JP2004052131A - Method for producing polyester undrawn fiber - Google Patents
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【０００１】
【発明の属する技術分野】
本発明は、ポリエステル未延伸糸（部分配向糸）の製造方法に関する。さらに詳しくは、本発明は、長期にわたり溶融紡糸操作を中断することなく、好ましい色調、優れた品質を有する、複屈折率が０．０３〜０．０６のポリエステル未延伸糸（部分配向糸）を、安定して製造する方法に関するものである。
【０００２】
【従来の技術】
ポリエステル、特にポリエチレンテレフタレートの溶融紡糸においては、紡糸時間の経過と共に、紡糸口金吐出孔周辺に異物（以下、単に口金異物と称する場合もある）が発現し、付着・堆積し、溶融ポリマーの正常な流れを阻害し、吐出糸条の屈曲、ピクツキ、旋回等（以下、単に異常吐出現象と称する場合もある）が進行し、ついには吐出ポリマー糸条が紡糸口金面に付着して断糸するという現象が起こる。特に、分子配向度が複屈折率で０．０３以上のポリエステル未延伸糸（部分配向糸）を紡糸引き取りする際には、該口金異物が溶融ポリマー吐出状態に及ぼす影響が大きく、短時間の間に、異常吐出現象が発生することが多くなる。このような異常吐出現象が起こると、紡糸運転に支障をきたすのみならず、冷却・固化の過程で繊維構造斑が発生し、得られたポリエステル未延伸糸（部分配向糸）は品質斑（延伸仮撚加工時毛羽、断糸発生など）を内在したものとなる。
【０００３】
このような口金異物の付着・堆積原因は、ポリエステル中に存在するアンチモンに起因することが知られているが、そのアンチモンは、ポリエステル、特にポリエチレンテレフタレートの触媒として、優れた重縮合触媒性能を有する、また色調の良好なポリエステルが得られるなどの理由から、最も広く使用されているアンチモン系触媒に由来するものであり、通常のポリエステル中には必然的に存在している。したがって、通常のポリエステルの溶融紡糸においては、紡糸口金吐出孔周辺に付着・堆積した口金異物を拭き取る為に、紡糸引き取り操作を一定間隔で中断し、再び正常運転を繰り返さねばならないという問題がある。
【０００４】
一方、該アンチモン化合物以外の重縮合触媒として、チタンテトラブトキシドのようなチタン化合物を用いることも提案されているが、このようなチタン化合物を使用した場合、上記のような、口金異物の付着・堆積は減少するが、ポリエステル自身の黄色味が強くなり、ポリエステル繊維として衣料用途に使用できない色調となるという問題があった。
【０００５】
【発明が解決しようとする課題】
本発明は、上記従来技術を背景になされたもので、その目的は、長期にわたり溶融紡糸操作を中断することなく、好ましい色調、優れた品質を有し、分子配向度が複屈折率で０．０３〜０．０６のポリエステル未延伸糸（部分配向糸）を、安定して製造する方法を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者らは、上記従来技術に鑑み、鋭意検討を重ねた結果、本発明を完成するに至った。すなわち、本発明の目的は、「複屈折率が０．０３〜０．０６のポリエステル未延伸糸を製造するに際し、トリメリット酸チタンおよび下記一般式（Ｉ）で表されるホスホネート化合物を使用し、かつポリエステル中のチタン（Ｔｉ）およびリン（Ｐ）含有量が下記式（１）を満足するようにして合成されたポリエチレンテレフタレート系ポリエステルを溶融し、冷却・固化しつつ、２５００〜４０００ｍ／ｍｉｎの速度で紡糸引き取りすることを特徴とする、ポリエステル未延伸糸の製造方法」によって達成される。
【０００７】
２≦Ｐ／Ｔｉ≦１５ （１）
【０００８】
【化２】
【発明の実施の形態】
以下本発明の実施形態について詳細に説明する。
本発明でいうポリエステルとは、主たる繰り返し単位としてエチレンテレフタレート単位が８５モル％以上、好ましくは９５モル％以上からなるポリエステルである。テレフタル酸成分および／またはエチレングリコール成分以外の成分を少量（通常は、テレフタル酸成分またはエチレングリコール成分に対して２０モル％以下）共重合したものであっても良い。
【００１０】
本発明においては、実質的にアンチモン（Ｓｂ）を含まず、トリメリット酸チタンおよび下記一般式（Ｉ）で表されるホスホネート化合物を使用して合成されたポリエチレンテレフタレート系ポリエステルを使用する。
【００１１】
【化３】
このように、アンチモン（Ｓｂ）を含まず、トリメリット酸チタンおよび特定のホスホネート化合物を使用して合成されたポリエチレンテレフタレート系ポリエステルを溶融吐出すると、口金異物の発生が劇的に低減し、吐出ポリマー糸条が安定となり、紡糸操作を中断することなく、長期にわたり、品質斑の少ない、分子配向度が複屈折率で０．０３〜０．０６のポリエステル未延伸糸（部分配向糸）を連続して製造することができる。
【００１３】
該トリメリット酸チタンはポリエステルポリマー中に可溶であり、このような化合物を、ポリエステルを構成する全ジカルボン酸成分を基準として、チタン金属元素として２〜１５ｍｍｏｌ％となるように重縮合工程で添加することが好ましい。尚、ここで言う”チタン金属元素量”とは、エステル交換反応による第１段階反応を行う場合は、エステル交換反応触媒として使用されたチタン化合物と重縮合反応触媒として使用されたチタン化合物との合計量を示す。
【００１４】
トリメリット酸チタンは、全添加量の一部及び／又はその全量をエステル交換反応開始前に反応系内に添加され、エステル交換反応と重縮合反応触媒とに兼用する方法が好ましく採用される。
【００１５】
上記一般式（Ｉ）で表されるホスホネート化合物としては、ホスホン酸のジメチルエステル、ジエチルエステル、ジプロピルエステル及びジブチルエステルを挙げることができ、具体的にはカルボメトキシメタンホスホン酸、カルボエトキシメタンホスホン酸、カルボプロポキシメタンホスホン酸、カルボブトキシメタンホスホン酸、カルボメトキシ−ホスホノ−フェニル酢酸、カルボエトキシ−ホスホノ−フェニル酢酸、カルボプロポキシ−ホスホノ−フェニル酢酸、カルボブトキシ−ホスホノ−フェニル酢酸等のジメチルエステル、ジエチルエステル、ジプロピルエステル及びジブチルエステルが挙げられる。
【００１６】
上記のホスホネート化合物は、通常安定剤として使用されるリン化合物に比較して、チタン化合物との反応が比較的緩やかに進行するので、反応中における、チタン化合物の触媒活性持続時間が長く、結果として、該チタン化合物のポリエステルへの添加量を少なくすることができ、また、本発明のように触媒に対し多量に安定剤を添加する場合であっても、ポリエステルの熱安定性を損ない難い特性を有している。
【００１７】
これら、ホスホネート化合物の添加時期は、ポリエステル製造時における、エステル交換反応が実質的に終了した後であればいつでもよく、例えば、重縮合反応を開始する以前の大気圧下でも、重縮合反応を開始した後の減圧下でも、重縮合反応の末期でもまた、重縮合反応の終了後、すなわちポリマーを得た後に添加してもよい。
【００１８】
さらに、ポリエステル中のチタン（Ｔｉ）およびリン（Ｐ）含有量が下記式（１）を満足するようにして合成されたポリエチレンテレフタレート系ポリエステルを溶融紡糸して得られたポリエステル未延伸糸（部分配向糸）は、アンチモン系触媒を使用して合成された従来のポリエステルから得られた未延伸糸（部分配向糸）と同じレベルの色調を有している。
【００１９】
２≦Ｐ／Ｔｉ≦１５ （１）
（上記式中、Ｔｉはポリエステル中に含有されるチタン金属元素の濃度（ｍｍｏｌ％）、Ｐはポリエステル中に含有されるリン元素の濃度（ｍｍｏｌ％）を示す。）
すなわち、（Ｐ／Ｔｉ）が２未満の場合、合成されたポリエステルは著しく黄味を帯び、該ポリエステルからの未延伸糸（部分配向糸）を延伸糸あるいは仮撚加工糸（以下、単に繊維と称する）とした時、衣料用途に使用できない色調となる。ここで「繊維とした時、衣料用途に使用できない色調」とは、繊維を筒編状として測定したカラーＬ＊値とカラーｂ＊値との差（以下（Ｌ＊−ｂ＊）と称する）が８０未満の場合をいう（逆に好ましい色調とはＬ＊−ｂ＊が８０以上の場合をいう）。一方（Ｐ／Ｔｉ）が１５を越えるとポリエステルの重合反応性が大幅に低下し、目的のポリエステルを得ることができない。なお、（Ｐ／Ｔｉ）が３〜１２の範囲であるとき、好ましい色調の繊維となるポリエチレンテレフタレート系ポリエステルが得られる。
【００２０】
本発明における溶融紡糸は、溶融押出機（スクリュウーエクストルーダー）を装備した通常のポリエステル溶融紡糸機を用い、上述のポリエチレンテレフタレート系ポリエステルを通常のポリエステル溶融紡糸温度（２７０〜３１０℃）で溶融し、紡糸口金より吐出し、冷却・固化しつつ、回転ローラーあるいは計量ノズル型給油装置で油剤を付与しながら２５００〜４０００ｍ／ｍｉｎの速度で引き取りする方法で、行う。紡糸速度が２５００ｍ／ｍｉｎ未満の場合は得られたポリエステル未延伸糸（部分配向糸）の複屈折率が０．０３未満となり、延伸仮撚加工が困難となる。複屈折率が０．０６を越える場合はポリエステル未延伸糸（部分配向糸）からの延伸仮撚加工糸の強度、伸度が実用範囲以下に低下する。
【００２１】
このように、本発明によれば、長期にわたり連続的に、安定して、好ましい色調を有し、かつ品質斑の少ない、分子配向度が複屈折率で０．０３〜０．０６のポリエステル未延伸糸（部分配向糸）を製造することができる。
【００２２】
【実施例】
以下、実施例により、本発明を更に具体的に説明するが、本発明はこれにより何ら限定を受けるものでは無い。なお、実施例における各項目は次の方法で測定した。
【００２３】
（１）チタン金属元素含有量、リン元素含有量
粒状のポリエステル試料をアルミ板上で加熱溶融した後、圧縮プレス機で平坦面を有する試験成型体を作成し、理学電気工業株式会社製蛍光Ｘ線測定装置３２７０Ｅを用いてチタン金属元素含有量およびリン元素含有量を測定した。
【００２４】
（２）固有粘度
常法に従い、オルソクロロフェノールを溶媒として使用し３５℃で測定した。
【００２５】
（３）複屈折率
常法に従い、光学顕微鏡とコンペンセーターを用いて、繊維の表面に観察される偏光のリターデーションから求めた。
【００２６】
（４）口金異物高さ
各実施例に示す方法、条件で溶融紡糸を行い、３、６、９日後に紡糸口金表面に離型剤を吹き付けて、吐出ポリマーが付着しないようにして、紡糸口金を取り外し、顕微鏡にて吐出孔周辺に付着・堆積した口金異物の高さを測定した。全ての吐出孔について口金異物の高さを測定し、それらの平均値で表した。
【００２７】
（５）紡糸断糸率（％）
人為的あるいは機械的要因に起因する断糸を除き、紡糸機運転中に発生した紡糸断糸回数を記録し下記式で紡糸断糸率（％）を計算した。
【００２８】
紡糸断糸率（％）＝［断糸回数／（稼動ワインダー数×ドッフ数）］×１００
ここで、ドッフ数とは未延伸糸パッケージを既定量（１０ｋｇ）まで捲き取った回数をいう。
【００２９】
（６）毛羽個数（個／１０４ｍ）
東レ（株）製ＤＴ−１０４型毛羽カウンター装置を用いて、延伸仮撚加工糸を５００ｍ／ｍｉｎの速度で２０分間連続測定して発生毛羽数をカウントした。
【００３０】
（７）延伸仮撚断糸率（％）
人為的あるいは機械的要因に起因する断糸を除き、延伸仮撚機運転中に発生した断糸回数を記録し下記式で延伸仮撚断糸率（％）を計算した。
延伸仮撚断糸率（％）＝［断糸回数／（稼動錘数×ドッフ数）］×１００
ここで、ドッフ数とは仮撚加工糸パッケージを既定量（２．５ｋｇ）まで捲き取った回数をいう。
【００３１】
（８）（Ｌ＊−ｂ＊）値
ポリエステル繊維を１２ゲージ丸編機で３０ｃｍ長の筒編みとし、ミノルタ株式会社社製ハンター型色差計ＣＲ−２００を用い、Ｌ＊値、ｂ＊値を測定し、その差を（Ｌ＊−ｂ＊）値とした。
【００３２】
（９）強度・伸度
ＪＩＳ−Ｌ１０１３に準拠して測定した。
【００３３】
［実施例１〜３、比較例１］
ポリエステル中に含有されるチタン金属元素量（Ｔｉ）およびリン元素濃度（Ｐ）を各々表１に示す量となるようにして、トリメリット酸チタンおよびトリエチルホスホネートを用いて、テレフタル酸ジメチルとエチレングリコールとを重縮合し、固有粘度０．６３０のポリエチレンテレフタレートを得た。
【００３４】
該ポリエチレンテレフタレートをペレット状となし、１５０℃で５時間乾燥した後、スクリュウー式押出機を装備した溶融紡糸設備にて溶融し、２９５℃のスピンブロックに導入し、孔径０．２３ｍｍの吐出孔が同心円状に７２個配列してある紡糸口金から、４８ｇ／分の流量で吐出し、ポリマー流を、クロスフロー式の送風筒から噴出される空気流で冷却・固化しつつ、紡糸口金から８０ｃｍ下方に設置された計量ノズル式給油装置で、給油しながら集束し、エアーノズルで交絡処理を施した後に３３００ｍ／分の速度で引き取り、１４５ｄｔｅｘ／７２ｆｉｌａｍｅｎｔｓの未延伸糸（部分配向糸）として、１０ｋｇをパッケージ状に巻き取った。上記溶融紡糸操作は９日間連続して行った。
【００３５】
本例においては、表１から明らかなように、何れの例においても、紡糸経時に伴う口金異物の付着・堆積が極めて少なく、ポリマー吐出状態は長期にわたり安定であり、紡糸断糸率も低いレベルであった。
【００３６】
次に、得られたポリエステル未延伸糸（部分配向糸）パッケージを、直径４５ｍｍのウレタンディスクを仮撚具として装備した帝人製機株式会社製ＨＴＳ−１５００型延伸仮撚加工機にて、延伸倍率１．６５、第１ヒーター前半部温度５００℃、後半部温度３１０℃、延伸仮撚速度７００ｍ／ｍｉｎの延伸仮撚条件で、延伸仮撚加工を行い８５ｄｔｅｘ／７２ｆｉｌａｍｅｎｎｔｓの仮撚加工糸を得た。なお、１０ｋｇ捲の未延伸パッケージから２．５ｋｇ捲の仮撚加工糸パッケージを４個作成する方法で延伸仮撚加工を行った。
【００３７】
表１から明らかなように、何れの例においても、紡糸経時に関連した毛羽発生の増加および延伸仮撚断糸率の上昇は認められなかった。しかし、比較例１における仮撚加工糸の筒編地色調（Ｌ＊−ｂ＊）値は８０未満であり、衣料用途に使用できない色調を有していた。
【００３８】
【表１】
［比較例２］
３酸化アンチモン（Ｓｂ２Ｏ３）を重合触媒として、テレフタル酸ジメチルとエチレングリコールとを常法にて重縮合し、固有粘度０．６３０のポリエチレンテレフタレートを得た。
【００４０】
該ポリエチレンテレフタレートをペレット状となし、実施例１〜３と同じ方法、条件で溶融紡糸を行い、１４５ｄｔｅｘ／７２ｆｉｌａｍｅｎｔｓのポリエステル未延伸糸（部分配向糸）を製造した。
【００４１】
本例においては、表１から明らかなように、紡糸時間の経過にともない口金異物が急速に成長し、吐出糸条の屈曲、ピクツキおよび旋回が増加するに従い、紡糸断糸の急激な増加が認められた。なお、紡糸３日経過後は、紡糸断糸が多発し、正常な紡糸操作が困難となり、運転を中止した。
【００４２】
得られたポリエステル未延伸糸（部分配向糸）パッケージを、実施例１〜３と同じ方法、条件で延伸仮撚加工を行い８５ｄｔｅｘ／７２ｆｉｌａｍｅｎｎｔｓの仮撚加工糸を得た。表１から明らかなように、本比較例における紡糸３日後ポリエステル未延伸糸（部分配向糸）では、延伸仮撚時、毛羽および断糸の発生が極めて多かった。
【００４３】
【発明の効果】
本発明によれば、長期にわたり連続的に、安定して、好ましい色調を有し、かつ品質斑の少ない、分子配向度が複屈折率で０．０３〜０．０６のポリエステル未延伸糸（部分配向糸）を製造することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an undrawn polyester yarn (partially oriented yarn). More specifically, the present invention provides a polyester unstretched yarn (partially oriented yarn) having a preferable color tone and excellent quality and a birefringence of 0.03 to 0.06 without interrupting the melt spinning operation for a long period of time. And a method for stable production.
[0002]
[Prior art]
In the melt spinning of polyester, particularly polyethylene terephthalate, as the spinning time elapses, foreign substances (hereinafter, sometimes simply referred to as cap foreign substances) appear around the spinneret discharge hole, adhere and deposit, and the normality of the molten polymer is reduced. The flow is hindered, and the discharge yarn is bent, spiked, swirled, etc. (hereinafter sometimes simply referred to as abnormal discharge phenomenon), and finally, the discharged polymer yarn adheres to the spinneret surface and breaks. A phenomenon occurs. In particular, when spinning off a polyester undrawn yarn (partially oriented yarn) having a molecular orientation degree of 0.03 or more in birefringence, the foreign matter of the die has a large effect on the molten polymer ejection state, Then, an abnormal ejection phenomenon often occurs. Such an abnormal discharge phenomenon not only hinders the spinning operation, but also causes unevenness in the fiber structure during the cooling and solidification process, and the resulting polyester undrawn yarn (partially oriented yarn) has uneven quality (drawing). Fluff during false twisting, yarn breakage, etc.) are inherent.
[0003]
It is known that the cause of adhesion and deposition of such base foreign matter is caused by antimony present in polyester, and the antimony has excellent polycondensation catalytic performance as a catalyst for polyester, especially polyethylene terephthalate. It is derived from the most widely used antimony-based catalyst because a polyester having a good color tone can be obtained, and is inevitably present in ordinary polyester. Therefore, in the usual melt spinning of polyester, there is a problem that the spinning take-off operation has to be interrupted at regular intervals and the normal operation has to be repeated again in order to wipe off foreign matter adhered and deposited around the spinneret discharge hole.
[0004]
On the other hand, it has been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than the antimony compound. Deposition is reduced, but there is a problem that the yellow color of polyester itself becomes strong and the polyester fiber has a color that cannot be used for clothing.
[0005]
[Problems to be solved by the invention]
The present invention has been made on the background of the above-mentioned prior art, and its object is to provide a preferable color tone, excellent quality, and a birefringence of a molecular orientation of 0.1 without interrupting the melt spinning operation for a long period of time. An object of the present invention is to provide a method for stably producing an unstretched polyester yarn (partially oriented yarn) having a thickness of from 03 to 0.06.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in view of the above-described conventional technology, and as a result, completed the present invention. That is, an object of the present invention is to use a titanium trimellitate and a phosphonate compound represented by the following general formula (I) when producing a polyester undrawn yarn having a birefringence of 0.03 to 0.06. The polyethylene terephthalate-based polyester synthesized so that the content of titanium (Ti) and phosphorus (P) in the polyester satisfies the following formula (1) is melted, solidified, and cooled to 2500 to 4000 m / min. A method for producing a polyester undrawn yarn, characterized in that the yarn is drawn off at a speed of 1.
[0007]
2 ≦ P / Ti ≦ 15 (1)
[0008]
Embedded image
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 a polyester comprising ethylene terephthalate units as a main repeating unit in an amount of 85 mol% or more, preferably 95 mol% or more. A small amount (typically, 20 mol% or less based on the terephthalic acid component or the ethylene glycol component) of a component other than the terephthalic acid component and / or the ethylene glycol component may be used.
[0010]
In the present invention, a polyethylene terephthalate-based polyester substantially containing no antimony (Sb) and synthesized using titanium trimellitate and a phosphonate compound represented by the following general formula (I) is used.
[0011]
Embedded image
As described above, when polyethylene terephthalate-based polyester synthesized using titanium trimellitate and a specific phosphonate compound without containing antimony (Sb) is melt-discharged, the occurrence of foreign matter in the die is dramatically reduced, and the discharge polymer The yarn becomes stable and continuous polyester unstretched yarn (partially oriented yarn) having a birefringence of 0.03 to 0.06 with a small degree of quality irregularity and a low birefringence without interruption of the spinning operation. Can be manufactured.
[0013]
The titanium trimellitate is soluble in the polyester polymer, and such a compound is added in the polycondensation step so that the titanium metal element is 2 to 15 mmol% based on the total dicarboxylic acid component constituting the polyester. Is preferred. In the case where the first-stage reaction is carried out by transesterification, the term "amount of titanium metal element" used herein means that the titanium compound used as the transesterification catalyst and the titanium compound used as the polycondensation reaction catalyst are used. Shows the total amount.
[0014]
Titanium trimellitate is preferably added to a reaction system in which a part of and / or the entire amount of titanium trimellitate is added to the reaction system before the start of the transesterification reaction, and a method is also employed in which the catalyst is used as both a transesterification reaction and a polycondensation reaction catalyst.
[0015]
Examples of the phosphonate compound represented by the general formula (I) include dimethyl ester, diethyl ester, dipropyl ester and dibutyl ester of phosphonic acid, and specific examples thereof include carbomethoxymethanephosphonic acid and carboethoxymethanephosphonate. Dimethyl esters such as acid, carbopropoxymethanephosphonic acid, carbobutoxymethanephosphonic acid, carbomethoxy-phosphono-phenylacetic acid, carboethoxy-phosphono-phenylacetic acid, carbopropoxy-phosphono-phenylacetic acid, carbobutoxy-phosphono-phenylacetic acid, Examples include diethyl ester, dipropyl ester and dibutyl ester.
[0016]
Since the above-mentioned phosphonate compound proceeds relatively slowly with the titanium compound as compared with the phosphorus compound usually used as a stabilizer, the duration of the catalytic activity of the titanium compound during the reaction is long, and as a result, In addition, the amount of the titanium compound added to the polyester can be reduced, and even when a large amount of a stabilizer is added to the catalyst as in the present invention, the property that the thermal stability of the polyester is not easily impaired is reduced. Have.
[0017]
These phosphonate compounds may be added at any time after the transesterification reaction is substantially completed during the production of the polyester.For example, the polycondensation reaction can be started even at atmospheric pressure before the start of the polycondensation reaction. It may be added under reduced pressure after the reaction, at the end of the polycondensation reaction, or after the completion of the polycondensation reaction, that is, after the polymer is obtained.
[0018]
Furthermore, a polyester unstretched yarn (partial orientation) obtained by melt-spinning a polyethylene terephthalate-based polyester synthesized so that the content of titanium (Ti) and phosphorus (P) in the polyester satisfies the following formula (1): Yarn) has the same level of color as an undrawn yarn (partially oriented yarn) obtained from a conventional polyester synthesized using an antimony-based catalyst.
[0019]
2 ≦ P / Ti ≦ 15 (1)
(In the above formula, Ti represents the concentration (mmol%) of the titanium metal element contained in the polyester, and P represents the concentration (mmol%) of the phosphorus element contained in the polyester.)
That is, when (P / Ti) is less than 2, the synthesized polyester has a remarkably yellowish tinge, and undrawn yarn (partially oriented yarn) from the polyester is drawn or false-twisted (hereinafter simply referred to as fiber). ), The color tone cannot be used for clothing. Here, the “color tone that cannot be used for clothing when made into fibers” refers to the difference between the color L * value and the color b * value measured in the form of a tubular knitted fiber (hereinafter referred to as (L * −b * )). Is less than 80 (conversely, a preferable color tone means that L * -b * is 80 or more). On the other hand, when (P / Ti) exceeds 15, the polymerization reactivity of the polyester is greatly reduced, and the desired polyester cannot be obtained. When (P / Ti) is in the range of 3 to 12, a polyethylene terephthalate-based polyester which is a fiber having a preferable color tone is obtained.
[0020]
The melt spinning in the present invention uses a normal polyester melt spinning machine equipped with a melt extruder (screw extruder) to melt the above-mentioned polyethylene terephthalate-based polyester at a normal polyester melt spinning temperature (270 to 310 ° C), The method is carried out by discharging from a spinneret, cooling and solidifying, and applying oil at a speed of 2500 to 4000 m / min with a rotating roller or a metering nozzle type oiling device. When the spinning speed is less than 2500 m / min, the obtained polyester undrawn yarn (partially oriented yarn) has a birefringence of less than 0.03, and it is difficult to draw false twist. If the birefringence exceeds 0.06, the strength and elongation of the drawn false twisted yarn from the polyester undrawn yarn (partially oriented yarn) will fall below the practical range.
[0021]
As described above, according to the present invention, a polyester having a stable color, a favorable color tone, a small quality unevenness, and a molecular orientation degree of 0.03 to 0.06 in birefringence is provided continuously for a long time. A drawn yarn (partially oriented yarn) can be manufactured.
[0022]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. Each item in the examples was measured by the following method.
[0023]
(1) Titanium metal element content and phosphorus element content After a granular polyester sample was heated and melted on an aluminum plate, a test molded body having a flat surface was prepared with a compression press, and a fluorescent X made by Rigaku Denki Kogyo Co., Ltd. The titanium metal element content and the phosphorus element content were measured using a line measuring device 3270E.
[0024]
(2) Intrinsic viscosity In accordance with a conventional method, measurement was made at 35 ° C. using orthochlorophenol as a solvent.
[0025]
(3) Birefringence The birefringence was determined from the retardation of polarized light observed on the fiber surface using an optical microscope and a compensator according to a conventional method.
[0026]
(4) Spinneret height The spinneret is melt-spun under the method and conditions shown in each example, and after 3, 6, and 9 days, a releasing agent is sprayed on the surface of the spinneret to prevent the discharged polymer from adhering. Was removed, and the height of the cap foreign matter adhered and deposited around the discharge hole was measured with a microscope. The height of the cap foreign matter was measured for all the ejection holes, and the height was represented by an average value thereof.
[0027]
(5) Spinning rate (%)
The number of spinning breaks that occurred during the operation of the spinning machine was recorded, excluding the yarn breakage caused by artificial or mechanical factors, and the spinning breakage rate (%) was calculated by the following equation.
[0028]
Spinning breakage rate (%) = [number of breaks / (number of operating winders × number of doffs)] × 100
Here, the doff number refers to the number of times the undrawn yarn package is wound up to a predetermined amount (10 kg).
[0029]
(6) Number of fluff (pcs / 10 4 m)
The drawn false twisted yarn was continuously measured at a speed of 500 m / min for 20 minutes using a DT-104 fluff counter device manufactured by Toray Industries, Inc., and the number of fluffs generated was counted.
[0030]
(7) Draw false twist rate (%)
Except for the yarn breakage caused by artificial or mechanical factors, the number of yarn breaks occurring during the operation of the draw false twisting machine was recorded, and the draw false twist ratio (%) was calculated by the following formula.
Draw false twist yarn ratio (%) = [number of yarn breaks / (number of operating weights × number of doffs)] × 100
Here, the doff number refers to the number of times the false twisted yarn package is wound up to a predetermined amount (2.5 kg).
[0031]
(8) (L * -b * ) value Using a 12 gauge circular knitting machine, the polyester fiber was knitted into a tube having a length of 30 cm, and the L * value and b * value were measured using a hunter type color difference meter CR-200 manufactured by Minolta Co. It measured, and made the difference into (L * -b * ) value.
[0032]
(9) Strength / elongation Measured in accordance with JIS-L1013.
[0033]
[Examples 1 to 3, Comparative Example 1]
Dimethyl terephthalate and ethylene glycol were prepared using titanium trimellitate and triethylphosphonate so that the amount of titanium metal element (Ti) and the concentration of phosphorus element (P) contained in the polyester were as shown in Table 1, respectively. Was subjected to polycondensation to obtain polyethylene terephthalate having an intrinsic viscosity of 0.630.
[0034]
The polyethylene terephthalate was pelletized, dried at 150 ° C. for 5 hours, melted in a melt spinning equipment equipped with a screw extruder, introduced into a spin block at 295 ° C., and a discharge hole having a hole diameter of 0.23 mm was formed. It is discharged at a flow rate of 48 g / min from the 72 spinnerets concentrically arranged, and the polymer stream is cooled and solidified by an air stream blown from a cross-flow type blower cylinder, while being 80 cm below the spinneret. In a measuring nozzle type refueling device installed in the factory, the oil is bundled while refueling, subjected to entanglement treatment with an air nozzle, taken up at a speed of 3300 m / min, and 10 kg as undrawn yarn (partially oriented yarn) of 145 dtex / 72 filaments. It was wound into a package. The above melt spinning operation was performed continuously for 9 days.
[0035]
In this example, as is clear from Table 1, in each of the examples, the adhesion and accumulation of the foreign matter in the die with the lapse of spinning were extremely small, the polymer discharge state was stable for a long time, and the spinning rate was low. Met.
[0036]
Next, the obtained polyester unstretched yarn (partially oriented yarn) package was stretched using a HTS-1500 type draw false twisting machine manufactured by Teijin Seiki Co., Ltd. equipped with a urethane disk having a diameter of 45 mm as a false twisting tool. 1.65, the first false temperature of the first heater was 500 ° C., the second half temperature was 310 ° C., and the false texturing was performed under the conditions of the false texturing speed of 700 m / min to obtain a false twisted yarn of 85 dtex / 72 filmants. . In addition, drawing false twisting was performed by a method of forming four 2.5 kg wound false twisted yarn packages from a 10 kg wound undrawn package.
[0037]
As is evident from Table 1, none of the examples showed an increase in the generation of fluff and an increase in the draw false twisted yarn ratio associated with the spinning time. However, the color tone (L * -b * ) of the tube knitted fabric of the false twisted yarn in Comparative Example 1 was less than 80, and had a color tone that could not be used for clothing.
[0038]
[Table 1]
[Comparative Example 2]
Using antimony trioxide (Sb 2 O 3 ) as a polymerization catalyst, dimethyl terephthalate and ethylene glycol were polycondensed by a conventional method to obtain polyethylene terephthalate having an intrinsic viscosity of 0.630.
[0040]
The polyethylene terephthalate was formed into pellets and melt-spun under the same method and conditions as in Examples 1 to 3 to produce a polyester undrawn yarn (partially oriented yarn) of 145 dtex / 72 filaments.
[0041]
In this example, as is clear from Table 1, foreign matter in the die rapidly grows with the lapse of spinning time, and a sharp increase in spun yarn breakage is observed as bending, spike and swirling of the discharged yarn increase. Was done. In addition, after 3 days of spinning, spinning breakage occurred frequently, making normal spinning operation difficult, and the operation was stopped.
[0042]
The obtained polyester undrawn yarn (partially oriented yarn) package was subjected to draw false twisting under the same method and conditions as in Examples 1 to 3 to obtain a false twisted yarn of 85 dtex / 72 filmants. As is clear from Table 1, the undrawn polyester yarn (partially oriented yarn) 3 days after the spinning in this comparative example generated extremely large amounts of fluff and breakage during the false twisting.
[0043]
【The invention's effect】
According to the present invention, a polyester unstretched yarn (partly having a birefringence of 0.03 to 0.06 in molecular birefringence, having a stable color tone, a stable color tone, and a small quality unevenness over a long period of time) Oriented yarn).
Claims (1)
２≦Ｐ／Ｔｉ≦１５ （１）
（上記式中、Ｔｉはポリエステル中に含有されるチタン金属元素の濃度（ｍｍｏｌ％）、Ｐはポリエステル中に含有されるリン元素の濃度（ｍｍｏｌ％）を示す。）
2 ≦ P / Ti ≦ 15 (1)
(In the above formula, Ti represents the concentration (mmol%) of the titanium metal element contained in the polyester, and P represents the concentration (mmol%) of the phosphorus element contained in the polyester.)
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|---|---|---|---|
| JP2002208002A JP2004052131A (en) | 2002-07-17 | 2002-07-17 | Method for producing polyester undrawn fiber |
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|---|---|---|---|
| JP2002208002A JP2004052131A (en) | 2002-07-17 | 2002-07-17 | Method for producing polyester undrawn fiber |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238769A (en) * | 2003-02-07 | 2004-08-26 | Toray Ind Inc | Polyester drawn yarn |
| JP2004244770A (en) * | 2003-02-17 | 2004-09-02 | Toray Ind Inc | Drawn polyester yarn |
| WO2012068264A2 (en) * | 2010-11-17 | 2012-05-24 | Frx Polymers, Inc. | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
-
2002
- 2002-07-17 JP JP2002208002A patent/JP2004052131A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004238769A (en) * | 2003-02-07 | 2004-08-26 | Toray Ind Inc | Polyester drawn yarn |
| JP2004244770A (en) * | 2003-02-17 | 2004-09-02 | Toray Ind Inc | Drawn polyester yarn |
| WO2012068264A2 (en) * | 2010-11-17 | 2012-05-24 | Frx Polymers, Inc. | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| WO2012068264A3 (en) * | 2010-11-17 | 2012-08-16 | Frx Polymers, Inc. | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| CN103328702A (en) * | 2010-11-17 | 2013-09-25 | Frx聚合物股份有限公司 | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| US9290653B2 (en) | 2010-11-17 | 2016-03-22 | Frx Polymers, Inc. | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| US10724154B2 (en) | 2010-11-17 | 2020-07-28 | Frx Polymers, Inc. | Phosphonate polymers, copolymers, and their respective oligomers as flame retardants for polyester fibers |
| US10167377B2 (en) | 2013-01-22 | 2019-01-01 | Frx Polymers, Inc. | Phosphorus containing epoxy compounds and compositions therefrom |
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