves and spins through a spinneret to produce 7 5/2 4 polyester fibers. :
比較範例II 以類似比較範例I的方法備製75 / 24聚酯纖維，但使用 ，重量比_9 5份之聚.醋Γ與重’量比5份之聚.I旨I I.I.。__ 測量各範例與各比較範例所獲得的聚醋之物理性貧， __其結果如以下表1所示。 表1 物理性質 範例 I II C.I. CJI 丹尼爾 75/24 75/24 75/24 75/24 .強度（g/丹尼爾） 4.78 4.78 4.79 4.79 延伸度W 38.64 38.32 38.90 38.91 吸水性（蜇量％). 8.2 4.3 1.4 L2 從表1 .數據可明顯看出，根據本發明之方法提供的聚 酯纖維具有優越的吸水性，而其物理性質與習式方法類 似。此外，本發明超越習式方法的優點在於，其生產成本 由於無機微粒價格低廉而顯著減少。 以上以舉例方式說明本方法，但應了解其中所用術語 之目的係屬說明性質而非限制。根據以上揭示可以作多種 修改與變化。因此，應了解本發明可在所附申請專利範圍Comparative Example II A 75/24 polyester fiber was prepared in a similar manner to Comparative Example I, but using a weight ratio of _9 5 parts of poly. Vinegar Γ and a weight of 5 parts of poly. I purpose I I.I. __ Measurement of the physical depletion of polyacetate obtained from each example and each comparative example, __ The results are shown in Table 1 below. Table 1 Example of physical properties I II CI CJI Daniel 75/24 75/24 75/24 75/24 .Strength (g / Daniel) 4.78 4.78 4.79 4.79 Elongation W 38.64 38.32 38.90 38.91 Water absorption (% by weight). 8.2 4.3 1.4 L2 It is clear from the data in Table 1. The polyester fiber provided by the method of the present invention has superior water absorption, and its physical properties are similar to the conventional method. In addition, the present invention has an advantage over the conventional method in that its production cost is significantly reduced due to the low price of the inorganic fine particles. The method has been described above by way of example, but it should be understood that the terminology used therein is illustrative and not restrictive. Various modifications and changes can be made based on the above disclosure. Therefore, it should be understood that the present invention
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