200427880 玖、發明說明： 【發明所屬之技術領域】 本發明係關於氟聚合物紗與其它紗之混紗。 【先前技術】 美國專利公開案第2002/0079610 A1號揭示在一高於說 聚合物熔點之高溫下氟聚合物紗之熔融紡絲，相對於先前 氣聚合物紗及方法’其以更高生產率來生產高強度紗。該 公開案揭示在紗成形前向氟聚合物添加著色劑，意即，在 熔T紡絲之前向共聚物添加顏料以使熔融紡絲紗具有視顏 料濃度而定之顏料的顏色。在溶融紡絲之前將著色劑⑽ 料）加入氟聚合物的原因是氟聚合物紗之化學惰性使之實 際上不能在紡絲後藉由習知的的紡織纖維染色方法及染料 進行染色。染色優於顏料著色，其提供更大的能將未經染 色的紗轉換成各式各樣顏色的多用性（versatility)。氟聚合 物未能提供這種多用性。因此，在無顏料著色的情況下， 氟聚合物顯示出自然色，其自白色到乳白色（半透明），再 到透明。氟聚合物的另一問題在於其不具有普通高強度合 成紡織纖維紗之強度，意即聚酯及聚醯胺之強度，該強度 通*大於5.9 gpd(克/旦尼爾(den))。如專利公開案之實例9 斤揭示，PFAxk合物（四氟乙烯/全氟（丙基乙烯基醚）丑聚 物以不同速度炼融纺絲，以生産具有1〇咖/6請％ 伸長率及1.41 gPd/25%伸長率之強度/伸長率比值，該值揭 露了當強度上升時伸長率τ降的通常情況。該專利公開案 中所製備的最高強度紗揭示於實例26中，其中乙烯/四氟 91716 200427880 乙烯，、來物紗具有2·44 gpd之強度及18·8%之伸長率。 【發明内容】 本毛月之悲樣解決向未加顏色之氟聚合物提供顏色的 1題〜即氟水合物既未著色亦未染色，後者因為氟聚合 物不能籍由習知的纺織纖維染料及染色方法進行染色。可 將解決該問題之實施例描述為至少第—紗與第二、紗之^ 紗，該第-紗包含氟聚合物纖維且該第二紗包含至少―種匕 I工木色或可染色纖維，其包含聚醋、聚醯胺或丙婦酸系纖 維。雖然可藉由撚合在一起來將第-紗與第二紗組合成混 、’y組口紗之較佳方法係藉由空氣喷射混紡方法來進行多 根併合（C=mingling)。與第一紗相組合時該第二紗可^二 染色，接著將混紗進行染色，其只對第二紗著色。或者， 該第二紗可在與第一紗組合之前進行染色。在兩者中之任 -實施例中，混紗具有第二紗之顏色外觀，當藉由多根併 合組合紗時其顏色最為均句。混紗之氣聚合物紗&份之耐 候性（化學穩定性、潮濕、日照、高溫及低溫曝露）使复特 別適用於室外之應用。—特佳應用為勒線包含混紗^多 經紗（multiple end)以達成所要之斷裂強度。縫紉線可為= 種各樣的顏色以匹配各種可得之著色織物。由於構成第二 紗之聚酯、聚醯胺及/或丙烯酸系纖維的 一 j」木性，本發明 之縫紉線具有可染成各種各樣顏色之多用性。 +勢明之較 佳缝幼、線包括黏合齊】。第二紗之黏纟劑一般不附著於氣聚 合物，因為氟聚合物之衆所周知的不黏特性。人1貺承 7 為s牙的 疋，將黏合劑施加至混紗上可將氟聚合物與 ^ 一紗黏合在 200427880 使仔所侍之黏合縫紉線可藉由使用習知的工業縫紉 設備來提供最無故障之（無擦毛（叫㈣）缝幼。 毛月之另悲、樣解決氟聚合物本身之強度小於某些應 用所而之度的問題。該問題藉由上述第_及第二紗之混紗 來解决：其中該第二紗之伸長率與強度為使得該混紗之總 強度比第本身之強度大至少1 gpd。聚S旨及聚酸胺紗 通常具有高伸長率，使得僅比第-紗結實之第二紗並不會 產生更結實之混紗，若第二紗僅在施加於混紗之張力下伸 長同才超出第紗之伸長率時，會引起第一紗的斷裂。因 此車乂L地第二紗之伸長率不應大於第—紗之伸長率K 而，這报難達成，因為高強度第二紗具有高伸長率，例： 大於鄕，而高強度第 '紗通常具有較低伸長率，例如小 於15 /。。令吾人吃驚的是，儘管已發現第二紗具有較 紗更高之伸長率，但繁-糾w 、 、卜 一、、’y仍可增加混紗之強度。較佳 地’弟二紗之伸县率卜楚— 弟一、々、之伸長率高10%以下，咅 即，若第一紗具有10%伸長率，貝11第二紗之伸長率應小： 20%。 氟聚合物紗較佳儘可能結實’使得在室外使用時隨著第 二紗之強度由於氣候而減弱時，混紗之第—紗組份提供特 別應用所需的足夠殘餘強度。因&，混、紗中第—紗較佳具 有至V 2 gpd之強度且該第二紗之強度至少為5 9，第 二紗具有-前文所述之伸長率。第一紗之強度一般不超過 5 gpd ° 令人驚釾的是，已發現混紗中所存在之氟聚合物紗會增 200427880 加第二紗之耐候性，如此，由第二紗本身曝露於相同氣候 條件下時強度之退化看來，由於第二紗（當其為聚酯或聚 醯胺時）的存在而産生的混紗之高強度出奇地高。 【實施方式】 為首先描述構成本發明之混紗的紗，用以製成第一紗之 氟聚合物的實例包括下列：（A)非溶融可塑（fabricable)聚 四氟乙烯，包括改質聚四氟乙烯，意即，其中有少量共聚 單體與四氟乙烯共聚合；及（B)熔融可塑氟聚合物，包括 均聚體而非聚四氟乙烯（PTFE)，例如聚偏氟乙烯（PVDF); 及全氟化共聚物，例如以共聚單體（包括全氟烯烴 (perfluoroolefin)與全氟（烷基乙烯基醚）（PAVE))製備的四氟 乙烯（TFE)之共聚物，其中烷基含有1至6個碳原子且PAVE 可為一種以上PAVE ;或該等聚合物之混合物。就本發明 之目的而言，術語’’共聚物’’用於包括在單組份聚合物中包 含兩個或兩個以上共聚單體的聚合物。一種具有代表性的 全氟烯烴為六氟丙烯。具有代表性的全氟（烷基乙烯基醚） 為全氟（甲基乙烯基醚）(PMVE)、全氟（乙基乙烯基 醚）(PEVE)及全氟（丙基乙烯基醚）（PPVE)。較佳的高度氟 化之聚合物為自四氟乙稀與一種或多種全氟（烧基乙稀基 醚）所製備的共聚物及自四氟乙烯與六氟丙烯所製備的共 聚物。最佳共聚物為TFE與1-20莫耳％全氟烯烴共聚單體 (較佳3-10莫耳％六氟丙烯或3-10莫耳％六氟丙烯與0.2-2莫 耳％PEVE或PPVE)所形成之共聚物，通常稱為FEP ;及 TFE與0.5-10莫耳％全氟（烷基乙烯基醚）所形成之共聚物（包 200427880 括0.5-3莫*%ppVE或Peve)，通常稱為PFA ;或該等包含 PMVE與一種或多種PEve及ρρνΕ兩者之共聚物，通常稱 為MFA °上述氟聚合物（B)較佳顯示出1至約5〇克/1〇分鐘之 溶融流動速率，該流速可根據ASTM D2116、D3307、 D1238或用於其它高度氟化熱塑性聚合物的相應測試在 372°C下測定。聚偏氟乙烯較佳具有根據ASTM D3222量測 之ΙχΙΟ3至4xl〇3帕·秒（pa.s)的熔融黏度。 除上述氟化熱塑性四氟乙烯共聚物（B)之外，諸如乙烯/ 四氟乙烯共聚物（ETFE)及乙烯/三氟氯乙烯（ECTFE)之氟化 熱塑性（熔融可塑性）聚合物同樣可用於本發明，其中Etfe 較佳。該ETFE為乙烯與四氟乙烯之共聚物，較佳含有較 小比例之一種或多種額外單體以改良共聚體特性，例如抗 應力裂紋。美國專利第3,624,250號揭示該等聚合物。E(乙 烯）與TFE(四氟乙浠）之莫耳比率為約4〇:6〇至約6〇:4〇，較 佳約45··55至約55:45。共聚物較佳亦含有約〇1至約1〇莫耳 %之至少一種可共聚的乙烯系單體，該單體提供含有至少 2個碳原子之側鏈。全氟烷基乙烯為該種乙烯系單體，全 氟丁基乙烯為較佳單體。聚合物具有約25〇。(：至約27〇。〇， 較佳約255°C至約270°C之熔點。熔點根據ASTM 3159之程 序來測定。根據該ASTM程序，熔點為自熱分析儀中所獲 取之吸熱峰值。較佳地，用於本發明之ETFE具有根據 ASTM D3159使用5公斤負載測定之小於45克/1〇分鐘的熔 融流動速率（MFR)，其中熔融溫度規定為297γ。更佳 地，ETFE之MFR不高於35克/10分鐘且至少為15克/1〇分 91716 -10- 200427880 鐘：較佳為至少20克/10分鐘。當由於聚合物之分子量下 降導致MFR自35克/1〇公於μι# ^ ^ 兄刀鐘上升時，更高之熔融紡絲速度 的優勢由於聚合物之分子量降低引起紗強度（強度）降低而 抵消，使得-旦到達45克/1〇分鐘之聰時，強度的下降 之影響勝於生產率上升之影響。當驗自2〇克/1〇分鐘下 降時，擠塵更具黏性之聚合物的困難上升，在達到"克 /10刀鐘MFR之月’其將導致不經濟的义容融纺絲速度， MFR低於15克/10分鐘時，聚合物幾乎不可藉由紗所需之 小擠出孔來進行熔融紡絲。 同樣適於本舍明之貫踐的為高度氟化之熱塑性聚合物之 混紗，包括TFE共聚物之混紗。 氟來合物（A)可藉由已知方法形成紗，包括將氟聚合物 紡成紗或形成氟聚合物之薄片或股線（strand)，接著由此 切斷長絲。氟聚合物（B)較佳可藉由美國專利公開案第 2002/0079610 A1號所揭示之方法熔融紡絲成紗。 聚物紗可具有至少2 gPd及較佳至少2.5 gPd的強度。製得 具有至少3 gpd之強度的紗之較佳方法在下文實例中描 述。通常用於製得本發明之混紗的氟聚合物紗具有8至 25%的伸長率且較佳具有8至15%的伸長率以提供更高強 度0 根據ASTM D 1577之程序來測定本文所揭示之紗丹尼爾 數’且根據ASTM 2256中所揭示之程序來測定拉伸特性 (斷裂伸長率（即伸長率）及強度）。 "T在市％上購侍聚g旨、聚酸胺及丙稀酸系聚合物之紗， 91716 -11 - 200427880 且其可用作製得本發明之混紗之第二紗。該等紗與其製造 方法以及其染色方法揭示於Kirk_〇thma化學技術百科全 書（Encyclopedia of Chemical化化⑽叫从州句第#版第ι〇 卷之第559-565頁及第576-581頁（丙烯酸樹脂類）及第662_ 667頁、第670-677頁（聚酯類）中，及第19卷之第519_522 頁、第528頁、第530-539頁及第543-544頁（聚醯胺類）中。 聚酯及聚醯胺紗藉由熔融紡絲製得，而聚丙烯酸系紗一般 藉由濕法紡絲或乾法紡絲來製得。用於製造該等紗之聚 酯、聚醯胺及丙烯酸系聚合物可為均聚物或共聚物，且其 具有足夠而的分子量以提供本發明之混紗所需強度。可以 使用之合適的均聚物及/或共聚物包括（例如）聚（對苯二甲 酸乙二酯）、聚（對苯二甲酸丙二酯）、聚[對苯二甲酸乙二 醋/(5-鈉磺基）間苯二酸鹽]、聚己二醯己二胺、含有分別 易接收陽離子或深色酸性染料之磺基或胺基的聚己二醯己 二胺及其類似物，及其混合物。丙烯酸系聚合物之實例包 括：丙烯酸均聚物及共聚物，包括改質聚丙烯酸纖維，意 即包δ W至8 5重虿％丙浠酸結構單元的丙烯酸共聚物。 第一❼之強度將視自其製得之聚合物及紗成形後用以增 加強度之拉伸度而定。該強度同樣亦視第二紗是否為連續 長絲或人造短纖維而定。就給定聚合物而言，連續長絲紗 具有較人造短纖維紗更高的強度。為解決提供著色紗（其 含有未著色之氟聚合物紗）之問題，第二紗之強度較不重 要。因此，可以使用丙烯酸系聚合物紗，其僅可用作短纖 維紗且具有2至3 gPd之強度。聚酯人造短纖維紗通常顯示 91716 -12- 200427880 出2 · 4至7 gpd的強度’且聚醯胺人造短纖維紗顯示出2 · 9至 7·2 gpd的強度。但在更南強度水平上，即使對於丙烯酸系 聚合物紗而言，人造短纖維紗可提供與氟聚合物紗之混 紗，該混紗中氟聚合物紗顯示出較其本身更大的強度。一 般而s ’連績長絲聚S旨紗及聚驢胺紗亦是如此，都顯示出 至乂、3 · 5 gpd的強度。然而，為提供具有較氟聚合物紗組份 更大強度的混紗，較佳將高強度聚酯及聚醯胺紗用作第二 紗。該等紗顯示出至少5.9 gpd的強度，且較佳至少6·5 gpd。聚酯及聚醯胺紗之強度通常不超過9 gpd。 第二紗一般具有15至30%的伸長率。較佳地，第二紗之 伸長率不到高於第一紗伸長率之8%，更佳不到高於第一 ❸之5%，最佳不到高於第一紗的2%。該等伸長率的差異 施加至本文所述之每個第一及第二紗。混紗中第一紗較佳 亦具有至少2.5 gpd的強度，且更佳為至少3 gpd。第二紗 之強度較佳亦比第一紗之強度大至少2 gpd。 本卷月之第一紗可為單絲或複絲。當該紗為單絲時，其 通系具有50至1〇0〇微米之直徑。當該紗為複絲時，單根長 絲通㊉具有8至30微米的直徑，且該紗通常具有3〇至5〇〇〇 丹尼爾（demer)，較佳為1〇〇_1〇〇〇丹尼爾，且含有2〇至2⑼ 根長絲。在複絲紗之狀況下，單根長絲較佳為每根2至50 、爾車乂仏為5至40丹尼爾/長絲，且最佳為1〇-3〇丹尼爾 /長'糸就取鬲斷裂強度無過度剛性而言較佳為20-30丹尼 、糸胃第一紗較佳為複絲紗，其特徵化參數可與本段 中早先提及之特徵化複絲第一紗之參數相同。第一及第二 91716 -13- 200427880 紗亦可由人造短纖維而非連續長絲製得以增強外觀，且本 發明之混紗可為連續長絲與人造短纖維紗之混合物。在本 發明之混紗中使用人造短纖維第一紗及/或 ^ —、v之狀況 下，人造短纖維通常具有之丹尼爾，較佳為為丨至5丹 尼爾/纖維（或由其製成纖維之長絲）。 第一及第二紗可藉由習知的紡織纖維方法進行混紡，例 如撚合，且成對之已撚合之混紗可進一步撚合在一起，例 如按相對之撚合方向形成繩索。該等紗可紡織，意即，平 紗（flat yam)，或用習知的方法變形以增加紗之蓬鬆度。 無論在混紗成形之前或之後對第二紗染色，即使第一紗未 染色，亦會將第二紗顏色給予混紗、給予混紗之撚合紗對 及混紗之繩索。 將第一及第二紗混紡的較佳方法為多根併合，例如1989 年拉夫堡大學（Loughborough University)出版的，，空氣喷射 變形及多根併合（Air-Jet Texturing & Mingling),，中的描 述，該出版物為1989年9月在該大學召開之國際會議的論 文集’其中包括A.Demic提交之論文，，纏結/交纏 (Intermingle/Interlacing):普查（a Broad Survey )(第416〇 頁）。纏結描述為以與紗道成一角度將一束鬆散平紗或變 形紗經受擾動式冷空氣噴射衝擊（併合噴射）以打開各段長 絲，同時在已打開之各段長絲附近，長絲相互纏繞且相互 纏結形成緊始、段。多根併合描述為對兩種紗進行纏結，藉 此纏繞及纏結涉及兩種紗之長絲。由此形成之多根併合紗 為黏合紗，意即兩紗聯合形成單紗（混紗），且該所得混紗 91716 -14- 200427880 為與開口段（open section)週期交替之交纏段的形式。該描 述及製備之方法應用於本發明之多根併合之混紗。本發明 之多根併合混紗類似於Demic論文第59頁圖5中描繪為”混 合（blending)，，之混紗。用於多根併合之空氣噴射與執行多 根併合方法之條件為人所熟知，如Demic論文中所描述及 美國專利第4,〇25,595號所揭示之纏結。當送入多根併合喷 口（co-mingling jet)之紗進行變形時，該變形可包括不同類 型之變形，例如空氣喷射變形、假撚變形及熱流體變形。 本發明之多根併合混紗較佳每米具有3至5〇個扭結 (entanglement)(按美國專利第4,〇25,595號第3攔中所揭示來 測定）以達成變形過程所需之黏結性。沿混紗長度上的扭 結為結頭，該等結頭有時稱為夾持點（nip)或結點（n〇de)， 且忒等扭結為已混合之紗提供完整性。即使當第一紗為單 糸或人k紐纖維日守，第二紗長絲亦會與單絲或人造短纖維 、父纏以提供具有完整性的混紗。當混紗之一種或兩種紗 句為人k短纖維紗時情況亦是如此。在較佳混紗中，第一 與第二紗兩者都為複絲紗，其為混紗提供 提供混紗之最均句顏色外觀，該顏色為第二紗之所染顏 色。 毛月之另較佳混紗為包含芯（core)及外鞘（Sheath)之 此紗’其中Μ:紗存在於芯内且第—紗存在於外勒中。該 混紗藉由將第 '紗包纏圍繞第二紗製得，但較佳藉由多根 併合製造’其中相對於第二紗之進料到喷π，第—紗過量 進料到多根併合噴口，易於引起第—紗之長絲包纏圍繞在 91716 -15- 200427880 第二紗而每種紗之長絲藉由多根併合方法相互交纏在一 起。第一紗之過量進料藉由第一紗進料至多根併合噴口的 速度快於噴口下游之混紗的捲繞速度來達成。本發明之混 紗的構造具有更好地利用第二紗更大的強度以增加混紗之 強度超過第一紗強度之優點。本構造中外鞘紗（即第一紗） 的本質為未完全覆蓋芯紗（即第二紗），藉此第二紗之染色 仍然為混紗提供著色。第一紗藉由操取第二紗之顏色來使 混合紗著色，-些藉由反射且一些藉由光透射來掘取顏色 使得^過第-紗之長絲厚度可以看到第二紗之顏色。 將第-與第二紗組合成本發明的混紗之依據為混紗所需 ^丹尼爾。該丹尼爾藉由選擇第-與第二紗之丹尼爾及混 =種紗之數量來達成。混紗可以由相同數量之第一與 旦 弟ν之數ϊ可以超過第二紗之數 里’反之亦然。較佳之混紗具有兩種第-紗及一種第二 二，另-較佳之混紗具有兩種第二紗及—種第—紗。第 --人k及之較佳混紗最大化氟聚合 室外氣候強度最大。第二次提及 3里以使付化殘餘 ^ A ^ ^ 彳"°昆紗最大化初始混 v強度及顏色均勾度。該等目標亦 對丹尼爾數來達成。例如，當僅存在一種二、夕、相 更高丹尼爾數之第二紗傾向於 -、’…具有 初始混紗強度，視第一紗與第顏色均勾性及較高的 定。在本發％ 〇 # ^ y間的丹尼爾之差異而 月之夕根併合混紗之狀況下，“， 紗之一種或兩種紗均為人造短纖維紗時，：：一办與弟二 人造短纖維紗以增加紗之間及每種父佳使用複數根 y r人造短纖維之間的 91716 -16- 200427880 纏結機會。 第二紗可以藉由習知的紡織纖維染色方法及使用習知的 纺織纖維染料進行染色，視第二紗是否由聚酯、聚驢胺或 丙烯酸系纖維製成而定。對該等染色方法與染料及對組成 該紗之聚合物的改質的進一步描述揭示於上述幻吐-Othmer中。第二紗可在組合成混紗之前或之後進行染色。 對混紗之染色使得第一紗未染色。 較佳之混紗含有至少兩種第二紗，其中一種為丙烯酸系 人造短纖維且另一種為聚酯與聚醯胺中之任一種或兩者。 該混紗特別適用於曝露氣候下之應用，其中丙烯酸系纖維 之染料堅牢度維持混紗之顏色，而氟聚合物紗則提供長期 強度。 實例 實例中使用之紗為Tefzel® ETFE氟聚合物，其為乙烯、 四氟乙烯與至少5莫耳％的全氟烷基乙烯三聚單體之三聚 物，具有258°C熔融溫度（峰值）及29.6克/10分鐘的熔融流 速，兩值均根據ASTM 3159來測定，使用5公斤重量用於 測定MFR。 在熔融紡絲後塗覆紗之潤滑劑為下列：88.9重量％ (：1&1^加八负1&1^??多元醇聚酯、5重量％11111961^@0-1144經乙氧基化多元醇覆蓋之酯油乳化劑、0.67重量％ Cytek Aerosol® OT磺基丁二酸二辛酯潤濕劑（75重量％水 溶液）、5重量％ Cognis Emersol 871脂肪酸界面活性劑、 0_26重量％ Uniroal Naugard® PHR亞鱗酸酉旨類抗氧化劑、 91716 -17- 200427880 用於脂肪酸之〇·67重量％氫氧化鈉（45重量％水溶液）穩定劑 及0.04重量％Dow Corning聚二甲基矽氧烷（加工助劑_最大 降低潤滑劑在熱輥上的沈積）。 在環境溫度中，氟聚合物及潤滑劑分別具有25達因 (dyne)/公分及23.5達因/公分的表面張力。 除單面上膠輥112與導輥111不存在外，使用美國專利公 開案第2002/0079610 A1號圖9中所示之設備配置來進行氟 聚合物之熔融紡絲，且使用位於緩冷器n 〇下方、方向導 親（direction guide)中變化之上游的施料器導輥來施加潤滑 劑。此施料器導輥與Luro-Jet®敷料器導輥相似，具有一 v 形槽’該槽將經擠壓之大量長絲聚集入槽内且其包括一在 V形基底的施料器，該施料器又包括一孔，當潤滑劑通過 施料器時，可穿過該孔將潤滑劑泵送（定量供給）至紗上。 擠壓機係與齒輪泵連接之直徑為1.5英吋（3·8公 分）Hastelloy C_276單螺桿擠壓機，其又藉由配接器連接至 噴絲頭組件，喷絲頭組件包括過濾網組合以過濾熔融聚合 物。噴絲頭組件係美國專利公開案圖8之組件7〇且包括一 輸送管及喷絲頭面板，在圖8中分別描繪為元件78及75。 噴絲頭面板有30個孔，該等孔排列在直徑為2英吋（51公 分）的一個圓圈内，每孔（擠壓模孔）具有3〇密爾（mii)的直徑 及90山爾的長度。緩冷杰為實例丨2及美國專利公開案之圖 10A與10B中的緩冷器。 才呆作溫度如下： 擠壓機：在擠壓機區_進料，#1及#2分別為25〇。〇、 91716 -18 - 200427880 〇C、27(TC， 輪送管：317°C， 噴絲頭面板：350°C， 緩冷器··在位置#1，#2及#3處分別為2〇4t：、21(^及158 °C。 藉由齒輪泵將氟聚合物生產量（氟聚合物離開噴絲頭）設 為最大值，意即僅不足以引起擠壓長絲發生熔融破裂，此 最大值為50.5克/分鐘（6.7磅/小時）。所得之紗在距離噴絲 頭大於50x擠壓孔直徑的距離處固化。上述潤滑劑僅施加 至緩冷器下方的紗上，且進料輥溫度約為18〇它且其表面 速度為309米/分鐘。將拉伸輥加熱至i5(rc且以124〇米/分 鐘之表面速度旋轉以提供4·01的拉伸比。藉由Lees〇na捲繞 機將紗捲繞至一筒管上。所得至紗具有下列特性：強度 3.45 gpd、伸長率7·7%、拉伸模量55 gpd。當藉由將拉伸 輥之表面速度減小至1140米/分鐘從而將拉伸比降至3 69 時’將獲得下列紗之特性：強度-3.14 gpd、伸長率_ 9·4°/〇、模量51 gpd。紗丹尼爾數自374上升至407。 紗丹尼爾數之變異係數小於2%。變異係數為5段連續十 米長之紗的平均重量除以標準偏差（xl 〇〇)。 實例1 除了拉伸比務微降低以獲得更南伸長率紗（其具有更低 強度）外，本實例中所使用之氟聚合物紗係藉由上述方法 一般製備而成的紗。此紗為400丹尼爾，含有13根長絲且 具有2 · 9 gp d之強度及14 _ 3 %的伸長率。本實例中所使用之 91716 -19- 200427880 其它紗為聚酯紗。一種該紗具有100根長絲，拉伸後為633 丹尼爾（初始丹尼爾640)且具有7·89 gpd之強度及24%的伸 長率（PET紗A)。將PET紗A染為白色且從特拉華州威爾明 頓 DuPont公司（DuPont Company，Wilmington，DE)獲得。另 一種該紗具有108根長絲，拉伸且染色後為885丹尼爾（初 始丹尼爾為840)，且具有7.49 gpd之強度及2〇%的伸長率 (PET紗B)。PET紗B&Akra公司紗，其自新澤西州，町以聯 合紗公司（United Yarn Co·，Wayne，NJ)獲得，且將其染為 藍色。 藉由空氣噴射混合（多根併合）製得ETFE共聚物紗的一根 經紗與PET紗A的一根經紗之混合紗，方法如下：使用一 FOO扭結機器。該機器使用自Winst〇n_Salem N c•國際機 器銷售有限公司（IMS)獲得之IMS 3-2型空氣交纏喷口。氟 聚合物紗以5克之紗張力穿過喷口過量進料，pE1^^、a以2〇 克之紗張力穿過喷口來供給，用於多根併合該等紗之空氣 壓力為40磅/平方英吋（psi)且捲繞速度為25〇碼/分鐘 (ypm)。所得之多根併合之混紗為外鞘/芯混紗，其中混紗 表面主要為氟聚合物紗且其具有1〇7〇丹尼爾、4·45 gpd之 強度及21.83%的伸長率。 另一種混紗由相同的空氣喷射多根併合方法製得，使用 相同的ETFE共聚物紗及PET紗B(每種紗之一根經紗）以獲 得多根併合之外鞘/芯混紗，其具有1326丹尼爾、5_5 gpd 之強度及21.5%的伸長率，且顯示出均勻的藍色。 使用相同ETFE共聚物紗之兩根經紗及pet紗B之一根經 91716 -20- 200427880 紗藉由相同的空氣喷射多根併合方法來製得另一種混紗， 兩種ETFE紗在相同張力（5克）下穿過噴口進料且pet紗張 力為20克，從而獲得具有1728丹尼爾、3.93 gpd之強度及 16.24%伸長率的多根併合紗。ETFE與PET紗A之混紗為白 色’且由於使用藍色PET紗B，所以ETFE與PET紗B之混紗 為藍色。 當PET紗替換成聚ϋ胺或丙浠酸系紗時，可獲得類似結 果。 實例2 紗之缝紉線由多根併合紗（其在實例1中使用ETFE共聚物 紗之一根經紗與PET紗B之一根經紗製得）製成，其製法為 (a)對一撚/公分之混紗施加撚（b)以一撚/公分但與紗中之撚 方向相反將該紗之三根經紗合股在一起，且（〇在14〇-15() C之張力下對所得線進行熱定形。所得之縫紉線具有3978 之丹尼爾。若需要，則可向縫紉線上施加黏合劑或塗飾 劑。所得縫紉線為均衡經捆紮之（c〇rded)構造，具有均勻 丹尼爾且顯示出優異的縫線毛圈形成（stitch 1〇〇p formation)，無任何結頭或纏亂傾向。 實例3 如實例1所述，利用對PVDF紗的過量進料條件將4〇〇丹 尼爾Kynar® 710(PVDF紗）之一根經紗與885丹尼爾pED0、B 之一根經紗空氣噴射多根併合在一起，由此産生129〇丹尼 爾、5·56 gpd強度及20.0%伸長率的藍色混紗。⑧71〇 PVDF連續長絲紗本身具有M §1)(1之強度及391%伸長率。 91716 -21 - 200427880 實例4 8 85丹尼爾PET紗B之一根經紗與20s/2股（ply)(512丹尼 爾）深藍色丙烯酸系人造短纖維之一根經紗及400丹尼爾 ETFE紗之一根經紗如實例3如述空氣噴射多根併合，ETFE 與丙烯酸系紗以相同張力過量進料，由此産生1 885丹尼 爾、3.97 gpd強度及20.5%伸長率的色調為藍色之混紗。該 5 12丹尼爾丙烯酸系人造短纖維由Pharr Yarns有限公司獲 得，且具有1.7 gpd之強度及38.34%之伸長率。 實例5 將840丹尼爾（840-140_400T)(自DuPont公司獲得的白色 高強度尼龍）之一根經紗與400丹尼爾ETFE之一根經紗如實 例3所述空氣喷射多根併合，由此産生1263丹尼爾、615 gpd強度及25.5%伸長率的白色混紗。840丹尼爾尼龍長絲 紗具有9.30 gpd之強度及25.5%之伸長率。 本實例描述其中混紗含有用於第二紗之黏合劑的實施 例，該黏合劑之實例為以聚胺基甲酸酯或聚矽氧為主要成 分的聚合物。該等黏合劑不會黏附氟聚合物，但可用於黏 合複合紗。施用黏合劑（黏結劑）之一般程序為形成含_ :齊:之液態介質，且藉由習知方法如使用單面上膠輕將： (黏結劑）施力σ至紗上、軋浸（paddmg)黏合劑介質到紗 上或藉由浸染或噴灑方法將介質施加至紗上，教/ 並在最終卷裝上捲繞。 ，、、、定形 作為實例，多根併合之紗由丹尼爾、13 dpf E咖紗 91716 •22- 200427880 之-根經紗與220丹尼爾、3·25咐聚醋紗之—根經紗组 成。單紗之特徵為9S撚數（9圈/英吋（每英吋撚數⑽)），9 圈/2.54公分），意即”s”方向9圈。將該等紗之兩種紗合股 在一起，該合股特徵為7Z(7撚每英吋，7圈/2.54公分），意 即Z方向7圈。黏合劑為得自NuB〇nd⑧(合成線， Bethlehem，PA)之水性聚胺基甲酸醋，|藉由|面上膠輕 將其施加至具有總量測為145〇丹尼爾的合股紗上，熱定形 亚在最終卷裝上捲繞。與使用相同紗但無黏合劑時相比， 所付黏合紗藉φ能夠使縫幼在更長時間内連續執行而在工 業縫幼中效能表現更好。因此使用黏合劑會導致出現更少 的斷紗或紗扭結，該等情況係機器停止運轉的典型原因。 該經改良之縫切效能類似於聚g旨紗本身與相同黏合劑一起 使用表現出的縫紉效能。黏合劑對聚酯紗本身之作用類似 於黏合劑對複合EFTE/聚酯紗之作用。藉由將相同紗之混 紗合股在一起以產生量測為2572丹尼爾、施加有聚胺基甲 酸酯黏合劑且熱定形的複合紗，從而獲得類似的改良^縫 紉效能。 實例7 广實例係針對如下實施例，其中當第二紗與氟聚合物紗 聯合成為複合紗時第二紗耐候效能更好，意即混紗中第二 紗之強度退化小於其本身耐候下時的強度退化，藉此混紗 拉伸強度南於預期。當第二紗為聚醋或聚醯胺時獲得此 效果。本實例中的紗係實例6中所描述的紗。 根據SAE J1960使用氙弧加速耐候性裝置來測定加速耐 91716 -23- 200427880 候效能，此裝置可自Illinois州Chicago市Atlas公司購得。 在曝露於450千焦耳能量（相當於在Florida州朝南45度曝露 於室外4個多月）之前及之後來測定紗之強度及伸長率。該 曝露足以引起ETFE紗本身之伸長率下降34%及聚酯紗本身 之伸長率下降63%。與之相比，複合ETFE/聚酯紗之伸長 率僅下降37%，此大約與ETFE紗本身的伸長率下降相同且 大大小於聚酯紗本身的伸長率下降。此外，曝露後 删紗本身的強度(gpd)幾乎不受影響，而聚 保持其初始強度的例。與之_，複合紗保持其初 度的91%。200427880 2. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a blended yarn of fluoropolymer yarn and other yarns. [Prior Art] US Patent Publication No. 2002/0079610 A1 discloses that melt spinning of a fluoropolymer yarn at a high temperature higher than the melting point of the polymer, compared with the previous aeropolymer yarn and method, it has a higher productivity To produce high-strength yarns. This publication discloses adding a colorant to a fluoropolymer before yarn forming, that is, adding a pigment to a copolymer before melt-spinning so that the melt-spun yarn has a color of the pigment depending on the pigment concentration. The reason why the coloring agent is added to the fluoropolymer before melt spinning is that the chemical inertness of the fluoropolymer yarn makes it practically impossible to dye it after spinning by the conventional textile fiber dyeing method and dye. Dyeing is superior to pigmentation, which provides greater versatility in converting undyed yarns into a wide variety of colors. Fluoropolymers fail to provide this versatility. Therefore, without pigmentation, the fluoropolymer shows a natural color, from white to milky white (translucent), and then transparent. Another problem with fluoropolymers is that they do not have the strength of ordinary high-strength synthetic textile fiber yarns, that is, the strength of polyester and polyamide, which strength * is greater than 5.9 gpd (g / den). As disclosed in Example 9 of the patent publication, a PFAxk compound (tetrafluoroethylene / perfluoro (propyl vinyl ether) ugly polymer is smelted and spun at different speeds to produce a product with 10% / 6% elongation. And 1.41 gPd / 25% elongation strength / elongation ratio, which reveals the general situation that elongation τ decreases when strength increases. The highest strength yarn produced in this patent publication is disclosed in Example 26, where ethylene / Tetrafluoride 91716 200427880 Ethylene, rayon yarn has a strength of 2.44 gpd and an elongation of 18 · 8%. [Contents of the invention] The tragic situation of this month is to solve the problem of providing color to uncolored fluoropolymers. The problem is that the fluorohydrate is neither colored nor dyed, because the fluoropolymer cannot be dyed by conventional textile fiber dyes and dyeing methods. Embodiments that solve this problem can be described as at least the first yarn and the second Yarn yarn, the first yarn includes fluoropolymer fibers and the second yarn includes at least one kind of wood color or dyeable fiber, which includes polyester, polyamide, or acetic acid fiber. Although The first and second yarns can be twisted together The best method for synthesizing the blended yarns of the “y” group is to perform multiple merging (C = mingling) by the air jet blending method. When combined with the first yarn, the second yarn can be dyed twice, and then the mixed yarn is dyed. Dyeing, which only dyes the second yarn. Alternatively, the second yarn may be dyed before being combined with the first yarn. In either of the embodiments, the mixed yarn has the color appearance of the second yarn. The color is the most even when multiple combined yarns are combined. The weather resistance (chemical stability, humidity, sunlight, high temperature and low temperature exposure) of the air-polymer yarn of the mixed yarn makes the compound particularly suitable for outdoor applications. — A particularly good application is that the thread contains blended yarns ^ multiple warp yarns (multiple end) to achieve the desired breaking strength. The sewing thread can be = a variety of colors to match the various colored fabrics available. The properties of polyester, polyamide and / or acrylic fiber are as follows. The sewing thread of the present invention has versatility that can be dyed into a variety of colors. + The preferred sewing is fine, and the thread includes bonding together. Adhesives of the two yarns are generally not attached to the air polymer Material, because of the well-known non-stick properties of fluoropolymers. People 1 and 7 are sacral teeth. Applying an adhesive to the blended yarn can bind the fluoropolymer and ^ one yarn to 200427880. The bonded sewing thread can provide the most trouble-free (brushless (seamless)) seams by using the conventional industrial sewing equipment. Mao Yue's other sadness, so the strength of the fluoropolymer itself is less than some applications. This problem is solved by the mixed yarn of the first and second yarns: wherein the elongation and strength of the second yarn are such that the total strength of the mixed yarn is at least 1 gpd greater than the strength of the first yarn. Poly S purpose and polyurethane yarns usually have high elongation, so that the second yarn that is stronger than the first yarn does not produce a stronger mixed yarn. If the second yarn is only stretched under the tension applied to the mixed yarn When the elongation of the first yarn is exceeded, the first yarn will break. Therefore, the elongation of the second yarn of the car 乂 L should not be greater than the elongation K of the first yarn. However, this report is difficult to achieve because the high-strength second yarn has a high elongation. For example: greater than 鄕, and the high-strength first yarn It usually has a lower elongation, for example less than 15 /. . To my surprise, although it has been found that the second yarn has a higher elongation than the yarn, the complex-correction w,, Bu ,, y can still increase the strength of the mixed yarn. It is better that the younger brother of the second yarn has a higher elongation rate of less than 10%, that is, if the first yarn has 10% elongation, the elongation of the second yarn should be small. : 20%. The fluoropolymer yarn is preferably as strong as possible 'so that when the strength of the second yarn weakens due to the weather when used outdoors, the first-yarn component of the blended yarn provides sufficient residual strength for special applications. Because of &, the first yarn in the mixed yarn preferably has a strength of up to V 2 gpd and the strength of the second yarn is at least 59, and the second yarn has an elongation as described above. The strength of the first yarn generally does not exceed 5 gpd °. It is surprising that the fluoropolymer yarn present in the blended yarn has been found to increase the weather resistance of 200427880 plus the second yarn. Thus, the second yarn itself is exposed to The degradation in strength under the same climatic conditions appears to be a surprisingly high strength of the blended yarn due to the presence of the second yarn (when it is polyester or polyamide). [Embodiment] To first describe the yarn constituting the mixed yarn of the present invention, examples of the fluoropolymer used to make the first yarn include the following: (A) Non-meltable plastic polytetrafluoroethylene, including modified polytetrafluoroethylene Tetrafluoroethylene, which means that a small amount of comonomer is copolymerized with tetrafluoroethylene; and (B) molten plastic fluoropolymers, including homopolymers rather than polytetrafluoroethylene (PTFE), such as polyvinylidene fluoride ( PVDF); and perfluorinated copolymers, such as copolymers of tetrafluoroethylene (TFE) made from comonomers, including perfluoroolefins and perfluoro (alkyl vinyl ethers) (PAVE), where Alkyl contains 1 to 6 carbon atoms and PAVE can be more than one PAVE; or a mixture of these polymers. For the purposes of the present invention, the term 'copolymer' 'is used to include polymers containing two or more comonomers in a single component polymer. One representative perfluoroolefin is hexafluoropropylene. Typical perfluoro (alkyl vinyl ether) are perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), and perfluoro (propyl vinyl ether) ( PPVE). Preferred highly fluorinated polymers are copolymers prepared from tetrafluoroethylene and one or more perfluoro (ethylene glycol ethers) and copolymers prepared from tetrafluoroethylene and hexafluoropropylene. The best copolymer is TFE and 1-20 mole% perfluoroolefin comonomer (preferably 3-10 mole% hexafluoropropylene or 3-10 mole% hexafluoropropylene and 0.2-2 mole% PEVE or Copolymer formed by PPVE), commonly known as FEP; and copolymer formed by TFE and 0.5-10 mole% perfluoro (alkyl vinyl ether) (including 200427880 including 0.5-3 mole *% ppVE or Peve) , Commonly referred to as PFA; or these copolymers containing PMVE and one or more PEve and ρρνΕ, commonly referred to as MFA ° The above fluoropolymer (B) preferably shows 1 to about 50 g / 10 minutes The melt flow rate can be determined at 372 ° C according to ASTM D2116, D3307, D1238 or corresponding tests for other highly fluorinated thermoplastic polymers. The polyvinylidene fluoride preferably has a melt viscosity of 1 × 10 3 to 4 × 103 Pa · s (pa.s) measured according to ASTM D3222. In addition to the above fluorinated thermoplastic tetrafluoroethylene copolymers (B), fluorinated thermoplastic (melt plasticity) polymers such as ethylene / tetrafluoroethylene copolymer (ETFE) and ethylene / trifluorochloroethylene (ECTFE) can also be used for Of the present invention, Etfe is preferred. The ETFE is a copolymer of ethylene and tetrafluoroethylene, and preferably contains a small proportion of one or more additional monomers to improve interpolymer characteristics, such as resistance to stress cracking. U.S. Patent No. 3,624,250 discloses such polymers. The molar ratio of E (ethylene) to TFE (tetrafluoroacetamidine) is about 40:60 to about 60:40, more preferably about 45 · 55 to about 55:45. The copolymer preferably also contains from about 0.01 to about 10 mole% of at least one copolymerizable vinyl-based monomer which provides a side chain containing at least 2 carbon atoms. Perfluoroalkylethylene is such a vinyl-based monomer, and perfluorobutylethylene is a preferred monomer. The polymer has about 25 °. (: To about 27.0 °, preferably a melting point of about 255 ° C to about 270 ° C. The melting point is determined according to the procedure of ASTM 3159. According to the ASTM procedure, the melting point is the endothermic peak obtained in an autothermal analyzer. Preferably, the ETFE used in the present invention has a melt flow rate (MFR) of less than 45 g / 10 minutes measured with a 5 kg load according to ASTM D3159, wherein the melting temperature is specified as 297γ. More preferably, the MFR of ETFE is not Above 35 grams / 10 minutes and at least 15 grams / 10 minutes 91716-10-200427880 minutes: preferably at least 20 grams / 10 minutes. When the MFR is reduced from 35 grams / 10 minutes due to the decrease of the molecular weight of the polymer μι # ^ ^ When the bell knife rises, the advantage of higher melt spinning speed is offset by the decrease in yarn strength (strength) caused by the decrease of the molecular weight of the polymer, so that when the denier reaches 45 g / 10 minutes, the strength The impact of the decline in the productivity is higher than the impact of the increase in productivity. When the test drops from 20 g / 10 minutes, the difficulty of extruding the more viscous polymer from dust rises, reaching the "gram / 10 knife clock MFR month" It will lead to uneconomical spinning speed of Yung-yong, MFR below 15g / 10min During the hour, polymers can hardly be melt-spun through the small extrusion holes required for the yarn. Blending yarns of highly fluorinated thermoplastic polymers, including blends of TFE copolymers, which are also suitable for Ben Sheming's practice Yarn. The fluoropolymer (A) can be formed into yarn by known methods, including spinning a fluoropolymer into a yarn or forming a sheet or strand of a fluoropolymer, and then cutting the filaments therefrom. Fluoropolymerization The object (B) is preferably melt-spun into a yarn by the method disclosed in US Patent Publication No. 2002/0079610 A1. The polymer yarn may have a strength of at least 2 gPd and preferably at least 2.5 gPd. A preferred method of 3 gpd yarn is described in the examples below. The fluoropolymer yarns typically used to make the blended yarns of the present invention have an elongation of 8 to 25% and preferably an elongation of 8 to 15% To provide higher strength 0, the yarn denier number disclosed herein was determined according to the procedure of ASTM D 1577 and the tensile properties (elongation at break (ie, elongation) and strength) were determined according to the procedure disclosed in ASTM 2256. " T purchases polyg, polyamines and acrylics on the market Polymer yarn, 91716 -11-200427880 and it can be used as the second yarn for producing the mixed yarn of the present invention. These yarns, their manufacturing methods and their dyeing methods are disclosed in the Encyclopedia of Chemical Technology The tweet is from the state sentence No. # edition Vol. Pp. 559-565 and 576-581 (acrylic resin) and 662_ 667, 670-677 (polyester), and 19 vols. 519_522, 528, 530-539, and 543-544 (polyamines). Polyester and polyamide yarns are made by melt spinning, while polyacrylic yarns are generally made by wet spinning or dry spinning. The polyester, polyamide, and acrylic polymer used to make these yarns may be homopolymers or copolymers, and have a sufficient molecular weight to provide the required strength of the blended yarn of the present invention. Suitable homopolymers and / or copolymers that can be used include, for example, poly (ethylene terephthalate), poly (trimethylene terephthalate), poly [ethylene terephthalate / ( 5-sodium sulfo) isophthalate], polyhexamethylene adipamide, polyhexamethylene adipamide containing sulfo or amine groups that are susceptible to cationic or dark acid dyes, and the like, And its mixture. Examples of acrylic polymers include acrylic homopolymers and copolymers, including modified polyacrylic fibers, which means acrylic copolymers containing δ W to 85 weight percent propionic acid structural units. The strength of the first reed will depend on the degree of elongation used to increase the strength of the polymer and yarn formed from it. This strength also depends on whether the second yarn is continuous filament or staple fiber. For a given polymer, continuous filament yarns have higher strength than rayon yarns. To address the problem of providing colored yarns that contain uncolored fluoropolymer yarns, the strength of the second yarn is less important. Therefore, an acrylic polymer yarn can be used, which can be used only as a staple fiber yarn and has a strength of 2 to 3 gPd. Polyester staple fiber yarns usually show a strength of 91.716-12.200427880. 2 · 4 to 7 gpd 'and polyamide staple fibers have a strength of 2 · 9 to 7.2 gpd. However, at a more southern strength level, even for acrylic polymer yarns, rayon yarns can provide a blended yarn with fluoropolymer yarns, in which the fluoropolymer yarns show greater strength than themselves. . In general, the same is true for s ’continuous filament poly-S purpose yarns and poly-donylamine yarns, both of which show strengths of up to 3.5 gpd. However, in order to provide a mixed yarn having a stronger strength than the fluoropolymer yarn component, it is preferable to use a high-strength polyester and polyamide yarn as the second yarn. These yarns show a strength of at least 5.9 gpd, and preferably at least 6.5 gpd. The strength of polyester and polyamide yarns usually does not exceed 9 gpd. The second yarn typically has an elongation of 15 to 30%. Preferably, the elongation of the second yarn is less than 8%, more preferably less than 5% of the first yarn, and most preferably less than 2% of the first yarn. These differences in elongation are applied to each of the first and second yarns described herein. The first yarn in the blended yarn preferably also has a strength of at least 2.5 gpd, and more preferably at least 3 gpd. The strength of the second yarn is preferably greater than the strength of the first yarn by at least 2 gpd. The first yarn of this month can be monofilament or multifilament. When the yarn is a monofilament, the yarn has a diameter of 50 to 1,000 m. When the yarn is a multifilament, a single filament tuft has a diameter of 8 to 30 micrometers, and the yarn usually has 30 to 5,000 demers, preferably 100 to 100. Daniel and contains 20 to 2⑼ filaments. In the case of multifilament yarns, a single filament is preferably 2 to 50 denier per filament, 5 to 40 denier / filament, and most preferably 1 to 30 denier per filament.鬲 Break strength without excessive rigidity is preferably 20-30 denier, 糸 stomach first yarn is preferably multifilament yarn, and its characteristic parameters can be compared with the characteristic multifilament first yarn mentioned earlier in this paragraph. The parameters are the same. The first and second 91716 -13- 200427880 yarns can also be made of artificial staple fibers instead of continuous filaments to enhance the appearance, and the blended yarn of the present invention can be a mixture of continuous filaments and artificial staple fibers. In the case where the first yarn of artificial staple fiber and / or ^, v is used in the mixed yarn of the present invention, the artificial staple fiber usually has a denier, preferably from 5 to 5 denier / fiber (or a fiber made of the same) Of filaments). The first and second yarns can be blended by conventional textile fiber methods, such as twisting, and the paired twisted mixed yarns can be further twisted together, such as forming a rope in the opposite twisting direction. These yarns can be woven, that is, flat yam, or deformed by conventional methods to increase the bulk of the yarn. Regardless of whether the second yarn is dyed before or after the formation of the mixed yarn, the color of the second yarn will be given to the mixed yarn, the twisted yarn pair to the mixed yarn, and the rope of the mixed yarn even if the first yarn is not dyed. The preferred method for blending the first and second yarns is multi-strand merging. For example, published by Loughborough University in 1989, Air-Jet Texturing & Mingling, Description, the publication is the Proceedings of an International Conference held at the University in September 1989, which includes papers submitted by A. Demic, Intermingle / Interlacing: a Broad Survey ( P. 416). Entangling is described as subjecting a bundle of loose flat yarns or textured yarns to a perturbative cold air jet impact (combined jet) at an angle to the yarn path to open the sections of filaments, while near the opened sections of filaments, the filaments Intertwined and intertwined to form a tight start and segment. Multiple merging is described as entanglement of two yarns, whereby entanglement and entanglement involve filaments of both yarns. The plurality of combined yarns thus formed are bonded yarns, which means that the two yarns jointly form a single yarn (mixed yarn), and the resulting mixed yarn 91716 -14- 200427880 is an entangled section alternating with the open section period. form. The described and prepared method is applied to a plurality of combined blended yarns of the present invention. The multiple blending yarns of the present invention are similar to the blending yarns described as "blending" in Figure 5 on page 59 of the Demic paper. The conditions for air jetting and performing multiple blending methods for multiple mergers are well known. It is well known, as described in the Demic paper and disclosed in U.S. Patent No. 4,025,595. When yarns fed into multiple co-mingling jets are deformed, the deformation may include different types of deformation , Such as air jet deformation, false twist deformation and thermal fluid deformation. The plurality of blended blended yarns of the present invention preferably have 3 to 50 entanglements per meter (according to the third block of US Patent No. 4,025,595). Measured to reveal) to achieve the cohesiveness required for the deformation process. Kinks along the length of the blended yarn are knots, and these knots are sometimes referred to as nips or knots, and Kink and other kinks provide integrity for the blended yarn. Even when the first yarn is monofilament or human knuckle fiber day guard, the second yarn filament will be entangled with monofilament or rayon staple fiber to provide integrity The blended yarn. When one or two kinds of blended yarn are human k short fiber yarn This is also the case. In a better blended yarn, both the first and second yarns are multifilament yarns, which provide the blended yarn with the most uniform color appearance of the blended yarn, which color is dyed by the second yarn. Color. Another best mixed yarn for Maoyue is this yarn including a core and a sheath (where M: yarn exists in the core and the first yarn exists in the outer loop. The mixed yarn is made by The first yarn wrap is made around the second yarn, but is preferably manufactured by combining multiple yarns. Wherein, relative to the feeding of the second yarn to the spray π, the first yarn is excessively fed to the multiple merge nozzles, which easily causes the first yarn — The filament of the yarn is wrapped around the second yarn of 91716 -15- 200427880 and the filaments of each yarn are entangled with each other by a plurality of merging methods. The excess feed of the first yarn is fed by the first yarn The speed of up to multiple merging nozzles is achieved faster than the winding speed of the mixed yarn downstream of the nozzle. The structure of the mixed yarn of the present invention has better use of the greater strength of the second yarn to increase the strength of the mixed yarn beyond the strength of the first yarn The advantage of the sheath yarn (ie the first yarn) in this construction is that the core yarn (ie the second yarn) is not completely covered ), So that the dyeing of the second yarn still provides coloring for the mixed yarn. The first yarn colors the mixed yarn by manipulating the color of the second yarn, some reflecting and some transmitting light to extract the color so that ^ The color of the second yarn can be seen through the thickness of the filament of the first-yarn. The basis of combining the second-and second-yarn into the blended yarn of the invention is the need for the blending yarn. Daniel. The Daniel chooses the first and the second by The two yarns can be achieved by the number of Daniels and mixed yarns. The mixed yarns can be the same number of the first and the second brother ν can be more than the number of the second yarn 'and vice versa. The better mixed yarn has two types The first-yarn and a second-two, and the other preferred yarn have two kinds of second-yarn and one kind of first-yarn. The best blended yarn of the first and second k-max maximizes the outdoor weathering strength of fluoropolymer. Second mention of 3 miles to make the residual ^ A ^ ^ 彳 " ° Kun yarn to maximize the initial mixing v intensity and color uniformity. These goals are also achieved with Daniel numbers. For example, when there is only one type of second yarn with a higher Daniel number, the second yarn tends to have an initial mixed yarn strength, depending on the first yarn and the second color are uniform and relatively high. In the case of the difference between the Daniel of this hair and the difference between Daniel and the yue yue root blended yarn, ", when one or both of the yarns are artificial staple fiber yarns :: one office and two second artificial Staple fiber yarn to increase the chance of entanglement between yarns and between each of the fathers using a number of yr artificial staple fibers 91716 -16- 200427880. The second yarn can be dyed by conventional textile fiber methods and using conventional Textile fiber dyes are dyed depending on whether the second yarn is made of polyester, polyamine or acrylic fibers. Further descriptions of these dyeing methods and dyes and the modification of the polymers that make up the yarn are disclosed in In the above-mentioned vomit-Othmer. The second yarn can be dyed before or after being combined into a mixed yarn. The mixed yarn is dyed so that the first yarn is not dyed. A preferred mixed yarn contains at least two second yarns, one of which is acrylic It is a staple fiber and the other is either one or both of polyester and polyamide. The blended yarn is particularly suitable for applications exposed to the weather, in which the dye fastness of acrylic fibers maintains the color of the blended yarn, and fluorine Polymer yarn Provides long-term strength. Examples The yarn used in this example is a Tefzel® ETFE fluoropolymer, which is a terpolymer of ethylene, tetrafluoroethylene, and at least 5 mole% of a perfluoroalkylethylene trimer, having 258 ° C melting temperature (peak value) and 29.6 g / 10 minute melt flow rate, both values are measured according to ASTM 3159, and a weight of 5 kg is used to determine MFR. The lubricant for the coated yarn after melt spinning is the following: 88.9 weight % (: 1 & 1 ^ plus eight negative 1 & 1 ^ ?? polyol polyester, 5% by weight 11111961 ^ @ 0-1144 ester oil emulsifier covered with ethoxylated polyol, 0.67% by weight Cytek Aerosol® OT dioctyl sulfosuccinate wetting agent (75% by weight aqueous solution), 5% by weight Cognis Emersol 871 fatty acid surfactant, 0-26% by weight Uniroal Naugard® PHR linolenic acid antioxidant, 91716 -17- 200427880 Used as a stabilizer for fatty acids of 0.667% by weight sodium hydroxide (45% by weight in water) and 0.04% by weight of Dow Corning polydimethylsiloxane (processing aid _ maximum reduction of lubricant deposition on hot rolls) At ambient temperature, fluoropolymers and lubricants The agent has a surface tension of 25 dyne / cm and 23.5 dyne / cm, respectively. Except that the single-sided rubber roller 112 and the guide roller 111 do not exist, US Patent Publication No. 2002/0079610 A1 is used in FIG. 9 The equipment shown is configured to melt-spin a fluoropolymer and to apply lubricant using an applicator guide roller located below the moderator n 0, upstream of the change in the direction guide. This application The applicator guide is similar to the Luro-Jet® applicator guide, with a v-shaped groove. The groove collects a large amount of extruded filaments into the groove and includes an applicator on a V-shaped substrate. The applicator It also includes a hole through which lubricant can be pumped (dosed) to the yarn as it passes through the applicator. The extruder is a 1.5-inch (3.8 cm) Hastelloy C_276 single screw extruder connected to a gear pump, which is connected to a spinneret assembly through an adapter. The spinneret assembly includes a filter assembly To filter the molten polymer. The spinneret assembly is the assembly 70 of FIG. 8 of the U.S. Patent Publication and includes a delivery tube and a spinneret panel, which are depicted as elements 78 and 75 in FIG. 8, respectively. The spinneret panel has 30 holes, which are arranged in a circle with a diameter of 2 inches (51 cm). Each hole (extrusion die hole) has a diameter of 30 mils (mii) and 90 shanks. length. The slow cooler is an example of the slow cooler in Figures 10A and 10B of the U.S. Patent Publication. The working temperature is as follows: Extruder: In the extruder area_feed, # 1 and # 2 are 25 °. 〇, 91716 -18-200427880 〇C, 27 (TC, carousel: 317 ° C, spinneret panel: 350 ° C, slow cooler · 2 at positions # 1, # 2 and # 3 respectively 〇4t :, 21 (^ and 158 ° C. The fluoropolymer production (the fluoropolymer leaves the spinneret) is set to the maximum value by a gear pump, which means that it is not enough to cause melt fracture of the extruded filament. This maximum is 50.5 g / min (6.7 lb / hr). The resulting yarn is cured at a distance greater than 50x the diameter of the extrusion hole from the spinneret. The above lubricant is applied only to the yarn below the moderator and is fed into the yarn. The temperature of the roll is about 180 ° and its surface speed is 309 m / min. The stretching roll is heated to i5 (rc and rotated at a surface speed of 1240 m / min to provide a stretch ratio of 4.01. By The Leesona winding machine winds the yarn onto a bobbin. The obtained yarn has the following characteristics: the strength is 3.45 gpd, the elongation is 7.7%, and the tensile modulus is 55 gpd. When the speed is reduced to 1140 m / min to reduce the draw ratio to 3 69 ', the following yarn characteristics will be obtained: strength-3.14 gpd, elongation _ 9.4 ° / 〇, modulus 51 gpd. Yarn The Daniel number has increased from 374 to 407. The coefficient of variation of the yarn Daniel number is less than 2%. The coefficient of variation is the average weight of five consecutive ten-meter-long yarns divided by the standard deviation (x100). Example 1 Except that the draw ratio is slightly reduced In order to obtain a more southern elongation yarn (which has a lower strength), the fluoropolymer yarn used in this example is a yarn generally prepared by the above method. This yarn is 400 denier, contains 13 filaments, and It has a strength of 2 · 9 gp d and an elongation of 14 _ 3%. The other yarns used in this example are 91716 -19- 200427880. The other yarns are polyester yarns. One kind of yarn has 100 filaments and 633 denier after stretching (Initial Daniel 640) and has a strength of 7.89 gpd and an elongation of 24% (PET Yarn A). PET Yarn A was dyed white and was obtained from DuPont Company, Wilmington, DE ) Obtained. Another yarn with 108 filaments, stretched and dyed 885 denier (initial denier 840), and has a strength of 7.49 gpd and an elongation of 20% (PET yarn B). PET yarn B & Akra Company Yarn, which United Yarn Co., Wayne, NJ) and dyed it blue. A mixed yarn of one warp yarn of ETFE copolymer yarn and one warp yarn of PET yarn A was prepared by air-jet mixing (multiple merging). The method is as follows: A FOO kink machine is used. The machine uses an IMS 3-2 air-entangled spout obtained from Winstom_Salem Nc International Machine Sales Co., Ltd. (IMS). The fluoropolymer yarn was fed excessively through the nozzle with a yarn tension of 5 grams, and pE1 ^^, a was supplied through the nozzle with a yarn tension of 20 grams. The air pressure for combining these yarns was 40 psi. Inches (psi) and the winding speed was 25 yards per minute (ypm). The obtained multiple combined blended yarns are sheath / core blended yarns, in which the blended yarn surface is mainly a fluoropolymer yarn and has a strength of 1070 denier, a strength of 4.45 gpd, and an elongation of 21.83%. Another blended yarn is made by the same air-jet multiple blending method, using the same ETFE copolymer yarn and PET yarn B (one warp yarn per yarn) to obtain multiple blended outer sheath / core mixed yarns, which It has 1326 denier, 5-5 gpd strength and 21.5% elongation, and shows a uniform blue color. Two warp yarns of the same ETFE copolymer yarn and one warp of pet yarn B warp 91716-20-200427880 yarns are produced by the same air-jet multiple merge method to obtain another mixed yarn. The two ETFE yarns are at the same tension ( 5 g) was fed through the nozzle and the tension of the pet yarn was 20 g, thereby obtaining a plurality of merging yarns having a density of 1728 denier, a strength of 3.93 gpd, and an elongation of 16.24%. The mixed yarn of ETFE and PET yarn A is white 'and since the blue PET yarn B is used, the mixed yarn of ETFE and PET yarn B is blue. Similar results were obtained when PET yarns were replaced with polyamide or propionate yarns. Example 2 The sewing thread of the yarn is made of a plurality of combined yarns (which are made by using one warp yarn of ETFE copolymer yarn and one warp yarn of PET yarn B in Example 1), and the manufacturing method is (a) Twist of centimeter mixed yarn (b) Twist the three warp yarns of the yarn at one twist / cm but opposite to the direction of twist in the yarn, and (0) make the resulting thread under a tension of 140-15 () C Heat-set. The obtained sewing thread has a denier of 3978. If necessary, an adhesive or a finishing agent can be applied to the sewing thread. The obtained sewing thread has a balanced crorded structure, has a uniform denier and shows excellent The stitch loop formation was free of any knots or tangles. Example 3 As described in Example 1, 400 Daniel Kynar® 710 (PVDF Yarn) one warp yarn and 885 Daniel pED0, one warp yarn air jet multiple and combined together, resulting in a blue mixed yarn of 129 denier, 5.56 gpd strength and 20.0% elongation. ⑧71〇PVDF The continuous filament yarn itself has a strength of M §1) (1 and an elongation of 391%. 917 16 -21-200427880 Example 4 8 One warp yarn of 85 denier PET yarn B and one warp yarn of 20s / 2 ply (512 denier) dark blue acrylic staple fiber and one warp yarn of 400 denier ETFE yarn such as Example 3 As described above, multiple air jets were combined, and ETFE and acrylic yarn were fed in excess with the same tension, thereby producing a blended yarn of 1 885 denier, 3.97 gpd strength, and 20.5% elongation. The 5 12 denier Acrylic staple fiber was obtained from Phar Yarns Co., Ltd. and had a strength of 1.7 gpd and an elongation of 38.34%. Example 5 A warp yarn of 840 denier (840-140_400T) (a white high-strength nylon obtained from DuPont) was used. Combined with one of the 400 denier ETFE warp yarns as described in Example 3 to produce a white mixed yarn with 1263 denier, 615 gpd strength and 25.5% elongation. 840 denier nylon filament yarn has a strength of 9.30 gpd and Elongation of 25.5%. This example describes an embodiment in which the blended yarn contains a binder for the second yarn, and an example of the binder is a polymer containing polyurethane or polysiloxane as a main component. These adhesives do not adhere to fluoropolymers, but can be used to bond composite yarns. The general procedure for applying adhesives (adhesives) is to form a liquid medium containing _: qi :, and by conventional methods such as using a single surface Glue lightly: (adhesive) apply σ to the yarn, paddmg the adhesive medium onto the yarn or apply the medium to the yarn by dipping or spraying, teach / and wind on the final package . ,,,, and setting As an example, multiple combined yarns are composed of Daniel, 13 dpf E coffee yarn 91716 • 22- 200427880-the root warp yarn and 220 Daniel, 3.25-the polyester yarn-the root warp yarn. The single yarn is characterized by 9S twists (9 turns / inch (twists per inch)), 9 turns / 2.54 cm), which means 9 turns in the "s" direction. The two yarns of these yarns are plied together. The plied feature is 7Z (7 twists per inch, 7 turns / 2.54 cm), which means 7 turns in the Z direction. The adhesive was an aqueous polyurethane vinegar from NuBond (R) (synthetic thread, Bethlehem, PA), which was lightly applied to a plied yarn having a total measured weight of 145 denier by | The setter is wound on the final package. Compared with the case of using the same yarn but no binder, the bonded yarn provided by φ enables the stitching to be performed continuously for a longer period of time and the performance is better in the industrial stitching. Therefore the use of adhesives results in fewer yarn breaks or kinks, which are typical causes of machine shutdowns. The improved stitch-cutting performance is similar to that of poly-g yarns when used with the same adhesive. The effect of the adhesive on the polyester yarn itself is similar to the effect of the adhesive on the composite EFTE / polyester yarn. A similarly improved sewing performance was obtained by plaiting mixed yarns of the same yarn together to produce a composite yarn measuring 2572 denier, applying a polyurethane adhesive, and heat setting. Example 7 A broad example is directed to the following example, in which the weather resistance of the second yarn is better when the second yarn and the fluoropolymer yarn are combined into a composite yarn, which means that the strength degradation of the second yarn in the mixed yarn is less than its own weather resistance. The strength of the blend is degraded, and the tensile strength of the blended yarn is lower than expected. This effect is obtained when the second yarn is polyester or polyamide. The yarn described in Yarn Example 6 in this example. According to SAE J1960, the xenon arc accelerated weather resistance device was used to measure the accelerated resistance 91716 -23- 200427880 weather resistance, which is commercially available from Atlas Company of Chicago, Illinois. The strength and elongation of the yarn were measured before and after exposure to 450 kilojoules of energy (equivalent to more than 4 months of outdoor exposure at 45 degrees south of Florida). The exposure was sufficient to cause a 34% decrease in the elongation of the ETFE yarn itself and a 63% decrease in the elongation of the polyester yarn itself. In contrast, the elongation of the composite ETFE / polyester yarn only decreased by 37%, which is about the same as the elongation of the ETFE yarn itself and much smaller than the elongation of the polyester yarn itself. In addition, the strength (gpd) of the deleted yarn itself was hardly affected after the exposure, and the original strength was maintained. In contrast, composite yarns retain 91% of their original value.
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