200831726 九、發明說明 【發明所屬之技術領域】 本發明係關於具有抗靜電性之芯鞘型聚酯極細假撚加 工紗及其製造方法以及含該抗靜電性芯鞘型聚酯極細假撚 k 加工紗之抗靜電織物。更詳細而言，本發明係關於可安定 ' 得到耐久性優異之具有抗靜電性之芯鞘結構之聚酯極細假 撚加工紗之製造方法者。 【先前技術】 聚酯纖維係藉由優異的品質及安定的物性，以衣料用 途爲首，廣泛地被使用。然而，因爲聚酯原本就是疏水 性，所以於要求抗靜電性之領域，多數提出嘗試賦予聚酯 親水性，以使表現抗靜電性。 作爲該例，已知例如使配合聚氧伸烷系聚醚化合物於 聚酯之方法（特公昭39-5214號公報）、使配合實質上非 φ 相溶性之聚氧伸烷系聚醚化合物與有機·無機之離子性化 合物於聚酯之方法（特公昭44-3 1 828號公報、特公昭 60-11 944號公報、特開昭53-80497號公報、特開昭 53 - 1 49247號公報、特開昭60-3 94 1 3號公報、特開平 3-139556號公報等）等。 然而，於上述方法中，通常之延伸紗（FOY )時，雖 然表現良好的抗靜電性’但於假撚加工紗時，因假撚變形 而發生毛羽，而有不能得到良好抗靜電性之問題。 另外，尤其近年來’關於編織物之觸感、肌膚觸感、 -4- 200831726 外觀等之要求逐漸升高，使用單絲纖度爲16 dtex以下之 極細纖度之聚酯假撚加工紗，可製造具有柔和觸感之布 料’但於聚酯假撚加工紗時，隨著極細纖度化進行，極難 以充份抑制靜電發生，至今於運動衣料、制服、防麈衣等 之用途’或多直接觸肌膚之女用襯衫或襯衫等之用途，可 說現今狀況係皆無具有充份抗靜電性之布料。 【發明內容】 發明之揭示 本發明之目的係提供可得到具有極細聚酯假撚加工 紗’維持柔和觸感、保濕性、吸水、吸濕性等之性能，並 且抗靜電性能亦優異的聚酯布料之芯鞘型聚酯極細假撚加 工紗及可安定製造其之芯鞘型聚酯極細假撚加工紗之製造 方法。 本發明者等爲達成上述目的，努力檢討的結果，發現 將以鞘成份被覆使含有與聚酯實質上非相溶性之聚氧伸烷 系聚醚化合物及有機離子性化合物之聚酯所成之芯成份之 芯鞘型聚酯極細複合纖維，於特定條件下，溶融紡紗後， 進行延伸假撚加工時，可達成本發明之目的。 亦即，依據本發明，提供 ①爲經假撚加工之芯鞘型複合纖維，該芯鞘型複合纖 維之芯部係由含有相對於1 00重量份之芳香族聚酯之作爲 抗靜電劑之 (a) 0.2〜30重量份之聚氧伸烷系聚醚、及 -5- 200831726 (b) 0.05〜10重量份之與該聚酯實質上非反應性之 有機離子性化合物 而成之抗靜電性聚酯組成物A所形成，另一方面，鞘部係 由芳香族聚酯組成物B所形成，而且，該芯鞘型複合纖維 係以同時滿足（1 )〜（3 )之條件爲特徵之抗靜電性芯鞘 型聚酯極細假撚加工紗。 (1 )假撚加工紗之單絲纖度爲1.6 dtex以下。 (2 )假撚加工紗之捲縮率爲3〜30%。 (3 )芯部的面積SA及鞘部的面積SB之比SA : SB 係於5 : 95〜80 : 20之範圍。 及 ② 芯部係由含有相對於1 00重量份之芳香族聚酯之作 爲抗靜電劑之 (a) 0·2〜30重量份之聚氧伸院系聚醚、及 (b ) 0.05〜10重量份之與該聚酯實質上非反應性之 有機離子性化合物 而成之抗靜電性聚酯組成物A所形成，另一方面，鞘部係 將由芳香族聚酯組成物B所形成之芯鞘型複合纖維溶融紡 紗時，於紡出時之噴出速度及拉取速度之比（拉取速度/ 噴出速度，以後簡稱爲牽引倍率（draft rate))爲150以 上，8 00未滿之範圍拉取後，進行假撚加工爲特徵之抗靜 電性芯鞘型聚酯極細假撚加工紗之製造方法。 以及 ③ 爲含芯鞘型聚酯假撚加工紗之織物，該芯鞘型聚酯 -6 - 200831726 假撚加工紗係如上述①記載之抗靜電性芯鞘型聚酯極細假 撚加工紗爲特徵之抗靜電性織物。 用以實施發明之最佳形態 以下係詳細說明關於本發明之實施形態。 本發明中之聚酯係於聚合物結構單位具有芳香環之芳 香族聚酯，二官能性芳香族羧酸或該酯形成性衍生物與二 元醇或該酯形成性衍生物之反應所得之聚合物爲對象。 在此所謂之二官能性芳香族羧酸係可舉例如對苯二甲 酸、間苯二甲酸、鄰苯二甲酸、1，5-萘二羧酸、2,5 -萘二 羧酸、2,6 -萘二羧酸、4,4’-聯苯二羧酸、3,3’ -聯苯二羧 酸、4,4’_聯苯醚二羧酸、4,4’-聯苯甲烷二羧酸、4,4’-聯 苯颯二羧酸、4，4’-聯苯異丙叉二羧酸、i，2-雙（苯氧基） 乙烷-4,4’-二羧酸、2,5-蒽二羧酸、2,6-蒽二羧酸、4,4，-對 苯二羧酸、2，5 -吡啶二羧酸、点一羥乙氧基苯甲酸、對羥 基苯甲酸等，以對苯二甲酸爲宜。 此等之二官能性芳香族羧酸，亦可倂用2種以上。另 外，若爲少量時，此等之二官能性芳香族羧酸亦可倂用1 種或2種之如己二酸、壬二酸、癸二酸、十二烷二酮酸之 二官能性脂肪族羧酸、如環己烷二羧酸之二官能性脂環族 羧酸、5-磺基間苯二甲酸鈉等。 另外，作爲二醇化合物，可舉例適合之如乙二醇、丙 二醇、丁二醇、己二醇、新戊二醇、2-甲基-1，3_丙二醇、 二乙二醇、三伸甲基二醇之脂肪族二醇、如1，4-環己烷二 200831726 甲醇之脂環族二醇等及此等之混合物等。另外，若爲少量 時’可使此等二元醇化合物與兩末端或單側末端未封鎖之 聚氧伸烷乙二醇共聚合。 另外’聚酯係可使用實質上爲線狀之範圍如偏苯三 酸、均苯四甲酸之聚羧酸、如甘油、三甲醇丙烷、季戊四 醇之多元醇。 具體上作爲適合之芳香族聚酯，可舉例如聚對苯二甲 酸乙二醇酯、聚對苯二甲酸丁二醇酯、聚對苯二甲酸己二 醇酯、聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯、聚 1，2-雙（苯氧基）乙烷_4,4，_二羧酸乙二醇酯等，以及如聚 間苯二甲酸乙二醇酯♦對苯二甲酸酯、聚對苯二甲酸丁二 醇酯·間苯二甲酸酯、聚對苯二甲酸丁二醇酯·癸烷二羧酸 酯等之共聚合聚酯。其中以取得機械性質、成形性等平衡 之聚對苯二甲酸乙二醇酯及聚對苯二甲酸丁二醇酯爲宜。 相關的芳香族聚酯係由任意的方法所合成。例如說明 關於聚對苯二甲酸乙二醇酯，藉由使對苯二甲酸與乙二醇 直接進行酯化反應、或使如對苯二甲酸二甲酯之對苯二甲 酸之低級烷基酯與乙二醇進行交換反應或使對苯二甲酸與 環氧乙烷反應，使產生對苯二甲酸之乙二醇酯及/或該低 聚合物之第1階段反應，以及接著將該產物於減壓下加 熱，使進行聚縮合反應至成爲所需之聚合度之第2階段反 應，可容易製造。 配合於本發明使用之組成物之聚氧伸烷系聚醚（a ) 若爲對聚酯實質上不溶性者，可爲由單一個聚氧伸烷單位 -8 - 200831726 而成之聚氧伸院乙二醇，亦可爲由二種以上之聚氧伸烷單 位而成之共聚合聚氧伸烷乙二醇，另外，亦可爲下述一般 式（I )所表示之聚氧伸烷系聚醚。 Z-[(CH2CH2〇)n(R1〇)m.R2]k …（I) (上述式（I )中，Z係表示具有1〜6個之活性氫原子 之有機化合物殘基，R1係表示碳數6個以上之伸烷基或取 代伸院基、R2係表不氫原子、碳數1〜40個之一價烴基、 碳數2〜40個之一價羥基烴或碳數2〜40個之一價醯基、 k係表示1〜6之整數、n係表示滿足n - 7 Ο/k之整數、m 係表示1以上之整數。） 作爲相關之聚氧伸烷系聚醚之具體例，可舉例如分子 量爲4000以上之聚氧伸乙基乙二醇、分子量爲1〇〇〇以上 之聚氧伸丙基乙二醇、聚氧四伸甲基乙二醇、分子量爲 2000以上之環氧乙烷、環氧丙烷共聚物、分子量爲4000 以上之三甲醇丙烷環氧乙烷加成物、分子量爲3 000以上 之壬基苯酚環氧乙烷加成物、以及於此等之末端OH基， 加成碳數6個以上之取代環氧乙烷之化合物，其中以分子 量爲1 0000〜100000之聚氧伸乙基乙二醇、及於分子量爲 5 000〜1 600 0之聚氧伸乙基乙二醇之兩末端，加成碳數8 〜40個之烷基取代環氧乙烷之化合物爲宜。 相關聚氧伸烷系聚醚化合物之配合量範圍係相對於 1〇〇重量份之上述芳香族聚酯爲0.2〜30重量份。少於0.2 -9 - 200831726 重量份時，親水性不足，不能呈現充份的抗靜電性。另一 方面，即使多於3 0重量份時，已經認爲不具有抗靜電性 之提升效果，相反地損害所得組成物之機械性質，並且， 因爲該聚醚變得容易滲出，所以溶融成形時，對切片押出 機之嵌合性降低，成形安定性亦惡化。 本發明之聚酯組成物中，尤其爲提升抗靜電性而配合 有機離子化合物。作爲有機離子性化合物，可舉例如下述 一般式（Π) 、（ΠΙ)所示之磺酸金屬鹽及磺酸4級錢鹽 作爲適合者。 (Π) rso3m (上述式（π )中，R係表示碳數3〜3 0個之烷基或碳數 7〜40個之芳基，Μ係表示鹼金屬或鹼土類金屬。） RSChPRm4 ……（瓜） (上述式（皿）中，R係碳數3〜30個之烷基或碳數7〜 40個之芳基，R1、R2、R3及R4係烷基或芳基，其中以低 級烷基、苯基或苯甲基爲宜。） 上述式（Π )中，R係烷基時，烷基可爲直鏈狀，亦 可具有支鏈。Μ係Na ' K、Li等之鹼金屬或Mg、Ca等之 鹼土類金屬，其中以Li、Na、K爲宜。相關的磺酸金屬鹽 係可單獨使用1種，亦可混合2種以上使用。 -10- 200831726 作爲適合之具體例，可舉例如硬脂基磺酸鈉、辛基磺 酸鈉、十二烷基磺酸鈉、碳數平均爲14之烷基磺酸鈉混 合物、十二烷基苯磺酸鈉混合物、十二烷基苯磺酸鈉（硬 型、軟型）、十二烷基苯磺酸鋰（硬型、軟型）、十二烷 基苯磺酸鎂（硬型、軟型）等。 另外，式（ΠΙ )中之磺酸4級鳞鹽係可單獨使用1 種，亦可混合2種以上使用。作爲適合之具體例，可舉例 如碳數平均爲14之烷基磺酸四丁基錢、碳數平.均爲14之 烷基磺酸丁基四苯基鐵、碳數平均爲14之烷基磺酸丁基 三苯基鱗、十二烷基苯磺酸四丁基錢（硬型、軟型）、十 二烷基苯磺酸四苯基鱗（硬型、軟型）、十二烷基苯磺酸 苯甲基三苯基鳞（硬型、軟型）等。 相關之有機離子性化合物係可爲1種，亦可倂用2種 以上，該配合量係相對於1 00重量份之芳香族聚酯，必須 於0·0 5〜10重量份之範圍。有機離子性化合物之配合量 未滿〇· 05重量份，提升抗靜電性之效果小，超過10重量 份時，損害組成物之機械性質，並且，因爲該離子性化合 物亦變得容易滲出，所以溶融成形時之切片對押出機之嵌 合性降低，成形安定性亦惡化。 另外，聚酯B中，於不阻礙本發明目的之範圍，亦可 配合已知之消光劑，例如二氧化鈦等。但是，消光劑若超 過1 0 wt%時，因爲成爲本發明主紗之未延伸紗之紡紗性 惡化，所以該範圍係以〇·〇1〜10 Wt%爲宜。 另外，本發明之極細假撚加工紗必須單絲纖度爲1.6 -11 - 200831726 dtex以下，捲縮率爲3〜30%，藉由於此範圍，可得到柔 和觸感優異之編織物。捲縮率未滿3 %時，編織物不能得 到足夠的蓬鬆感，另一方面，超過3 0 %時，抗靜電性能有 降低之虞，並不適宜。 另外，芯部的面積SA及鞘部的面積SB之比SA : SB 必須於5 : 95〜80 ·· 20之範圍。面積比若小於5 : 95時， 由聚酯A之抗靜電性能表現不足，若大於80: 20時，施 以1 〇%以上之鹼減量時，芯部之抗靜電性聚酯溶出，抗靜 電性能降低、或假撚加工紗之強度降低，爲3.0 cN/dtex 以下，因作爲布料之強度不足，所以不適合運動衣料等之 需要強度之用途，因用途受到限制，所以不適合。 以上說明之本發明之聚酯極細假撚加工紗係將成爲該 主紗之未延伸紗溶融紡紗時，於紡出時之噴出速度及拉取 速度之比（拉取速度/噴出速度，以後簡稱爲牽引倍率） 爲1 5 0以上，8 〇 0未滿之範圍拉取後之未延伸紗，進行假 撚加工，可得到安定的抗靜電性能。牽引倍率未滿1 5 0 時，由聚酯A之抗靜電性能表現不足，牽引倍率爲800以 上時，雖表現抗靜電性能，但紡紗性降低，所以不適合。 設定牽引倍率於上述範圍時，雖適當設定金屬口噴出 孔徑、紡紗速度即可，但噴出孔徑爲Φ 〇. 1〜〇 · 3 ，紡 紗速度爲2000〜4500 m/min，尤其2500〜3500 m/min之 範圍溶融紡紗時，可容易且有效率得到，所以適合。 此時之未延伸復合絲之複折射率係於0·02〜0·05之範 圍爲宜。該複折射率未滿0.02時，因爲假撚加工時之張 -12 - 200831726 力降低，容易發生突波（surging )、紗搖動，所以引起熱 定形斑、染斑不良、加工倍率升高而成弱紗，所以不適 合。另一方面，複折射率超過0.05時，容易發生原紗毛 羽，步驟將不順暢，所以不適合。 關於該未延伸紗之假撚加工法，雖無須特別的限定， 但可使用如下述記載之方法。 首先，空氣交絡處理係可與延伸假撚加工於不同步驟 進行，但如圖1所示，於延伸假撚加工裝置中設置交錯 (interlace )噴嘴，於延伸假撚加工前實施爲宜。藉此抑 制毛羽發生，亦對操作性帶來好的影響，另外，對熱定形 假撚後紗條施以空氣交絡，因爲將混纖交絡完美地均勻 化，有紗長方向均勻效果，具有抗靜電性而且使表現高級 感者。 接著，被施以交絡處理之未延伸紗係交予例如如圖1 所示之具備2段式加熱器之延伸假撚加工機，製成具有捲 縮之聚酯假撚加工紗。 另外，於圖1中記載，將上述聚酯未延伸紗（1 )， 藉由設置於2對送料滾輪（3、3 ’）間之交錯噴嘴（4、 4 ’），進行空氣交絡處理之步驟。在此，經交絡處理之未 延伸紗係於送料滾輪（3 ’）及第1傳送滾輪（8 )之間被 延伸，藉由與旋轉之假撚盤（7 )摩擦而加撚。其間以第1 階段加熱器（5 )熱處理，以冷卻板（6 )冷卻，通過假撚 盤（7 )解撚。另外，傳送紗條係因應需要，以第1傳送 滾輪（8 )與第2傳送滾輪（1 〇 )之間所設置之第2階段 -13- 200831726 加熱器（9 )再加熱處理，進而，對熱定形假撚後紗條’ 施以空氣交絡（4，）後，以捲取滾輪（11 )捲取成筒狀包 裝（1 2 )，製造聚酯假撚加工紗。 考慮高速之延伸假撚加工，以第1階段加熱器（5 ) 及第2階段加熱器（9 )爲非接觸式爲宜。尤其’第2階 段加熱器多不使用，但因應觸感等之需要’使用亦無妨。 本發明中，假撚器（7 )係如圖2所示之3軸摩擦盤 式，位於解撚部份最下方盤之材質係陶瓷’而且’傳送紗 條與該盤之接觸長度爲2.5〜0.5 mm，另外，該盤係具有 最近上游盤直徑之90〜98 %之直徑爲宜。 亦即，如圖2所示之假撚器（7 )係於3支旋轉軸 (15)分別安裝各2個假撚盤（13)之3軸摩擦盤式者， 各旋轉軸（1 5 )係藉由以驅動帶（1 7 )所驅動之同步帶 (1 6 )以所定速度旋轉，使各假撚盤（1 3 )旋轉。本發明 之方法中係使用假撚盤（1 3 )中至少位於解撚部份最下方 盤（圖2例中係安裝於左側旋轉軸下方的盤）爲陶瓷製， 而且，該盤之直徑係最近上游盤（圖2例中係安裝於中央 旋轉軸下方的盤）直徑之90〜98%之直徑者。接著，該陶 瓷製盤與傳送紗條之接觸長度爲2.5〜0.5 mm。 此時，就耐摩損之觀點，最下方盤之材質係以陶瓷爲 宜。依據本發明者等之硏究，本發明之複合假撚加工中， 以傳送紗條與該盤之接觸長度爲2.5〜0.5 mm，可極力減 少加撚結束之捲縮狀態的紗條進入最後之解撚部份時之接 觸面積，減少抵抗，該結果係確定毛羽明顯減少，作爲結 -14- 200831726 果之強度提升，接著，該盤徑爲正上方盤徑之90〜 範圍時，移動引線至下個步驟（具體上係熱定形） 抗値變少，就順利移動上係有效的等。其中，傳送 上述盤之接觸長度爲2.5〜0.5 mm，明顯減少加工 結果係確認使強度提升特別有效。 本發明中假撚加工溫度係玻璃轉移溫度（以_ TG ) TG + 1 00°C 〜TG + 200°C，具體上以 170 〜300°C 此溫度未滿1 7 0 °c，捲縮性能降低，觸感硬，超過 時，因爲加工紗極端趨向扁平，發生加工毛羽，所 合。作爲假撚加工機，使用具備非接觸式之加熱器 時係以第1階段非接觸式加熱器之設定溫度爲1 70〜 進行熱處理爲宜。而且，因爲在此所謂適當之加熱 係依據市售之假撚加工機（帝人製機製2 1 6錘建 15V )，設定非接觸式之1.0〜1.5m長度者，糸 8 00m/分等之仕樣者，因此，使用特殊加熱器，或, 速度加工時等，當然可適當調整設定溫度。 在此，加撚範圍之第1加熱器係用以提升未延 之延伸性及假撚加工性（加撚性）者，此溫度於非 熱器時，爲未滿1 7 0 °C之溫度，加撚性降低，不能 發明目的之捲縮，製成織編物時之觸感如紙。另外 假撚加工時之斷紗及毛羽發生變多，捲縮斑或染色 色斑亦容易發生，所以不適合。另一方面，第1加 溫度若超過3 00 °C時，因爲延伸假撚加工時，容易 紗斷裂，尤其高伸度側之未延伸紗條（B ’）容易發 9 8 %之 時之抵 #條與 毛羽， 下稱爲 爲宜。 3〇〇°C 以不適 之裝置 ^ 3 0 〇 °C 器溫度 HTS-少速爲 以超高 伸紗條 接觸加 賦予本 ，延伸 時之染 熱器之 發生單 生單紗 -15- 200831726 斷裂，因爲所得之聚酯複合假撚加工紗係毛羽多者，所以 不適合。另外，依延伸假撚加工機之型式，雖然第1階段 加熱器分爲前半部及後半部，但於本發明方法中，第1階 段加熱器之前半部及後半部，設定爲相同溫度即可。 另外，第1階段加熱器中之紗條之熱處理時間雖依加 熱器種類、該長度及該溫度等而適當設定即可，但熱處理 時間過短時，捲縮率將容易變得不足，另外，容易發生起 因於張力變動之延伸假撚斷紗、假撚加工紗之毛羽、編織 物之染斑，另一方面，過長時捲縮率有變得過大之傾向。 因此，以非接觸式加熱器進行熱處理時，通常爲0.04〜 0 . 1 2秒之範圍，尤其〇 . 〇 6〜0 · 1 0秒之範圍係適當的。 另外，關於加工時之延伸倍率，1·4〜2.4係最適合之 範圍，超出此範圍時，因爲於低倍率側發生因突波、紗搖 動之熱定形斑，於高倍率側加工紗趨向扁平，發生加工毛 羽，所以不適合。 假撚數係複合假撚加工紗之纖度爲Y ( dtex )時，設 定範圍爲[(15000 〜35000) /Y1/2]回 /m，以[(20000 〜 30000 ) /Y1/2]回/m爲宜。假撚數未滿150〇〇/Yw2回化 時’將難以賦予微細且堅固的捲縮，所得布料如紙狀，觸 感變硬。假撚數超過35000/Y172回/m時，斷紗及毛羽發 生變多。 如此所得之本發明之極細聚酯假撚加工紗係可得到亦 維持傳統之極細聚酯假撚加工紗具有之柔和觸感、保濕 性、吸水、吸濕性等之性能，抗靜電性能亦優異的聚酯布 -16- 200831726 【實施方式】 實施例 以下係藉由實施例及比較例而更具體地說明本發明。 另外，實施例中所示之各測定値係以下述方法測定之値。 另外，除非特別例外，例中之「份」係指「重量份」。 (1 )固有黏度 溶解於鄰氯酚，使用烏別洛特（Ubbelohde )黏度 管，以3 5 °C測定。 (2 )傳送角 拍攝於假撚盤上傳送紗條的照片，於照片上實際測量 各假撚盤圓盤上紗條的傳統角度Θ，以此等測定値之平均 値作爲傳送角。 (3 )捲縮率 對聚酯假撚加工紗試樣，施以 0.044 cN/dtex之張 力，捲取於絞紗框，製成約3 3 00 dtex之絞紗，於該絞紗 的一端，負荷 0.0177 cN/dtex 及 0.177 cN/dtex 之 2 個荷 重，測定經過1分鐘後之長度SO (cm)。接著，於除去 0.177 cN/dtex荷重之狀態，於100°C之沸水中處理20分 鐘。沸水處理後除去0.0177 cN/dtex荷重，於自由狀態自 -17- 200831726 然乾燥 24小時，再次負荷 0.0177 cN/dtex及 0.177 cN/dtex之荷重，測定經過1分鐘後之長度爲SI ( cm)。 接著，除去0.177 cN/dtex荷重，測定經過1分鐘後之長 度爲S2 ( cm )，以下述算式算出捲縮率，以1 〇次測定値 之平均値表示。 捲縮率（％) = [(S1-S2)/S0]xl00 (4 )觸感 以本發明之假撚加工紗爲布料，由專業人員之官能檢 查係分爲如下述之等級1〜3級。 (柔和感） 等級1 :具有柔和且彈力的觸感 等級2 :雖稍缺乏柔和感，但可感到反彈性 等級3 :粗糙觸感或硬的觸感。 (5 )毛羽個數200831726 IX. OBJECT OF THE INVENTION [Technical Field] The present invention relates to a core-sheath type polyester fine-twisted textured yarn having antistatic properties, a method for producing the same, and an antistatic core-sheath type polyester fine 捻k Antistatic fabric for processing yarn. More specifically, the present invention relates to a method for producing a polyester fine-fine false-twisted yarn which can be stabilized and has a core-sheath structure having excellent antistatic properties. [Prior Art] Polyester fibers are widely used because of their excellent quality and stable physical properties. However, since polyester is originally hydrophobic, in the field where antistatic properties are required, many attempts have been made to impart hydrophilicity to the polyester so as to exhibit antistatic properties. In this example, for example, a method in which a polyoxyalkylene-based polyether compound is blended in a polyester (Japanese Patent Publication No. Sho 39-5214), and a polyoxyalkylene-based polyether compound having substantially non-φ compatibility is known. Japanese Patent Publication No. Sho. No. Sho. No. Sho. Japanese Laid-Open Patent Publication No. Sho 60-3 94 1 3, JP-A-3-139556, etc.). However, in the above method, in general, when the yarn is stretched (FOY), although the antistatic property is good, the hairiness occurs due to false twist deformation in the case of false twisting of the yarn, and there is a problem that good antistatic property cannot be obtained. . In addition, in recent years, the requirements for the touch of the knitted fabric, the touch of the skin, and the appearance of the -4-200831726 have been gradually increased, and the polyester false twisted textured yarn having a fineness of 16 dtex or less can be used. A fabric with a soft touch. 'When the polyester false twisted yarn is processed, it is extremely difficult to suppress the static electricity generation with the extremely fine densification. So far, it has been used for sports fabrics, uniforms, smash-proof garments, etc. For the use of women's shirts or shirts for skin, it can be said that there is no fabric with sufficient antistatic properties in the current situation. DISCLOSURE OF THE INVENTION The object of the present invention is to provide a polyester which can provide a fine polyester false twisted textured yarn which maintains soft touch, moisture retention, water absorption, hygroscopicity and the like, and is excellent in antistatic property. A fabric core-sheath type polyester fine-twisted textured yarn and a method for producing a core-sheath type polyester fine-twisted textured yarn which can be stably produced. In order to achieve the above object, the inventors of the present invention have found that the sheath component is coated with a polyoxyalkylene polyether compound and an organic ionic compound which are substantially incompatible with the polyester. The core-sheath type polyester ultrafine composite fiber of the core component can be used for the purpose of the invention when the melt-spinning process is performed under the specific conditions and the elongation false twisting process is performed. That is, according to the present invention, there is provided a core-sheath type composite fiber which is subjected to false twist processing, and the core of the core-sheath type composite fiber is composed of an antistatic agent containing 100 parts by weight of an aromatic polyester. (a) 0.2 to 30 parts by weight of a polyoxyalkylene-based polyether, and -5 to 200831726 (b) 0.05 to 10 parts by weight of an organic ionic compound substantially non-reactive with the polyester The polyester composition A is formed, and on the other hand, the sheath portion is formed of the aromatic polyester composition B, and the core-sheath type composite fiber is characterized by satisfying the conditions of (1) to (3) at the same time. Antistatic core-sheath type polyester extremely fine false twist processing yarn. (1) The single yarn fineness of the false twisted textured yarn is 1.6 dtex or less. (2) The crimping rate of the false twisted processed yarn is 3 to 30%. (3) The ratio SA of the area SA of the core and the area SB of the sheath is SB in the range of 5: 95 to 80: 20. And the core portion is a polyoxyl extension polyether containing (a) 0·2 to 30 parts by weight as an antistatic agent with respect to 100 parts by weight of the aromatic polyester, and (b) 0.05 to 10 The antistatic polyester composition A is formed by adding an organic ionic compound which is substantially non-reactive with the polyester, and the sheath is a core formed of the aromatic polyester composition B. When the sheath-type composite fiber is melt-spun, the ratio of the ejection speed and the drawing speed at the time of spinning (pull speed/discharge speed, hereinafter referred to as draft rate) is 150 or more, and the range of less than 800 is insufficient. After the drawing, a method for producing an antistatic core-sheath type polyester fine-twisted textured yarn characterized by false twisting is performed. And 3 is a fabric containing a core-sheath type polyester false twist processing yarn, and the core-sheath type polyester-6 - 200831726 false twisted processed yarn is the antistatic core-sheath type polyester fine fine false twisted textured yarn described in the above 1 Features an antistatic fabric. BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail. The polyester in the present invention is obtained by reacting an aromatic polyester having an aromatic ring in a polymer structural unit, a difunctional aromatic carboxylic acid or the ester-forming derivative with a diol or an ester-forming derivative. The polymer is the object. Here, the difunctional aromatic carboxylic acid may, for example, be terephthalic acid, isophthalic acid, phthalic acid, 1,5-naphthalene dicarboxylic acid or 2,5-naphthalene dicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-biphenylmethane Carboxylic acid, 4,4'-biphenylfluorene dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, i,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid , 2,5-nonanedicarboxylic acid, 2,6-nonanedicarboxylic acid, 4,4,-terephthalic acid, 2,5-pyridinedicarboxylic acid, point-hydroxyethoxybenzoic acid, p-hydroxyl For benzoic acid, etc., terephthalic acid is preferred. These difunctional aromatic carboxylic acids may be used in combination of two or more kinds. Further, in the case of a small amount, these difunctional aromatic carboxylic acids may also be difunctional with one or two of adipic acid, sebacic acid, sebacic acid, and dodecanedioic acid. An aliphatic carboxylic acid, a difunctional alicyclic carboxylic acid such as cyclohexanedicarboxylic acid, sodium 5-sulfoisophthalate or the like. Further, as the diol compound, for example, ethylene glycol, propylene glycol, butylene glycol, hexanediol, neopentyl glycol, 2-methyl-1,3-propylene glycol, diethylene glycol, and tri-methyl An aliphatic diol of a diol, such as 1,4-cyclohexane II 200831726, an alicyclic diol of methanol, or the like, and the like. Further, in the case of a small amount, these diol compounds may be copolymerized with a polyoxyalkylene glycol which is blocked at both ends or at one end. Further, as the polyester, a substantially linear range such as a trimellitic acid, a polycarboxylic acid of pyromellitic acid, a polyol such as glycerin, trimethylolpropane or pentaerythritol can be used. Specific examples of suitable aromatic polyesters include polyethylene terephthalate, polybutylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate. Esters, polybutylene naphthalate, polyethylene 1,2-bis(phenoxy)ethane-4,4,dicarboxylic acid glycol, and the like, and polyethylene isophthalate ♦ a copolymerized polyester such as terephthalate, polybutylene terephthalate, isophthalate, polybutylene terephthalate or decane dicarboxylate. Among them, polyethylene terephthalate and polybutylene terephthalate having a balance of mechanical properties and formability are preferable. The related aromatic polyesters are synthesized by any method. For example, regarding polyethylene terephthalate, by directly esterifying terephthalic acid with ethylene glycol, or lower alkyl ester of terephthalic acid such as dimethyl terephthalate. Exchanging reaction with ethylene glycol or reacting terephthalic acid with ethylene oxide to produce a first stage reaction of ethylene glycol terephthalate and/or the low polymer, and then the product is The mixture is heated under reduced pressure to carry out a polycondensation reaction to a second-stage reaction which is a desired degree of polymerization, and can be easily produced. The polyoxyalkylene-based polyether (a) to be blended with the composition used in the present invention may be a polyoxygen extension unit formed from a single polyoxyalkylene unit-8 - 200831726 if it is substantially insoluble to the polyester. The ethylene glycol may be a copolymerized polyoxyalkylene glycol obtained from two or more polyoxyalkylene units, or may be a polyoxyalkylene system represented by the following general formula (I). Polyether. Z-[(CH2CH2〇)n(R1〇)m.R2]k (I) (In the above formula (I), Z represents an organic compound residue having 1 to 6 active hydrogen atoms, and R1 represents More than 6 carbon atoms or substituted alkyl groups, R2 series non-hydrogen atoms, carbon number 1 to 40 one-valent hydrocarbon groups, carbon number 2 to 40 one-valent hydroxy hydrocarbons or carbon number 2 to 40 One of the valence groups, k is an integer from 1 to 6, n is an integer satisfying n - 7 Ο/k, and m is an integer of 1 or more.) Specific as a polyoxyalkylene polyether For example, polyoxyethylene ethylene glycol having a molecular weight of 4,000 or more, polyoxypropylene glycol having a molecular weight of 1 Å or more, polyoxytetramethylene glycol, and a molecular weight of 2,000 or more Ethylene oxide, propylene oxide copolymer, trimethylolpropane ethylene oxide adduct having a molecular weight of 4000 or more, nonylphenol ethylene oxide adduct having a molecular weight of 3,000 or more, and the like a terminal OH group, a compound having a carbon number of 6 or more substituted ethylene oxide, wherein a polyoxyethylene ethylene glycol having a molecular weight of 1,000,000 to 100,000 and a molecular weight of 5 000 〜 Preferably, a compound having an alkyl group substituted with ethylene oxide having an alkyl group of 8 to 40 is added to the both ends of the polyoxyethylene ethylene glycol of 1 600 0. The compounding amount of the polyoxyalkylene-based polyether compound is 0.2 to 30 parts by weight based on 1 part by weight of the above aromatic polyester. When it is less than 0.2 -9 - 200831726 parts by weight, it is insufficient in hydrophilicity and does not exhibit sufficient antistatic property. On the other hand, even if it is more than 30 parts by weight, it is considered that there is no effect of improving the antistatic property, and the mechanical properties of the obtained composition are adversely impaired, and since the polyether becomes easy to bleed out, it is formed during melt forming. The fitting of the slicing machine is lowered, and the form stability is also deteriorated. In the polyester composition of the present invention, an organic ionic compound is blended especially for enhancing the antistatic property. The organic ionic compound may, for example, be a sulfonic acid metal salt or a sulfonic acid quaternary acid salt represented by the following general formulas (Π) and (ΠΙ). (Π) rso3m (In the above formula (π), R represents an alkyl group having 3 to 30 carbon atoms or an aryl group having 7 to 40 carbon atoms, and the lanthanide group is an alkali metal or an alkaline earth metal.) RSChPRm4 ...... (Melon) (In the above formula (dish), R is an alkyl group having 3 to 30 carbon atoms or an aryl group having 7 to 40 carbon atoms, and R1, R2, R3 and R4 are alkyl groups or aryl groups, of which An alkyl group, a phenyl group or a benzyl group is preferred.) In the above formula (Π), when R is an alkyl group, the alkyl group may be linear or branched. The lanthanide is an alkali metal such as Na ' K, Li or the like, or an alkaline earth metal such as Mg or Ca. Among them, Li, Na and K are preferred. The sulfonic acid metal salt may be used singly or in combination of two or more. -10- 200831726 Specific examples of suitable examples include sodium stearyl sulfonate, sodium octyl sulfonate, sodium dodecyl sulfonate, a mixture of sodium alkylsulfonates having an average carbon number of 14, and dodecane. Sodium benzenesulfonate mixture, sodium dodecylbenzene sulfonate (hard, soft), lithium laurylbenzene sulfonate (hard, soft), magnesium dodecylbenzenesulfonate (hard) , soft type, etc. In addition, the sulfonic acid quaternary salt of the formula (ΠΙ) may be used singly or in combination of two or more. Specific examples of suitable examples include, for example, tetrabutyl sulfonate of an alkyl sulfonate having an average carbon number of 14 and butyl tetraphenyl iron of an alkyl sulfonate having a carbon number of 14 and an average number of 14 carbon atoms. Butyl triphenyl sulfonate, tetrabutyl benzene sulfonate (hard, soft), tetraphenyl benzene sulfonate (hard, soft), twelve Alkylbenzenesulfonic acid benzyltriphenyl scale (hard, soft) and the like. The organic ionic compound may be used alone or in combination of two or more kinds, and the amount thereof is in the range of from 0.001 to 10 parts by weight based on 100 parts by weight of the aromatic polyester. When the amount of the organic ionic compound is less than 0.05 parts by weight, the effect of improving the antistatic property is small, and when it exceeds 10 parts by weight, the mechanical properties of the composition are impaired, and since the ionic compound is also likely to bleed out, The slicing of the chips at the time of melt forming is lowered to the extruder, and the form stability is also deteriorated. Further, in the polyester B, a known matting agent such as titanium oxide or the like may be blended in a range which does not inhibit the object of the present invention. However, when the amount of the matting agent exceeds 10% by weight, the spinning property of the undrawn yarn which is the main yarn of the present invention is deteriorated, so the range is preferably 1 to 10 Wt%. Further, the extremely fine false twisted textured yarn of the present invention has a single yarn fineness of 1.6 -11 - 200831726 dtex or less and a crimp ratio of 3 to 30%, and by this range, a knitted fabric excellent in softness and touch can be obtained. When the crimp ratio is less than 3%, the woven fabric does not have sufficient fluffiness. On the other hand, when it exceeds 30%, the antistatic property is lowered, which is not preferable. Further, the ratio SA: SB of the area SA of the core portion and the area SB of the sheath portion must be in the range of 5: 95 to 80 · · 20. When the area ratio is less than 5:95, the antistatic performance of the polyester A is insufficient. When the ratio is more than 80:20, when the alkali reduction of more than 1% is applied, the antistatic polyester of the core is dissolved, and the antistatic is antistatic. The performance is lowered, or the strength of the false-twisted yarn is reduced to 3.0 cN/dtex or less. Since the strength of the fabric is insufficient, it is not suitable for applications requiring strength such as sportswear, and is not suitable because of limited use. The polyester ultrafine false twist processing yarn of the present invention described above will be the ratio of the discharge speed and the pull speed at the time of spinning when the untwisted yarn of the main yarn is melted and spun (pulling speed/discharge speed, after Abbreviated as the traction magnification), the unstretched yarn after the range of 1 0 0 or less is not fully loaded, and the false anti-stretching is performed to obtain stable antistatic performance. When the draw ratio is less than 150, the antistatic performance of the polyester A is insufficient, and when the draw ratio is 800 or more, the antistatic property is exhibited, but the spinning property is lowered, which is not suitable. When the draw ratio is set to the above range, the metal orifice discharge aperture and the spinning speed may be appropriately set, but the discharge aperture is Φ 〇 1 〇 · 3 , and the spinning speed is 2000 to 4500 m/min, especially 2500 to 3500. When the m/min range is melted, it can be easily and efficiently obtained, so it is suitable. At this time, the complex refractive index of the unstretched composite yarn is preferably in the range of 0·02 to 0.05. When the complex refractive index is less than 0.02, the force of the sheet -12 - 200831726 during the false twist processing is reduced, and the surging and the yarn are likely to be shaken, so that the heat-set spots, the stains are poor, and the processing magnification is increased. Weak yarn, so it is not suitable. On the other hand, when the complex refractive index exceeds 0.05, the original yarn hairiness tends to occur, and the steps are not smooth, so it is not suitable. The false twist processing method for the unstretched yarn is not particularly limited, but a method described below can be used. First, the air entanglement process can be performed in different steps from the extended false twist process. However, as shown in Fig. 1, an interlace nozzle is provided in the extended false twist processing device, which is preferably performed before the extended false twist process. In this way, the occurrence of hairiness is suppressed, and the operability is also affected. In addition, air entanglement is applied to the heat-fixed false twisted gauze, because the mixed fiber entanglement is perfectly uniformed, and the yarn has a uniform direction in the longitudinal direction, and has antistatic properties. Sexuality and performance. Next, the unstretched yarn to which the entanglement treatment is applied is supplied to, for example, an extended false twisting machine equipped with a two-stage heater as shown in Fig. 1, to obtain a polyester false twisted textured yarn having a crimp. Further, as shown in Fig. 1, the polyester undrawn yarn (1) is subjected to an air entanglement treatment by a staggered nozzle (4, 4') provided between two pairs of feed rollers (3, 3'). . Here, the undrawn yarn which has been subjected to the entanglement process is stretched between the feed roller (3') and the first transfer roller (8), and is twisted by rubbing against the rotating false disk (7). In the meantime, it is heat-treated by the first stage heater (5), cooled by the cooling plate (6), and untwisted by the false plate (7). In addition, the conveying sliver is reheated by the second stage-13-200831726 heater (9) provided between the first conveying roller (8) and the second conveying roller (1 〇) as needed, and further, After the heat-setting false twisted yarn is applied to the air entanglement (4,), the take-up roller (11) is taken up into a cylindrical package (1 2) to produce a polyester false twisted textured yarn. In consideration of the high-speed extension false twist processing, the first stage heater (5) and the second stage heater (9) are preferably non-contact type. In particular, the second stage heater is not used, but it may be used in response to the need for touch. In the present invention, the false twister (7) is a 3-axis friction disc type as shown in FIG. 2, and the material of the lowermost disc located in the untwisting portion is a ceramic 'and the contact length of the conveying sliver with the disc is 2.5~ 0.5 mm, in addition, the disc has a diameter of 90 to 98% of the diameter of the nearest upstream disc. That is, the false twister (7) shown in FIG. 2 is a three-axis friction disc type in which two rotating shafts (13) are respectively mounted on three rotating shafts (15), and each rotating shaft (15) Each of the false twist disks (13) is rotated by rotating the timing belt (16) driven by the drive belt (17) at a predetermined speed. In the method of the present invention, at least the lowermost disk of the untwisting portion (the disk mounted under the left-hand rotating shaft in the example of FIG. 2) is made of ceramic, and the diameter of the disk is used. Recently, the upstream disk (the disk mounted under the central rotating shaft in the example of Fig. 2) has a diameter of 90 to 98%. Next, the contact length of the ceramic plate with the conveying sliver is 2.5 to 0.5 mm. At this time, in terms of wear resistance, the material of the lowermost plate is preferably ceramic. According to the inventors of the present invention, in the composite false twist processing of the present invention, the contact length of the conveying sliver and the disc is 2.5 to 0.5 mm, and the sliver of the crimping state at the end of the twisting can be minimized to enter the final state. The contact area of the part is reduced, and the resistance is reduced. The result is that the hairiness is significantly reduced, as the strength of the knot is increased, and then the disk diameter is 90 to the range of the upper disk diameter, and the lead is moved to The next step (specifically, heat setting) is less effective, and it is effective to move the upper system. Among them, the contact length of the transfer tray is 2.5 to 0.5 mm, which significantly reduces the processing result and confirms that the strength increase is particularly effective. In the present invention, the false twist processing temperature is the glass transition temperature (by _TG) TG + 1 00 ° C ~ TG + 200 ° C, specifically 170 ~ 300 ° C, the temperature is less than 170 ° C, crimping performance Reduced, the touch is hard, when it is over, because the processed yarn is extremely flat, the processing of hairiness occurs. When a non-contact type heater is used as the false twist processing machine, it is preferable to heat-treat the first stage non-contact heater at a set temperature of 1 70 〜. Moreover, because the so-called appropriate heating system is based on a commercially available false twisting machine (the Teijin system 2 1 6 hammer built 15V), the non-contact type is set to a length of 1.0 to 1.5 m, and the number is 00 m/min. In this case, it is of course possible to adjust the set temperature appropriately by using a special heater or during speed machining. Here, the first heater in the twisting range is used to increase the elongation of the unextended and the workability of the false twist (the twisting property), which is a temperature less than 170 ° C in the non-heater. The twisting property is lowered, and the shrinkage of the object cannot be invented, and the touch is made of paper when the weaving is made. In addition, the yarn breakage and hairiness at the time of false twisting are increased, and the curling or staining spots are also likely to occur, so it is not suitable. On the other hand, when the first heating temperature exceeds 300 ° C, the yarn is easily broken when the false twisting is processed, and especially when the unstretched yarn (B ') on the high-stretch side is easily released by 98%. #条与毛羽, the next is called Yi. 3〇〇°C Unsuitable device ^ 3 0 〇°C Temperature HTS-Low speed is the contact with the super high-stretched yarn, and the single-single yarn of the dyeing machine when extended is -15-200831726 Because the obtained polyester composite false twist processing yarn has many hairiness, it is not suitable. Further, according to the type of the extension false twisting machine, although the first stage heater is divided into the front half and the rear half, in the method of the present invention, the first half and the second half of the first stage heater are set to the same temperature. . In addition, the heat treatment time of the yarn in the first-stage heater may be appropriately set depending on the type of the heater, the length, the temperature, and the like. However, when the heat treatment time is too short, the crimp ratio is likely to be insufficient. It is prone to occur due to the extension of the tension fluctuation, the hairiness of the false twisted yarn, and the dyeing of the knitted fabric. On the other hand, the curling ratio tends to be too large when the length is too long. Therefore, when heat treatment is performed by a non-contact heater, it is usually in the range of 0.04 to 0.12 seconds, especially 〇. The range of 〇 6 to 0 · 10 seconds is appropriate. In addition, regarding the stretching ratio at the time of processing, the range of 1·4 to 2.4 is the most suitable range. When it exceeds this range, the processing yarn on the high-magnification side tends to be flat due to the heat-set spot on the low-magnification side due to the swell and the yarn swaying. , processing hairiness occurs, so it is not suitable. When the fineness of the composite false twisted yarn is Y (dtex), the setting range is [(15000 ～35000) /Y1/2] back/m, with [(20000 ～ 30000 ) /Y1/2] back / m is appropriate. When the number of false twists is less than 150 〇〇/Yw2, it will be difficult to impart a fine and strong crimp, and the resulting fabric is paper-like, and the touch is hard. When the number of false twists exceeds 35,000/Y172/m, the yarn breakage and hairiness increase. The ultrafine polyester false twist processing yarn of the present invention thus obtained can obtain the properties of soft touch, moisture retention, water absorption, moisture absorption, etc. which are also maintained by the conventional ultrafine polyester false twisted textured yarn, and excellent in antistatic property. Polyester Cloth-16 - 200831726 [Embodiment] Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. Further, each of the measurement oximes shown in the examples was measured by the following method. In addition, unless otherwise specified, "parts" in the examples means "parts by weight". (1) Intrinsic viscosity Dissolved in o-chlorophenol, measured using a Ubbelohde viscosity tube at 35 °C. (2) Transfer angle The photograph of the sliver is taken on the false twist disc, and the conventional angle 纱 of the sliver on each false disc disc is actually measured on the photograph, and the average 値 of the 値 is determined as the transfer angle. (3) The crimping rate is applied to the polyester false twisted textured yarn sample by applying a tension of 0.044 cN/dtex, and is taken up in a skein frame to make a skein of about 3 3 00 dtex at one end of the skein. Two loads of 0.0177 cN/dtex and 0.177 cN/dtex were measured, and the length SO (cm) after one minute was measured. Subsequently, the state of 0.177 cN/dtex was removed and treated in boiling water at 100 ° C for 20 minutes. After the boiling water treatment, the load of 0.0177 cN/dtex was removed, and the free state was dried from -17 to 200831726 for 24 hours, and the load of 0.0177 cN/dtex and 0.177 cN/dtex was again loaded, and the length after 1 minute was measured as SI (cm). Subsequently, the load of 0.177 cN/dtex was removed, and the length after one minute of measurement was measured as S2 (cm), and the crimp ratio was calculated by the following formula, and the average enthalpy of 値 was measured in 1 time. Crimping rate (%) = [(S1-S2)/S0]xl00 (4) Tactile sensation The false-twisted processed yarn of the present invention is used as a cloth, and the functional inspection by a professional is classified into the following grades 1 to 3 . (Soft feeling) Level 1: Soft and elastic touch Level 2: Although it is slightly soft, it feels rebound. Level 3: Rough touch or hard touch. (5) the number of hairiness
Toray (股）製DT-104型毛羽計數裝置，以 500 m/min之速度，連續測定聚酯假撚加工紗試樣20分鐘， 計數發生的毛羽數，以每1萬m試樣長度之個數表示。 (6 )帶電性試驗方法 (摩擦帶電壓測定法） 使試驗片旋轉，以摩擦布摩擦，測定發生之帶電壓。 -18- 200831726 依據L 1 094帶電性試驗方法B法（摩擦帶電壓測定法）。 關於抗靜電效果，摩擦帶電壓約爲2000V以下（以1 500V 以下爲宜）時，可達到抗靜電效果。 實施例1 加入100份之對苯二甲酸二甲酯、60份之乙二醇、 〇.〇6份（相對於對苯二甲酸二甲酯爲0.066莫耳％)之醋 酸鈣1水鹽及0.013份（相對於對苯二甲酸二甲酯爲〇.〇1 莫耳％ )之作爲整色劑之醋酸鈷4水鹽於酯交換反應罐， 將此反應物於氮氣環境下，以4小時，自140 °C升溫至 220 °C，一邊將反應罐中產生的甲醇餾去於系統外，一邊 使進行酯交換反應。 酯交換反應結束後，加入〇·〇58份（相對於對苯二甲 酸二甲酯爲0.080莫耳％)之作爲安定劑之磷酸三甲酯、 及〇.〇24份之作爲消泡劑之二甲基聚矽氧烷於反應混合 物。接著，於10分鐘後，添加0.041份（相對於對苯二 甲酸二甲酯爲0.027莫耳％ )之三氧化銻於反應混合物， 同時餾去過剩的乙二醇下，升溫至2 4 0 °C，之後，將反應 混合物移至聚合反應罐。接著，以1小時40分鐘，自760 mmHg減壓至1 mmHg，並且自240X：升溫至280T：，使進 行聚縮合反應後，於真空下添加如下述式所示之4份之水 不溶性之聚氧伸烷系聚醚及2份之十二烷基苯磺酸鈉，再 使進行聚縮合反應240分鐘，接著，於真空下添加〇.4份 之作爲抗氧化劑之Ciba-Geigy社製irganoxi〇i〇後，再進 -19- 200831726 行聚縮合反應3 0分鐘。聚合反應步驟係添加抗靜電劑， 所得之聚酯係依常法製成切片。 0卜趨一fCHg CHg 〇今一 c J Hi i+i H « C H O h » I io C 3 H1 jtl ⑩ (但是，j係18〜28之整數，平均爲21，P係平均値爲 100, m係平均値爲5。在此所謂的平均値係指2種以上之 氧伸乙基單位所成之共聚合聚氧伸烷系聚醚中之氧伸氧基 單位之數之平均値。） 所得聚合物之固有黏度爲0.6 5 7，軟化點爲2 5 8 °C。 將所得之切片，以及含0.4重量％之氧化鈦微粒子之 固有黏度爲0.65之通常之聚對苯二甲酸乙二醇酯切片， • 由常法乾燥後，於紡紗設備將該切片以各種常法溶融，通 過旋轉裝置，導入.各複合纖維用紡絲孔板（spin pack)。 . 由該紡絲孔板所安裝之穿設72個芯鞘型複合圓形噴出孔 之紡紗金屬口，以通常之橫流型紡紗筒之冷卻風冷卻、硬 化，賦予紡紗油劑，集束成爲一個紗條，以3 000 m/min 之速度（牽引倍率·· 200 )捲取，得到140 dtex/72單絲之 芯/鞘的面積比率爲70 : 30之聚酯芯鞘型複合未延伸紗。 將該聚酯未延伸紗，供予帝人製機製216錘建HTS-15V，如圖1之（4,4’），於前段、後段，使通過具有孔 -20- 200831726 徑爲1.8 mm之壓空吹出孔之交錯噴嘴，以60nL/min之流 量，施以空氣交絡，使交絡度成50個/m，延伸倍率爲 1.60，設定第1加熱器（非接觸型）溫度爲250 °C之條 件，以直徑爲60 mm，厚度爲9 mm之氨基甲酸乙酯盤作 爲假撚盤，傳送角爲43度，進行延伸假撚，使假撚數X (假撚紗纖度（dtex )) 1/2爲26000附近，以速度爲800 m/min捲取成筒狀，得到84 dtex/72單絲（平均單絲纖度 爲1 _ 17 dtex )之芯鞘比率爲70 : 30之聚酯假撚加工紗。 使用此等聚酯假撚加工紗，製造筒編物，測定抗靜電 性。所得之聚酯假撚加工紗之摩擦帶電壓爲1 200V。另 外，由常法將此等之聚酯假撚加工紗製成織物，官能評估 該品質時，非常具有深度，而且，具有高級感，呈現柔和 感者。該結果如表1所示。 比較例1 於鹼觸媒之存在下，使聚乙二醇與丙烯腈反應，再藉 由進行氫化反應，合成兩末端之9 7%以上爲胺基之聚乙二 醇二胺（數平均分子量爲4000 )，藉由以定法使其與己二 酸進行鹽反應，得到45 %之聚乙二醇二銨己二酸酯水溶 液。 於容量爲2m3之濃縮罐中，加入200 kg之上述45% 之聚乙二醇二銨己二酸酯水溶液、120 kg之8 5%之己內醯 胺水溶液、16 kg之40 %之六伸甲基二銨間苯二甲酸酯水 溶液，加熱約2小時至常壓下內溫爲110 °C，濃縮成8 0 % -21 - 200831726 濃度。接著，將上述濃縮液移至容量爲8001之聚合罐， 於聚合罐內以2.5 Ι/min氮氣流動下開始加熱。 內溫成1 2 (TC時，添加5 · 2 kg ( 2 · 5重量％ )之十二烷 基苯磺酸鈉及5.2 kg(2.5重量％)之1，5,5三甲基- 2,4,6-三（3,5·二叔丁基4-羥基苯）苯（ΤΤΒ )，開始攪拌，加 熱18小時至內溫成245 °C，結束聚合反應。聚合反應結束 後，以通常方法製粒，得到由嵌段聚醚醯胺組成物而成之 顆粒。 於固有黏度爲0.65之通常的不含氧化鈦之聚對苯二 甲酸乙二醇酯切片中，混合成爲1.4重量％之由上述嵌段 聚醚醯胺組成物而成之顆粒，以此爲芯成份以外，與實施 例1同樣地實施，得到84 dtex/72單絲（平均單絲纖度爲 1.17 dtex)之芯鞘比率爲70 : 30之聚酯假撚加工紗。由 此纖維而成之布料雖顯示與實施例1同樣的柔和優異觸 感，但摩擦帶電壓非常差，爲3400V者。結果歸納如表」 所示。 實施例2〜3 除了改變聚合物噴出量以外，與實施例1同樣地實 施，得到56 dtex/72單絲（平均單絲纖度♦爲0.78 dtex)以 及1 1 1 dtex/72單絲（平均單絲纖度爲1.54 dtex )之芯鞘 比率爲70 : 3 0之芯鞘型複合聚酯假撚加工紗。由此等紗 製作的布料係摩擦耐電壓、觸感皆優異。結果歸納如袠i 所示。 -22- 200831726 比較例2〜3 除了改變聚合物噴出量以外，與比較f 施，得到56 dtex/72單絲（平均單絲纖度爲 及111 dtex/72單絲（平均單絲纖度爲1.54 比率爲70 : 3 0之芯鞘型複合聚酯假撚加工 製作的布料雖然觸感與實施例1同樣地優異 壓局，不適於實用者。結果歸納如表1所Tpc 比較例4 除了增加聚合物噴出量以外，與實施书 施，得到133 dtex/72單絲（平均單絲纖度j 之芯鞘比率爲70: 30之芯鞘型複合聚酯假 此等紗製作的布料雖然摩擦帶電壓與實施伯 異，但觸感硬’不適於實用者。結果歸納如: 比較例5 除了改變金屬口成3 6孔以外，與實施， 施’得到84 dtex/36單絲（平均單絲纖度爲 芯鞘比率爲70: 30之芯鞘型複合聚酯假撚 等紗製作的布料雖然摩擦帶電壓與實施例1 但觸感硬，不適於實用者。結果歸納如表1 ^ 比較例6 丨1同樣地實 0·78 dtex)以 dtex)之芯鞘 紗。由此等紗 ，但摩擦帶電 丨1同樣地實 i 1·8 5 dtex ) 撚加工紗。由 j 1同樣地優 菱1所示。 利1同樣地實 2_33 dtex )之 加工紗。由此 同樣地優異， 斤示。 -23- 200831726 除了增加聚合物噴出量以外，與比較例1同樣地實 施’得到133 dtex/72單絲（平均單絲纖度爲1.85 dtex) 之芯鞘比率爲70 : 3 0之芯鞘型複合聚酯假撚加工紗。由 此等紗製作的布料雖然摩擦帶電壓比比較例1高，但仍不 足，加上觸感硬，不適於實用者。結果歸納如表1所示。 比較例7 除了改變金屬口成3 6孔以外，與比較例1同樣地實 施，得到84 dtex/36單絲（平均單絲纖度爲2·33 dtex)之 芯鞘比率爲7 0 : 3 〇之芯鞘型複合聚酯假撚加工紗。由此 等紗製作的布料雖然摩擦帶電壓比比較例1高，但仍不 足，加上觸感硬，不適於實用者。結果歸納如表1所示。 表1 牽引倍率 (倍） 單纖維纖度 (dtex) 捲縮率 (%) 毛羽個數 (個/1萬m) 摩擦帶電壓 (V) 觸感 (等級） 實施例1 200 U7 15 20 1200 1 實施例2 300 0.78 18 30 1200 1 實施例3 180 1.54 20 15 1100 1 比較例1 200 1.17 20 15 3400 1 比較例2 300 0.78 15 30 4000 1 比較例3 180 1.54 15 20 2700 1 比較例4 120 1.85 20 13 1000 3 比較例5 185 2.33 25 10 1000 3 比較例ό 120 1.85 18 10 2000 3 比較例7 185 2.33 25 10 2000 3 *PEG(分子量20000) **十二烷基苯磺酸鈉 -24- 200831726 【圖式簡單說明】 【伸同時假撚 、2係引線 係第1階段 盤（friction t段加熱器、 I酯假撚加工 I裝置之一種 、15係旋轉 圖1係本發明使用之製造假撚加工紗之远 加工機之槪略圖，1係芯鞘型聚酯未延伸紗 器、3、3 ’係送料滾輪、4、4，係交錯噴嘴、5 加熱器、6係冷卻板、7係假撚器（3軸摩擦 disk)裝置）、8係第1傳送滾輪、9係第2 _ 1 0係第2傳送滾輪、1 1係捲取滾輪、i 2係赛 紗筒。 另外，圖2係表示本發明中使用之假撚塵 實施形態之正面圖，1 3係假撚盤、1 4係導盤 盤、1 6係同步帶、1 7係驅動帶。 【主要元件符號說明】 1 :芯鞘型聚酯未延伸紗 2 :引線器 3 :送料滾輪 3 ’ ：送料滾輪 4 :交錯噴嘴 5 :第1階段加熱器 6 :冷卻板 7 =假撚盤（3軸摩擦盤裝置） 8 :第1傳送滾輪 9 :第2階段加熱器 1 〇 :第2傳送滾輪 -25- 200831726 1 1 :捲取滾輪 1 2 :聚酯假撚加工紗筒 13 :假撚盤 14 :導盤 1 5 :旋轉軸 1 6 :同步帶 1 7 :驅動帶Toray (stock) DT-104 hairiness counting device, continuously measuring the polyester false twisted yarn sample for 20 minutes at a speed of 500 m/min, counting the number of hairiness that occurred, to the length of each 10,000 m sample The number indicates. (6) Charge test method (friction band voltage measurement method) The test piece was rotated, rubbed with a rubbing cloth, and the generated band voltage was measured. -18- 200831726 According to L 1 094 charge test method B method (friction band voltage measurement method). Regarding the antistatic effect, when the friction band voltage is about 2000 V or less (preferably 1 500 V or less), the antistatic effect can be achieved. Example 1 100 parts of dimethyl terephthalate, 60 parts of ethylene glycol, 6 parts of ruthenium (0.066 mol% relative to dimethyl terephthalate) of calcium acetate monohydrate and 0.013 parts (relative to dimethyl terephthalate is 〇.〇1 mol%) of cobalt acetate 4 water salt as a color former in a transesterification reaction tank, the reaction was carried out under nitrogen for 4 hours The temperature was raised from 220 ° C to 220 ° C, and the methanol produced in the reaction tank was distilled off the system, and the transesterification reaction was carried out. After the end of the transesterification reaction, 58 parts of hydrazine (0.080 mol% relative to dimethyl terephthalate), trimethyl phosphate as a stabilizer, and 24 parts of hydrazine were added as an antifoaming agent. Dimethyl polyoxane is in the reaction mixture. Then, after 10 minutes, 0.041 parts (0.027 mol% relative to dimethyl terephthalate) of antimony trioxide was added to the reaction mixture while distilling off excess ethylene glycol, and the temperature was raised to 2 4 0 ° C, after that, the reaction mixture was transferred to a polymerization tank. Next, the pressure was reduced from 760 mmHg to 1 mmHg in 1 hour and 40 minutes, and from 240X: to 280T:, after the polycondensation reaction was carried out, 4 parts of water-insoluble aggregates as shown in the following formula were added under vacuum. An oxygen-terminated polyether and 2 parts of sodium dodecylbenzenesulfonate were further subjected to a polycondensation reaction for 240 minutes, and then 4 parts of irganoxi〇 manufactured by Ciba-Geigy Co., Ltd. as an antioxidant was added under vacuum. After i〇, proceed to -19-200831726 for a polycondensation reaction for 30 minutes. In the polymerization step, an antistatic agent is added, and the obtained polyester is formed into a slice by a usual method. 0卜向一fCHg CHg 〇今一c J Hi i+i H « CHO h » I io C 3 H1 jtl 10 (However, j is an integer from 18 to 28, with an average of 21, and the average P of the P system is 100, m The average enthalpy is 5. The average enthalpy referred to herein means the average enthalpy of the number of oxygen-extended oxy units in the copolymerized polyoxyalkylene polyether formed by two or more oxygen-extended ethyl units. The polymer has an intrinsic viscosity of 0.65 and a softening point of 2,58 °C. The obtained section, and a typical polyethylene terephthalate section having an intrinsic viscosity of 0.65 containing 0.4% by weight of titanium oxide fine particles, were dried by a conventional method, and the sections were subjected to various usual conditions in a spinning apparatus. The method is melted and introduced into a spin pack for each composite fiber by a rotating device. The spinning metal hole of the 72 core-sheath type composite circular ejection holes installed by the spinning orifice plate is cooled and hardened by the cooling air of a usual cross-flow type spinning bobbin, and the spinning oil agent is bundled. Become a sliver and take it at a speed of 3 000 m/min (traction magnification · 200) to obtain a polyester core-sheath composite with an area ratio of 70 dtex/72 monofilament core/sheath of 70:30. yarn. The polyester is not stretched and supplied to the Teijin mechanism 216 to build the HTS-15V, as shown in Fig. 1 (4, 4'). In the front and rear sections, the pressure is 1.8 mm with a hole of -20-200831726. The staggered nozzle of the air blowing hole is air-interconnected at a flow rate of 60 nL/min, the degree of symmetry is 50/m, the stretching ratio is 1.60, and the temperature of the first heater (non-contact type) is set to 250 °C. A urethane disc with a diameter of 60 mm and a thickness of 9 mm was used as a false twist disc, and the transfer angle was 43 degrees. The false twist was performed so that the number of false twists X (false twisted yarn (dtex)) 1/2 was In the vicinity of 26000, the tube was taken up at a speed of 800 m/min to obtain a polyester false twisted textured yarn having a core sheath ratio of 70:30 of 84 dtex/72 monofilament (average single filament fineness of 1 _ 17 dtex). These polyester false twisted textured yarns were used to produce a tubular fabric, and the antistatic property was measured. The friction band voltage of the obtained polyester false twisted textured yarn was 1 200V. In addition, these polyester false twisted textured yarns are made into fabrics by the conventional method, and when the quality is evaluated, the depth is very high, and the sense of high quality is mild. The results are shown in Table 1. Comparative Example 1 Polyethylene glycol was reacted with acrylonitrile in the presence of a base catalyst, and a polyethylene glycol diamine having an amine group at both ends was synthesized by hydrogenation reaction (number average molecular weight) It is 4000), and a salt reaction with adipic acid is carried out by a predetermined method to obtain a 45% aqueous solution of polyethylene glycol diammonium adipate. In a concentration tank of 2 m3, 200 kg of the above 45% aqueous solution of polyethylene glycol diammonium adipate, 120 kg of 85% aqueous solution of caprolactam, 16 kg of 40% of the six extensions were added. The aqueous solution of methyl diammonium isophthalate was heated for about 2 hours to an internal temperature of 110 ° C under normal pressure, and concentrated to a concentration of 80% -21 - 200831726. Next, the above concentrate was transferred to a polymerization tank having a capacity of 8001, and heating was started in a polymerization tank under a nitrogen flow of 2.5 Torr/min. When the internal temperature is 1 2 (TC, add 5 · 2 kg (2.5 % by weight) of sodium dodecylbenzene sulfonate and 5.2 kg (2.5% by weight) of 1,5,5 trimethyl- 2, 4,6-tris(3,5·di-tert-butyl 4-hydroxybenzene)benzene (ΤΤΒ), stirring, heating for 18 hours to an internal temperature of 245 ° C, the polymerization reaction is terminated. After the polymerization is completed, the usual method Granulation to obtain granules composed of a block polyether phthalamide composition. In a typical titanium oxide-free polyethylene terephthalate chip having an intrinsic viscosity of 0.65, the mixture is 1.4% by weight. The pellets of the above-mentioned block polyether phthalamide composition were used in the same manner as in Example 1 except that the pellets of the above-mentioned block polyether phthalamide composition were obtained, and the core sheath ratio of 84 dtex/72 monofilament (average single filament fineness: 1.17 dtex) was obtained. The polyester false twisted textured yarn of 70:30. The fabric made of the fiber showed the same soft and excellent feel as in Example 1, but the friction band voltage was very poor, and it was 3400 V. The results are summarized in the table. Examples 2 to 3 were carried out in the same manner as in Example 1 except that the amount of polymer discharged was changed to obtain 56 dtex/72 monofilament (average single-filament fineness). a 0.74 dtex) and 1 1 1 dtex/72 monofilament (average monofilament fineness of 1.54 dtex) with a core-sheath ratio of 70:30 core-sheath composite polyester false twisted textured yarn. The results are excellent in friction withstand voltage and touch. The results are summarized as 袠i. -22- 200831726 Comparative Example 2~3 In addition to changing the amount of polymer sprayed, compared with f, 56 dtex/72 monofilament was obtained (average single The fabric having a fineness of 111 dtex/72 monofilament (average single-filament fineness of 1.54 and a core-sheath type composite polyester false twist of 70:30) is excellent in the same feeling as in the first embodiment, and is uncomfortable. The results are summarized as shown in Table 1. Tpc Comparative Example 4 In addition to increasing the amount of polymer sprayed, the implementation of the book gives 133 dtex/72 monofilament (the average monofilament fineness j core sheath ratio of 70: 30 core) The sheath-type composite polyester is a fabric made of such a yarn, although the friction band voltage is different from that of the implementation, but the touch is hard 'not suitable for practical use. The results are summarized as follows: Comparative Example 5 In addition to changing the metal port into 36 holes, and implementing , Shi 'get 84 dtex / 36 monofilament (average single filament denier as the core sheath ratio The cloth made of 70:30 core-sheath type composite polyester false twisted yarn has a frictional band voltage and is hard to touch, and is not suitable for practical use. The results are summarized in Table 1 ^ Comparative Example 6 丨1 0·78 dtex) The core sheath yarn of dtex). This is equivalent to the yarn, but the frictional electrification 丨1 is the same as the i 1·8 5 dtex) 捻 processed yarn. Li 1 is the same as 2_33 dtex). This is equally excellent, and it shows. -23- 200831726 In the same manner as in Comparative Example 1, except that the amount of polymer discharged was increased, a core-sheath type composite in which a core sheath ratio of 133 dtex/72 monofilament (average single filament fineness of 1.85 dtex) was 70:30 was obtained. Polyester false twist processing yarn. The fabric made of these yarns has a higher frictional belt voltage than Comparative Example 1, but it is not sufficient, and the touch is hard, which is not suitable for practical use. The results are summarized in Table 1. Comparative Example 7 A core sheath ratio of 84 dtex/36 monofilament (average single filament fineness of 2·33 dtex) was obtained in the same manner as in Comparative Example 1, except that the metal port was changed to 36 holes. Core-sheath type composite polyester false twist processing yarn. The fabric made of such a yarn has a friction band voltage higher than that of Comparative Example 1, but it is insufficient, and the touch is hard, which is not suitable for practical use. The results are summarized in Table 1. Table 1 Traction magnification (times) Single fiber fineness (dtex) Crimping rate (%) Number of hairiness (number / 10,000 m) Friction band voltage (V) Tactile sensation (grade) Example 1 200 U7 15 20 1200 1 Implementation Example 2 300 0.78 18 30 1200 1 Example 3 180 1.54 20 15 1100 1 Comparative Example 1 200 1.17 20 15 3400 1 Comparative Example 2 300 0.78 15 30 4000 1 Comparative Example 3 180 1.54 15 20 2700 1 Comparative Example 4 120 1.85 20 13 1000 3 Comparative Example 5 185 2.33 25 10 1000 3 Comparative Example 120 1.85 18 10 2000 3 Comparative Example 7 185 2.33 25 10 2000 3 *PEG (molecular weight 20000) **Sodium dodecylbenzenesulfonate-24- 200831726 [Simple description of the drawing] [Extending simultaneous false twisting, 2 series leading system 1st stage disc (friction t section heater, I ester false twisting processing I device, 15 series rotation Fig. 1 is the manufacturing false twist used in the present invention) Sketch of the far processing machine for processing yarn, 1 series core-sheath type polyester undrawn yarn, 3, 3'-feed roller, 4, 4, staggered nozzle, 5 heater, 6-series cooling plate, 7-series捻 (3 axis friction disk) device), 8 series first conveying roller, 9 series 2 _ 1 0 series 2nd conveying roller, 1 1 winding roller , i 2 series yarn bobbin. Further, Fig. 2 is a front view showing an embodiment of a false dust used in the present invention, and a 13-type false twist disk, a 14-inch guide disk, a 16-series timing belt, and a 17-series drive belt. [Main component symbol description] 1 : Core-sheath type polyester unstretched yarn 2 : Leading device 3 : Feeding roller 3 ' : Feeding roller 4 : Staggered nozzle 5 : Stage 1 heater 6 : Cooling plate 7 = False plate ( 3-axis friction disc device) 8 : 1st transfer roller 9 : 2nd stage heater 1 〇 : 2nd transfer roller - 25 - 200831726 1 1 : Winding roller 1 2 : Polyester false twist processing yarn 13 : False Disk 14: Guide plate 1 5: Rotary shaft 1 6 : Timing belt 1 7 : Drive belt
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