JP2004285495A - Polyester false-twisted yarn - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester false-twisted yarn which comprises a polyester composition having a good hue and hood heat resistance and containing a new polymerization catalyst, has excellent gloss, little causes the formation of fuzzes and the occurrence of yarn breakage in a weaving process or in a knitting process, scarcely stops a loom or a knitting machine, and has a stable quality. <P>SOLUTION: This polyester false-twisted yarn is characterized by comprising a polyester composition produced in the presence of a catalyst consisting mainly of a titanium compound (excluding titanium dioxide) and not containing an antimony compound or containing the antimony compound in an amount of ≤30 ppm in terms of antimony atom based on the polyester, and containing inorganic oxide particles used as a matting agent in an amount of ≤0.04 wt.%, wherein the undrawn filaments have each a modified cross section before false-twisted. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００２３】
（式１〜式６中、Ｒ_１〜Ｒ_３はそれぞれ独立に水素、炭素数１〜３０の炭化水素基、アルコキシ基または水酸基またはカルボニル基またはアセチル基またはカルボキシル基またはエステル基またはアミノ基を有する炭素数１〜３０の炭化水素基を表す。）
本発明の式１としては、エトキシド、プロポキシド、イソプロポキシド、ブトキシド、２−エチルヘキソキシド等のアルコキシ基、乳酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシ多価カルボン酸系化合物からなる官能基が挙げられる。
【００２４】
また、式２としては、アセチルアセトン等のβ−ジケトン系化合物、アセト酢酸メチル、アセト酢酸エチル等のケトエステル系化合物からなる官能基が挙げられる。
【００２５】
また、式３としては、フェノキシ、クレシレイト、サリチル酸等からなる官能基が挙げられる。
【００２６】
また、式４としては、ラクテート、ステアレート等のアシレート基、フタル酸、トリメリット酸、トリメシン酸、ヘミメリット酸、ピロメリット酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、シクロヘキサンジカルボン酸またはそれらの無水物等の多価カルボン酸系化合物、エチレンジアミン四酢酸、ニトリロ三プロピオン酸、カルボキシイミノ二酢酸、カルボキシメチルイミノ二プロピオン酸、ジエチレントリアミノ五酢酸、トリエチレンテトラミノ六酢酸、イミノ二酢酸、イミノ二プロピオン酸、ヒドロキシエチルイミノ二酢酸、ヒドロキシエチルイミノ二プロピオン酸、メトキシエチルイミノ二酢酸等の含窒素多価カルボン酸からなる官能基が挙げられる。
【００２７】
また、式５としては、アニリン、フェニルアミン、ジフェニルアミン等からなる官能基が挙げられる。
【００２８】
中でも式１及び／または式４が含まれていることがポリマーの熱安定性及び色調の観点から好ましい。
【００２９】
また、チタン化合物としてこれら式１〜式６の置換基の２種以上を含んでなるチタンジイソプロポキシビスアセチルアセトナートやチタントリエタノールアミネートイソプロポキシド等が挙げられる。
【００３０】
また、チタン酸化物としては、主たる金属元素がチタン及びケイ素からなる複合酸化物等が挙げられる。
【００３１】
なお、本発明の触媒とは、ジカルボン酸またはそのエステル形成性誘導体及びジオールまたはそのエステル形成性誘導体から合成されるポリマーにおいて、以下の（１）〜（３）の反応全てまたは一部の素反応の反応促進に実質的に寄与する化合物を指す。
（１）ジカルボン酸成分とジオール成分との反応であるエステル化反応
（２）ジカルボン酸のエステル形成性誘導体成分とジオール成分との反応であるエステル交換反応
（３）実質的にエステル反応またはエステル交換反応が終了し、得られたポリエチレンテレフタレート低重合体を脱ジオール反応にて高重合度化せしめる重縮合反応
従って、繊維の艶消し剤等に無機粒子として一般的に用いられている二酸化チタン粒子は上記の反応に対して実質的に触媒作用を有しておらず、本発明の触媒として用いることができるチタン化合物とは異なる。
【００３２】
主たる金属元素がチタン及びケイ素からなる複合酸化物の製造方法は、特に限定されないが、例えば、チタンのアルコキシド化合物を原料として、加水分解反応により製造する方法において、この加水分解の速度を制御することによって得られる。具体的には、例えば主原料であるチタンアルコキシド化合物に対して、ケイ素やジルコニウム等の少量の他の金属アルコキシド化合物や多価アルコール化合物を共存させ、両者の共沈法、部分加水分解法、配位化学ゾル・ゲル法等によって合成することができる。ここで共沈法とは２種あるいはそれ以上の成分を含有する所定の組成の溶液を調製し、その組成のまま加水分解反応を進行させる方法である。また、部分加水分解法とは、一方の成分をあらかじめ加水分解した状態としておき、そこへもう一方の成分を加えさらに加水分解を進行させる方法である。また、配位化学ゾル・ゲル法とは、チタンアルコキシド原料とともに分子内に官能基を複数持つ多価アルコール化合物等を共存させ、両者の間であらかじめ反応物を形成させることによって、その後の加水分解反応の速度を制御しようとするものである。以上のような化合物の合成方法は、例えば、上野ら、「金属アルコキシドを用いる触媒調製」、第３２１頁第１行〜第３５３頁第１６行、（アイピーシー、１９９３年８月１０日発行）等に記載されている。
【００３３】
本発明におけるチタン化合物（二酸化チタン粒子を除く）は得られるポリマーに対してチタン原子換算で０．５〜１５０ｐｐｍ含有されていることが好ましい。１〜１００ｐｐｍであるとポリマーの熱安定性や色調が良好であり、重合反応終了からチップ化までのカルボ末端基やポリマの固有粘度の変化量も少ないため、均染性に優れたポリエステル仮撚加工糸となり好ましく、更に好ましくは３〜５０ｐｐｍである。
【００３４】
本発明のポリエステル組成物は、チタン化合物と共にリンがポリエステルに対してリン原子換算で０．１〜４００ｐｐｍ含有されていることが好ましい。なお、製糸時におけるポリエステル組成物の熱安定性や色調の観点からリン含有量は、１〜２００ｐｐｍが好ましく、さらに好ましくは３〜１００ｐｐｍである。
【００３５】
なお、本発明のポリエステル組成物に含有されるリンは、ポリエステル組成物の製造過程でリン化合物として添加される。このようなリン化合物としてはリン酸系、亜リン酸系、ホスホン酸系、ホスフィン酸系、ホスフィンオキサイド系、亜ホスホン酸系、亜ホスフィン酸系、ホスフィン系のいずれか１種または２種であることが好ましい。具体的には、例えば、リン酸、リン酸トリメチル、リン酸トリエチル、リン酸トリフェニル等のリン酸系、亜リン酸、亜リン酸トリメチル、亜リン酸トリエチル、亜リン酸トリフェニル等の亜リン酸系、メチルホスホン酸、エチルホスホン酸、プロピルホスホン酸、イソプロピルホスホン酸、ブチルホスホン酸、フェニルホスホン酸、ベンジルホスホン酸、トリルホスホン酸、キシリルホスホン酸、ビフェニルホスホン酸、ナフチルホスホン酸、アントリルホスホン酸、２−カルボキシフェニルホスホン酸、３−カルボキシフェニルホスホン酸、４−カルボキシフェニルホスホン酸、２，３−ジカルボキシフェニルホスホン酸、２，４−ジカルボキシフェニルホスホン酸、２，５−ジカルボキシフェニルホスホン酸、２，６−ジカルボキシフェニルホスホン酸、３，４−ジカルボキシフェニルホスホン酸、３，５−ジカルボキシフェニルホスホン酸、２，３，４−トリカルボキシフェニルホスホン酸、２，３，５−トリカルボキシフェニルホスホン酸、２，３，６−トリカルボキシフェニルホスホン酸、２，４，５−トリカルボキシフェニルホスホン酸、２，４，６−トリカルボキシフェニルホスホン酸、メチルホスホン酸ジメチルエステル、メチルホスホン酸ジエチルエステル、エチルホスホン酸ジメチルエステル、エチルホスホン酸ジエチルエステル、フェニルホスホン酸ジメチルエステル、フェニルホスホン酸ジエチルエステル、フェニルホスホン酸ジフェニルエステル、ベンジルホスホン酸ジメチルエステル、ベンジルホスホン酸ジエチルエステル、ベンジルホスホン酸ジフェニルエステル、リチウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ナトリウム（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、マグネシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、カルシウムビス（３，５−ジ−ｔｅｒｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル）、ジエチルホスホノ酢酸、ジエチルホスホノ酢酸メチル、ジエチルホスホノ酢酸エチル等のホスホン酸系化合物、次亜リン酸、次亜リン酸ナトリウム、メチルホスフィン酸、エチルホスフィン酸、プロピルホスフィン酸、イソプロピルホスフィン酸、ブチルホスフィン酸、フェニルホスフィン酸、トリルホスフィン酸、キシリルホスフィン酸、ビフェニリルホスフィン酸、ジフェニルホスフィン酸、ジメチルホスフィン酸、ジエチルホスフィン酸、ジプロピルホスフィン酸、ジイソプロピルホスフィン酸、ジブチルホスフィン酸、ジトリルホスフィン酸、ジキシリルホスフィン酸、ジビフェニリルホスフィン酸、ナフチルホスフィン酸、アントリルホスフィン酸、２−カルボキシフェニルホスフィン酸、３−カルボキシフェニルホスフィン酸、４−カルボキシフェニルホスフィン酸、２，３−ジカルボキシフェニルホスフィン酸、２，４−ジカルボキシフェニルホスフィン酸、２，５−ジカルボキシフェニルホスフィン酸、２，６−ジカルボキシフェニルホスフィン酸、３，４−ジカルボキシフェニルホスフィン酸、３，５−ジカルボキシフェニルホスフィン酸、２，３，４−トリカルボキシフェニルホスフィン酸、２，３，５−トリカルボキシフェニルホスフィン酸、２，３，６−トリカルボキフェニルホスフィン酸、２，４，５−トリカルボキシフェニルホスフィン酸、２，４，６−トリカルボキシフェニルホスフィン酸、ビス（２−カルボキシフェニル）ホスフィン酸、ビス（３−カルボキシフェニル）ホスフィン酸、ビス（４−カルボキシフェニル）ホスフィン酸、ビス（２，３−ジカルボキルシフェニル）ホスフィン酸、ビス（２，４−ジカルボキシフェニル）ホスフィン酸、ビス（２，５−ジカルボキシフェニル）ホスフィン酸、ビス（２，６−ジカルボキシフェニル）ホスフィン酸、ビス（３，４−ジカルボキシフェニル）ホスフィン酸、ビス（３，５−ジカルボキシフェニル）ホスフィン酸、ビス（２，３，４−トリカルボキシフェニル）ホスフィン酸、ビス（２，３，５−トリカルボキシフェニル）ホスフィン酸、ビス（２，３，６−トリカルボキシフェニル）ホスフィン酸、ビス（２，４，５−トリカルボキシフェニル）ホスフィン酸、及びビス（２，４，６−トリカルボキシフェニル）ホスフィン酸、メチルホスフィン酸メチルエステル、ジメチルホスフィン酸メチルエステル、メチルホスフィン酸エチルエステル、ジメチルホスフィン酸エチルエステル、エチルホスフィン酸メチルエステル、ジエチルホスフィン酸メチルエステル、エチルホスフィン酸エチルエステル、ジエチルホスフィン酸エチルエステル、フェニルホスフィン酸メチルエステル、フェニルホスフィン酸エチルエステル、フェニルホスフィン酸フェニルエステル、ジフェニルホスフィン酸メチルエステル、ジフェニルホスフィン酸エチルエステル、ジフェニルホスフィン酸フェニルエステル、ベンジルホスフィン酸メチルエステル、ベンジルホスフィン酸エチルエステル、ベンジルホスフィン酸フェニルエステル、ビスベンジルホスフィン酸メチルエステル、ビスベンジルホスフィン酸エチルエステル、ビスベンジルホスフィン酸フェニルエステル等のホスフィン酸系、トリメチルホスフィンオキサイド、トリエチルホスフィンオキサイド、トリプロピルホスフィンオキサイド、トリイソプロピルホスフィンオキサイド、トリブチルホスフィンオキサイド、トリフェニルホスフィンオキサイド等のホスフィンオキサイド系、メチル亜ホスホン酸、エチル亜ホスホン酸、プロピル亜ホスホン酸、イソプロピル亜ホスホン酸、ブチル亜ホスホン酸、フェニル亜ホスホン酸等の亜ホスホン酸系、メチル亜ホスフィン酸、エチル亜ホスフィン酸、プロピル亜ホスフィン酸、イソプロピル亜ホスフィン酸、ブチル亜ホスフィン酸、フェニル亜ホスフィン酸、ジメチル亜ホスフィン酸、ジエチル亜ホスフィン酸、ジプロピル亜ホスフィン酸、ジイソプロピル亜ホスフィン酸、ジブチル亜ホスフィン酸、ジフェニル亜ホスフィン酸等の亜ホスフィン酸系、メチルホスフィン、ジメチルホスフィン、トリメチルホスフィン、メエルホスフィン、ジエチルホスフィン、トリエチルホスフィン、フェニルホスフィン、ジフェニルホスフィン、トリフェニルホスフィン等のホスフィン系が挙げられ、これらのいずれか１種または２種であることが好ましい。特に熱安定性及び色調改善の観点から、リン酸系及び／またはホスホン酸系であることが好ましい。
【００３６】
本発明のポリエステル組成物においてはアンチモン化合物を含まないかあるいはポリエステルに対するアンチモン原子換算で３０ｐｐｍ以下含有することが必要である。この範囲とすることで、アンチモン触媒残渣に起因するポリエステル組成物の黒ずみや異物の発生を抑えることができ、光沢感を向上させることができる。また、溶融紡糸時にアンチモン触媒残渣の口金吐出孔周辺への堆積が少ないため、口金吐出孔での糸曲がり現象や吐出糸条のピクツキによる糸斑や断糸を防止でき、またアンチモンを主体とする異物の繊維中への混入やポリマー中のアンチモン触媒残渣、すなわち金属アンチモンも少ないため、仮撚加工時の毛羽や断糸も防止できる。さらに、比較的安価なポリマーを得ることができる。アンチモン化合物の含有量は、より好ましくは、１０ｐｐｍ以下、さらに好ましくは実質的に含有しないことである。
【００３７】
本発明のポリエステル組成物は、艶消し剤として使用する無機酸化物粒子の含有量が０．０４重量％以下であることが必要である。艶消し剤として使用する無機酸化物粒子の含有量を０．０４重量％以下とすることで該粒子による光の乱反射を抑えることができ、光沢感低下を防止できる。さらに光沢感を向上させるためには、０．０２重量％以下とするのが好ましい。
【００３８】
本発明のポリエステル仮撚加工糸は、ポリエステル仮撚加工前の未延伸糸を構成する繊維断面が異形であることが良好な光沢感を有する織編物とするために必要である。繊維の断面が円形であると、従来の素材に比べ優れた光沢感を得ることができない。異形断面とは円形以外の断面を指し、例えば、多葉、扁平、Ｃ型、Ｖ型、Ｗ型などが挙げられるが、これらに限定されるものではない。製糸性や光沢感を考慮すると、三葉断面が好ましい。また、その形状は下記式で示す未延伸糸での繊維断面の異形度：Ｒが１．５以上２．３未満であることが好ましい。
【００３９】
Ｒ＝ｒ２／ｒ１
［式中、ｒ１：繊維断面の内接円の直径、ｒ２：繊維断面の外接円の直径］
また、チタン化合物のチタン原子に対してリン原子としてモル比率でＴｉ／Ｐ＝０．１〜２０であるとポリエステル組成物の熱安定性や色調が良好となり好ましい。より好ましくはＴｉ／Ｐ＝０．２〜１０であり、さらに好ましくはＴｉ／Ｐ＝０．３〜５である。
【００４０】
本発明で用いるチタン化合物及びリン化合物は、ポリエステル組成物の反応系にそのまま添加してもよいが、予めエチレングリコールやプロピレングリコール等のポリエステル組成物を形成するジオール成分を含む溶媒と混合し、溶液またはスラリーとし、必要に応じてチタン化合物またはリン化合物合成時に用いたアルコール等の低沸点成分を除去した後、反応系に添加すると、ポリマー中での異物生成がより抑制されるため好ましい。添加時期はエステル化反応触媒やエステル交換反応触媒として、原料添加直後に触媒を添加する方法や、原料と同伴させて添加する方法がある。また、重縮合反応触媒として添加する場合は、実質的に重縮合反応開始前であればよく、エステル化反応やエステル交換反応の前、あるいは該反応終了後、重縮合反応触媒が開始される前に添加してもよい。この場合、チタン化合物とリン化合物が接触することによる触媒の失活を抑制するために、異なる反応槽に添加する方法や、同一の反応槽においてチタン化合物とリン化合物の添加間隔を１〜１５分とする方法や添加位置を離す方法がある。
【００４１】
また、本発明においてチタン化合物を予めリン化合物と反応させたものを触媒として用いることもできる。この場合には、（１）チタン化合物を溶媒に混合してその一部または全部を溶媒中に溶解し、この混合溶液にリン化合物を原液または溶媒に溶解希釈させ滴下する。（２）ヒドロキシカルボン酸系化合物や多価カルボン酸系化合物等のチタン化合物の配位子を用いる場合は、チタン化合物または配位子化合物を溶媒に混合してその一部または全部を溶媒中に溶解し、この混合溶液に配位子化合物またはチタン化合物を原液または溶媒に溶解希釈させ滴下する。また、この混合溶液にさらにリン化合物を原液または溶媒に溶解希釈させ滴下すると、熱安定性及び色調改善の観点から好ましい。上記の反応条件は０〜２００℃の温度で１分以上、好ましくは２０〜１００℃の温度で２〜１００分間加熱することによって行われる。この際の反応圧力には特に制限はなく、常圧でも良い。また、ここで用いる溶媒としては、チタン化合物、リン化合物及びカルボニル基含有化合物の一部または全部を溶解し得るものから選択することができるが、好ましくは、水、メタノール、エタノール、エチレングリコール、プロパンジオール、ブタンジオール、ベンゼン、キシレンから選ばれる。
【００４２】
本発明のポリエステル仮撚加工糸に用いるポリエステル組成物の製造方法において、任意の時点でマンガン化合物をポリエステルに対するマンガン原子換算で１〜４００ｐｐｍ含有し、マンガン化合物とリン化合物の比率がマンガン原子とリン原子のモル比率としてＭｎ／Ｐ＝０．１〜２００となるように添加すると重合活性の低下を抑制することができ、それにより得られるポリマーの色調が良好となり好ましい。この場合に用いるマンガン化合物としては特に限定はないが、具体的には、例えば、塩化マンガン、臭化マンガン、硝酸マンガン、炭酸マンガン、マンガンアセチルアセトネート、酢酸マンガン四水塩、酢酸マンガン二水塩等が挙げられる。
【００４３】
また、本発明のポリエステル仮撚加工糸に用いるポリエステル組成物の製造方法において、任意の時点でさらにコバルト化合物を添加すると得られるポリマーの色調が良好となり好ましい。この場合に用いるコバルト化合物としては特に限定はないが、具体的には、例えば、塩化コバルト、硝酸コバルト、炭酸コバルト、コバルトアセチルアセトネート、ナフテン酸コバルト、酢酸コバルト四水塩等が挙げられる。
【００４４】
また、得られるポリマーの色調やポリマーの耐熱性を向上させる目的で、アルカリ金属化合物、アルカリ土類金属化合物、アルミニウム化合物、亜鉛化合物、スズ化合物等を添加してもよい。
【００４５】
さらに、二酸化チタン、酸化ケイ素、炭酸カルシウム、チッ化ケイ素、クレー、タルク、カオリン、カーボンブラック等の粒子のほか、着色防止剤、安定剤、抗酸化剤等の添加剤を含有しても差支えない。
【００４６】
本発明のポリエステル仮撚加工糸に用いるポリエステル組成物の製造方法を説明する。具体例としてポリエチレンテレフタレートの例を記載するがこれに限定されるものではない。
【００４７】
ポリエチレンテレフタレートは通常、次のいずれかのプロセスで製造される。すなわち、（１）テレフタル酸とエチレングリコールを原料とし、直接エステル化反応によって低重合体を得、さらにその後の重縮合反応によって高分子量ポリマーを得るプロセス、（２）ジメチルテレフタレートとエチレングリコールを原料とし、エステル交換反応によって低重合体を得、さらにその後の重縮合反応によって高分子量ポリマーを得るプロセスである。ここでエステル化反応は無触媒でも反応は進行するが、チタン化合物を触媒として添加してもよい。また、エステル交換反応においては、マンガン、カルシウム、マグネシウム、亜鉛、リチウム等の化合物や前述のチタン化合物を触媒として用いて進行させ、またエステル交換反応が実質的に完結した後に、反応に用いた触媒を不活性化する目的で、リン化合物を添加することが行われる。
【００４８】
本発明の製造方法は、（１）または（２）の一連の反応の任意の段階、好ましくは（１）または（２）の一連の反応の前半で得られた低重合体に、艶消し剤として二酸化チタン粒子や、コバルト化合物等の添加物を添加した後、重縮合触媒として前述のチタン化合物を添加し重縮合反応を行い、高分子量のポリエチレンテレフタレートを得るというものである。
【００４９】
また、上記の反応は回分式、半回分式あるいは連続式等の形式に適応し得る。
【００５０】
本発明のポリエステル仮撚加工糸の製造方法は、具体的には、仮撚加工を施すポリエステル未延伸糸の溶融紡糸方法は、例えば、プレッシャーメルター方式、エクストルダー方式であって、紡糸速度も仮撚加工に適した紡糸速度を採用できる。
【００５１】
本発明のポリエステル仮撚加工糸の製造方法は、具体的には、フリクション型摩擦仮撚装置やベルトニップ型摩擦仮撚装置を用いることができ、仮撚加工速度は３５０〜１５００ｍ／ｍｉｎ、仮撚加工倍率は１．４〜２．０倍、仮撚ヒータ温度は１３０〜２５０℃、Ｄ／Ｙ比は１．３０〜２．５０、撚り数は１５００〜７５００ｔ／ｍの範囲とすることができる。ここで、Ｄ／Ｙ比とは、フリクションディスクやベルト等、仮撚具の周速度（Ｄ）と仮撚加工速度（Ｙ）との比率である。
【００５２】
本発明のポリエステル仮撚加工糸は、具体的には、マルチフィラメント繊度は１０〜６６０ｄｔｅｘ、伸度は１５〜５０％、沸騰水収縮率は２〜１５％、伸縮復元率は１０〜６０％、捲縮伸長率は２〜５０％であり、好ましくは、マルチフィラメント繊度は２２〜６００ｄｔｅｘ、伸度は１５〜４５％、沸騰水収縮率は４〜１２％、伸縮復元率は２０〜５５％、捲縮伸長率は１５〜４０％であり、更に好ましくは、マルチフィラメント繊度は２８〜５００ｄｔｅｘ、伸度は２０〜４０％、沸騰水収縮率は５〜７％、伸縮復元率は３０〜５０％、捲縮伸長率は２０〜３５％である。マルチフィラメント繊度、伸度、沸騰水収縮率、伸縮復元率、捲縮伸長率の測定方法は以下の通りである。
（１）マルチフィラメント繊度（Ｄ（ｄｔｅｘ）と称す。）
枠周１ｍの検尺機を用いて初張力：（０．０８８×マルチフィラメント繊度（ｄｔｅｘ））ｃＮで１００回転（１００ｍ）巻き取り、枷巻きの質量：Ｍ（ｇ）を電子天秤にて測定し、マルチフィラメント繊度：Ｄ＝１００×Ｍによりマルチフィラメント繊度を計算する。
（２）伸度（Ｅ（％）と称す。）
ＯＲＩＥＮＴＥＣ社製ＲＴＣ−１２１ＯＡ型にて、試料長：２０ｃｍ、引張速度：２０ｃｍ／ｍｉｎ、記録紙速度：３０ｃｍ／ｍｉｎ、初張力：（０．０８８×マルチフィラメント繊度（ｄｔｅｘ））ｃＮで伸長させ、破断時の試料長：Ｌ（ｃｍ）を用い、下式により伸度（Ｅ（％））を計算する。
【００５３】
Ｅ（％）＝３．３３×Ｌ
（３）沸騰水収縮率（Ｗｓ（％）と称す。）
枠周１ｍの検尺機を用いて初張力：（０．０８８×マルチフィラメント繊度（ｄｔｅｘ））ｃＮでカセ長５０ｃｍ、巻き数１０回のかせを作り、荷重：（１．７６７×マルチフィラメント繊度（ｄｔｅｘ））ｃＮを掛けた状態で試料長：ａを測定する。その後、１００℃で１５分間沸騰水処理を行い、風乾後、荷重：（１．７６７×マルチフィラメント繊度（ｄｔｅｘ））ｃＮを掛けた状態で試料長：ｂを測定し、下式により沸騰水収縮率：Ｗｓ（％）を計算する。
【００５４】
Ｗｓ（％）＝（（ａ−ｂ）／ａ）×１００
（４）伸縮復元率（ＣＲ（％）と称す。）
枠周１ｍの検尺機を用いて初張力：（０．０８８×マルチフィラメント繊度（ｄｔｅｘ））ｃＮで、カセ長５０ｃｍ、巻き数１０回のかせを作り、これを９０℃の熱水中に２０分間浸漬後、吸取紙または布で水を切り、水平状態で自然乾燥させる。このかせ巻きを室温の水中に入れ、規定の初荷重と定荷重を掛けた状態での試料長：ａを測定する。次に、定荷重を取り除き、試料に初荷重のみが負荷した状態で３分間水中で放置し、３分後の試料長：ｂを測定し、下式により伸縮復元率ＣＲ（％）を計算する。なお、初荷重と定荷重は下式により求めたものを使用する。
【００５５】
ＣＲ（％）＝（（ａ−ｂ）／ａ）×１００
初荷重（ｃＮ）＝（マルチフィラメント繊度（ｄｔｅｘ）／１．１１１）× ０．００２×０．９８０７×巻取回数×２
定荷重（ｃＮ）＝（マルチフィラメント繊度（ｄｔｅｘ）／１．１１１）× ０．１×０．９８０７×巻取回数×２
（５）捲縮伸長率（ＴＲ（％）と称す。）
枠周１ｍの検尺機を用いて初張力：（０．０８８×マルチフィラメント繊度（ｄｔｅｘ））ｃＮでカセ長５０ｃｍ、巻き数２０回のかせを作り、初荷重をかけ、１５０±２℃で５分間乾熱処理する。乾熱処理後、初荷重を掛けた状態での試料長：ａを測定する。次に、初荷重を外し、定荷重を掛けた状態での試料長：ｂを測定し、下式により捲縮伸長率ＴＲ（％）を計算する。なお、初荷重と定荷重は下式により求めたものを使用する。
【００５６】
ＴＲ（％）＝（（ｂ−ａ）／ｂ）×１００
初荷重（ｃＮ）＝（マルチフィラメント繊度（ｄｔｅｘ）／１．１１１）× ０．００１６６×０．９８０７×巻取回数×２
定荷重（ｃＮ）＝（マルチフィラメント繊度（ｄｔｅｘ）／１．１１１）× ０．１×０．９８０７×巻取回数×２
【００５７】
【実施例】
以下に本発明の実施例、および比較例により、本発明をさらに具体的に説明する。なお、実施例中の評価方法、測定方法は以下の方法を用いた。評価結果、測定結果は、表１、表２の通りである。
（１）ポリエステル中のチタン元素、リン元素、アンチモン元素、ゲルマニウム元素、及びマンガン元素の含有量
蛍光Ｘ線元素分析装置（堀場製作所社製、ＭＥＳＡ−５００Ｗ型）により求めた。なお、ポリエステルに二酸化チタン粒子が含有されている際には、次の前処理をした上で蛍光Ｘ線分析を行った。すなわち、ポリエステルをオルソクロロフェノールに溶解（溶媒１００ｇに対してポリマー５ｇ）し、このポリマー溶液と同量のジクロロメタンを加えて溶液の粘性を調製した後、遠心分離器（回転数１８０００ｒｐｍ、１時間）で粒子を沈降させる。その後、傾斜法で上澄み液のみを回収し、上澄み液と同量のアセトンを添加することによりポリマーを再析出させ、そのあと３Ｇ３のガラスフィルター（ＩＷＡＫＩ社製）で濾過し、濾上物をさらにアセトンで洗浄した後、室温で１２時間真空乾燥してアセトンを除去した。以上の前処理を施して得られたポリマーについてチタン元素、リン元素、アンチモン元素、ゲルマニウム元素及びマンガン元素の分析を行った。
【００５８】
一方、二酸化チタン粒子が含有されていない場合は、前処理を行う必要がないので、ポリマーをそのまま分析すればよい。
（２）ポリマーの固有粘度［η］
オルソクロロフェノールを溶媒として２５℃で測定した。
（３）融点
測定する試料１０ｍｇを精秤し、アルミニウム製オーブンパン及びパンカバーを用いて封入し、示差走査熱量計（パーキンエルマー社製、ＤＳＣ７型）を用いて、窒素気流下、２０℃から２８５℃まで１６℃／分の速度で昇温させ、その途中で観察される融点ピーク温度を融点とした。
（４）溶液ヘイズ
測定する試料を２．０ｇをオルソクロロフェノール２０ｍｌに溶解させ、ヘイズメーター（スガ試験機社製，ＨＧＭ−２ＤＰ型）を用い、積分球式光電光度法にて分析を行った。
（５）異形度（Ｒ）
下式により単糸の変形度を計算し、平均値を異形度（Ｒ）とする。
【００５９】
Ｒ＝ｒ２／ｒ１
［式中、ｒ１：繊維断面の内接円の直径、ｒ２：繊維断面の外接円の直径］
（６）光沢度
光沢度測定用編み地（縦５ｃｍ×横５ｃｍ）を専用サンプル固定枠に固定し、 スガ試験機株式会社製ＳＭカラーコンピューターにより、４５°拡散方式によ り、二個の光源から光を４５°で入射させ、サンプル固定枠下方に設置した受 光部で測定した光度を同一条件で標準板を測定したときの光度を１００とした ときの比率をもって光沢度とした。
【００６０】
光沢度測定用編み地の染色カラーは青色とした。
（７）光沢感評価
実施例、比較例で得られた仮撚加工糸を小池機械製作所社製一口型筒編み機（ゲージ数：２０）により長さ３５ｃｍの筒編みを作成し、プロコンパドル自動染色機を用いて常法により染色、水洗、乾燥を行った。以上の方法で得た布帛について、光沢感を１〜５級で官能評価し、３級以上を合格とした。
（８）仮撚加工性
未延伸糸を５００個用いて、５．０ｋｇ巻きの仮撚加工糸を得る際に糸切れや毛羽が発生しなかった仮撚加工糸の割合を仮撚加工性（％）とし、９８．０％以上を合格とした。
（９）毛羽発生数
東レエンジニアリング株式会社製ＭＵＬＴＩ ＰＯＩＮＴ ＦＬＡＹ ＣＯＵＮＴＥＲ ｍｏｄｅｌ ＭＦＣ−１１１ ０により糸速度４００ｍ／ｍｉｎで走行させながら、５分間毛羽数を測定し、５ ０本の平均値を毛羽発生数とした。毛羽発生数は、０．５０個／２０００ｍ以下を合 格とした。
（１０）製品評価
実施例、比較例で得られた仮撚加工糸を用いて以下に示す方法で織物および編物を作製し、常法により染色、水洗、乾燥を行った。以上の方法で得た布帛について、織布および編成工程での操業性、織物および編物の光沢感を１〜５級で総合評価し、３級以上を合格とした。
【００６１】
Ａ．織布方法
仮撚加工前の断面が丸断面である未延伸糸を仮撚加工して得た、５６ｄｔｅｘ、３６フィラメントの仮撚加工糸を経糸に用い、緯糸に実施例、比較例で得られた仮撚加工糸を幅１．７ｍ、織密度９０本／ｉｎｃｈ、織機回転数８００ｃｐｍで打ち込み、織物とする。
【００６２】
Ｂ．編成方法
実施例、比較例で得られた仮撚加工糸を３６０本用い、整経速度４００ｍ／ｍｉｎで整経を行い、得られたビームを２８ゲージ、シングルトリコット編み機を用いてハーフ組織にて編物とする。
【００６３】
実施例１
高純度テレフタル酸（三井化学社製）１００ｋｇとエチレングリコール（日本触媒社製）４５ｋｇのスラリーを予めビス（ヒドロキシエチル）テレフタレート約１２３ｋｇが仕込まれ、温度２５０℃、圧力１．２×１０^５Ｐａに保持されたエステル化反応槽に４時間かけて順次供給し、供給終了後もさらに１時間かけてエステル化反応を行い、このエステル化反応生成物の１２３ｋｇを重縮合槽に移送した。
【００６４】
引き続いて、エステル化反応生成物が移送された前記重縮合反応槽に、酸化チタン粒子のエチレングリコールスラリーを得られるポリマーに対して０．０２５重量％添加した。５分間撹拌した後、酢酸コバルト及び酢酸マンガンのエチレングリコール溶液を得られるポリマーに対してコバルト原子換算で３０ｐｐｍ、マンガン原子換算で１５ｐｐｍとなるように加えた。更に５分間撹拌した後、クエン酸キレートチタン化合物の２重量％エチレングリコール溶液を得られるポリマーに対してチタン原子換算で１０ｐｐｍとなるように添加し、５分後、フェニルホスホン酸ジメチルエステルの１０重量％エチレングリコール溶液を得られるポリマーに対してリン原子換算で６ｐｐｍとなるように添加し、その後、低重合体を３０ｒｐｍで攪拌しながら、反応系を２５０℃から２８５℃まで徐々に昇温するとともに、圧力を４０Ｐａまで下げた。最終温度、最終圧力到達までの時間はともに６０分とした。所定の攪拌トルクとなった時点で反応系を窒素パージし常圧に戻し重縮合反応を停止し、冷水にストランド状に吐出、直ちにカッティングしてポリマーのペレットを得た。なお、減圧開始から所定の撹拌トルク到達までの時間は３時間であった。
【００６５】
重合触媒として用いたクエン酸キレートチタン化合物の合成方法は、以下の通りである。
【００６６】
撹拌機、凝縮器及び温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にクエン酸・一水和物（５３２ｇ、２．５２モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトライソプロポキシド（２８８ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりイソプロパノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、次いでエチレングリコール（５０４ｇ、８０モル）と混合し、そして真空下で加熱してイソプロパノール／水を除去し、わずかに曇った淡黄色の生成物（Ｔｉ含有量３．８５重量％）を得た。
【００６７】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であり、アンチモン原糸の含有量は０ｐｐｍであることを確認した。
【００６８】
上記ポリエステル組成物を乾燥後、紡糸温度２８９℃、紡糸速度２６００ｍ／ｍｉｎで溶融紡糸を行い、１０８．０ｄｔｅｘ、３６フィラメントの繊維断面が三葉断面である未延伸糸（ＰＯＹ）を巻き取った。未延伸糸の異形度は１．８６であった。次いて、上記未延伸糸を図１に示す仮撚加工装置を用い、仮撚ヒーター４の温度２２０℃、延伸倍率１．８９倍、加工速度６００ｍ／ｍｉｎ、Ｄ／Ｙ比１．６４で仮撚加工を行った。得られた仮撚加工糸のマルチフィラメント繊度は５９．０ｄｔｅｘ、伸度は２７．５％、沸騰水収縮率は６．７％、伸縮復元率は４０．３％、捲縮伸長率は２２．４％であった。
【００６９】
仮撚加工糸の光沢度は、３８．６、光沢感は４級であり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．６％と良好であり、毛羽発生数も０．１８個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は良好であり、製品評価は４級であった。
【００７０】
実施例２
艶消し剤として添加する酸化チタン粒子のエチレングリコールスラリーの添加量を得られるポリマーに対して０．０４０重量％とすること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００７１】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【００７２】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．３％、沸騰水収縮率が６．７％、伸縮復元率が４０．４％、捲縮伸長率が２２．３％の仮撚加工糸を得た。
【００７３】
未延伸糸の異形度は１．８５であった。仮撚加工糸の光沢度は３７．８、光沢感は３〜４級であり、艶消し剤として添加した酸化チタン粒子のエチレングリコールスラリーの添加量が増加した分、光沢感は低下したが、合格レベルであり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．８％と良好であり、毛羽発生数も０．１４個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は良好であり、製品評価は４級であった。
【００７４】
実施例３
重合触媒に三酸化アンチモン（住友金属鉱山社製）を、得られるポリマーに対してアンチモン原子換算で２０ｐｐｍ添加したこと以外は実施例１と同様な方法でポリエステル組成物を得た。重合触媒に三酸化アンチモンを用いても重合反応性は良好に推移した。
【００７５】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．００であった。
【００７６】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．０ｄｔｅｘ、伸度が２７．２％、沸騰水収縮率が６．７％、伸縮復元率が４０．４％、捲縮伸長率が２２．３％の仮撚加工糸を得た。
【００７７】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３８．０、光沢感は３〜４級であり、重合触媒に三酸化アンチモンを用いた分、光沢感は低下したが、合格レベルであり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．６％と良好であり、毛羽発生数も０．２０個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【００７８】
実施例４
クエン酸キレートチタン化合物の２重量％エチレングリコール溶液を得られるポリマーに対してチタン原子換算で３ｐｐｍとなるように添加し、５分後、フェニルホスホン酸ジメチルエステルの１０重量％エチレングリコール溶液を得られるポリマーに対してリン原子換算で２ｐｐｍとなるように添加すること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００７９】
得られたポリエステル組成物のＩＶは、クエン酸キレートチタン化合物の２重量％エチレングリコール溶液の添加量が少ない分、重合活性が低いため、０．６４となったが、製糸性に問題ない範囲であった。また、ポリマーの融点は２５９℃であった。ポリマーから測定したチタン触媒由来のチタン原子の含有量は１ｐｐｍ、リン原子の含有量は０．８ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【００８０】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２６．３％、沸騰水収縮率が６．７％、伸縮復元率が３８．４％、捲縮伸長率が２１．３％の仮撚加工糸を得た。
【００８１】
未延伸糸の異形度は１．８５であった。仮撚加工糸の光沢度は４０．５、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９８．２％、毛羽発生数は０．２７個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【００８２】
実施例５
クエン酸キレートチタン化合物の２重量％エチレングリコール溶液を得られるポリマーに対してチタン原子換算で５０ｐｐｍとなるように添加し、５分後、フェニルホスホン酸ジメチルエステルの１０重量％エチレングリコール溶液を得られるポリマーに対してリン原子換算で４０ｐｐｍとなるように添加すること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００８３】
得られたポリエステル組成物のＩＶは、０．６６であった。また、ポリマーの融点は２５９℃であった。ポリマーから測定したチタン触媒由来のチタン原子の含有量は５０ｐｐｍ、リン原子の含有量は４０ｐｐｍであり、Ｔｉ／Ｐ＝０．８であった。
【００８４】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２６．３％、沸騰水収縮率が６．５％、伸縮復元率が３９．４％、捲縮伸長率が２１．８％の仮撚加工糸を得た。
【００８５】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３６．８、光沢感は３級であり、チタン触媒由来のチタン原子含有量とリン原子含有量が高い分、光沢感は低下したが、合格レベルであった。仮撚加工性は９８．０％、毛羽発生数は０．３５個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３級であった。
【００８６】
実施例６
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒にクエン酸キレートチタン化合物（フェニルホスホン酸混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００８７】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【００８８】
重合触媒として用いたクエン酸キレートチタン化合物（フェニルホスホン酸混合）の合成方法は、以下の通りである。
【００８９】
撹拌機、凝縮器及び温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にクエン酸・一水和物（５３２ｇ、２．５２モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトライソプロポキシド（２８８ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりイソプロパノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、次いでエチレングリコール（５０４ｇ、８０モル）と混合し、そして真空下で加熱してイソプロパノール／水を除去し、わずかに曇った淡黄色の生成物（Ｔｉ含有量３．８５重量％）を得た。この混合溶液に対し、フェニルホスホン酸（１５８ｇ、１．００モル）を加えることで、リン化合物を含有するチタン化合物を得た（Ｐ含有量２．４９重量％）。
【００９０】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．４％、沸騰水収縮率が６．６％、伸縮復元率が４０．２％、捲縮伸長率が２２．１％の仮撚加工糸を得た。
【００９１】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３９．１、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９９．０％と良好であり、毛羽発生数も０．１６個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は良好であり、製品評価は４級であった。
【００９２】
実施例７
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒にクエン酸キレートチタン化合物（フェニルホスホン酸、リン酸混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００９３】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は９ｐｐｍであり、Ｔｉ／Ｐ＝０．７であった。
【００９４】
重合触媒として用いたクエン酸キレートチタン化合物（フェニルホスホン酸、リン酸混合）の合成方法は、以下の通りである。
【００９５】
撹拌機、凝縮器及び温度計を備えた３Ｌのフラスコ中に温水（３７１ｇ）にクエン酸・一水和物（５３２ｇ、２．５２モル）を溶解させた。この撹拌されている溶液に滴下漏斗からチタンテトライソプロポキシド（２８８ｇ、１．００モル）をゆっくり加えた。この混合物を１時間加熱、還流させて曇った溶液を生成させ、これよりイソプロパノール／水混合物を真空下で蒸留した。その生成物を７０℃より低い温度まで冷却し、そしてその撹拌されている溶液にＮａＯＨ（３８０ｇ、３．０４モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えた。得られた生成物をろ過し、次いでエチレングリコール（５０４ｇ、８０モル）と混合し、そして真空下で加熱してイソプロパノール／水を除去し、わずかに曇った淡黄色の生成物（Ｔｉ含有量３．８５重量％）を得た。この混合溶液に対し、フェニルホスホン酸（１５８ｇ、１．００モル）及びリン酸の８５重量／重量％水溶液（３９．９ｇ、０．３５モル）を加えることで、リン化合物を含有するチタン化合物を得た（Ｐ含有量３．３６重量％）。
【００９６】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．４％、沸騰水収縮率が６．７％、伸縮復元率が４０．１％、捲縮伸長率が２２．２％の仮撚加工糸を得た。
【００９７】
未延伸糸の異形度は１．８７であった。仮撚加工糸の光沢度は４０．２、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９９．４％、毛羽発生数は０．０８個／２０００ｍであり、非常に良好であった。また、織布および編成工程においても仮撚加工糸要因での停台は発生せず、操業性に優れ、織物、編物の光沢感は良好であり、製品評価は５級であった。
【００９８】
実施例８
重合触媒に乳酸キレートチタン化合物を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【００９９】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【０１００】
重合触媒として用いた乳酸キレートチタン化合物の合成方法は、以下の通りである。
【０１０１】
撹拌機、凝縮器及び温度計を備えた１Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（２１８ｇ、３．５１モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応混合物を１５分間撹拌し、そしてその反応フラスコに乳酸アンモニウム（２５２ｇ、２．００モル）の８５重量／重量％水溶液を加えると、透明な淡黄色の生成物（Ｔｉ含有量６．５４重量％）を得た。
【０１０２】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．０％、沸騰水収縮率が６．８％、伸縮復元率が４０．１％、捲縮伸長率が２２．０％の仮撚加工糸を得た。
【０１０３】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３９．２、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９８．８％と良好であり、毛羽発生数も０．１６個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は良好であり、製品評価は４級であった。
【０１０４】
実施例９
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒に乳酸キレートチタン化合物（フェニルホスホン酸混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１０５】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．１であった。
【０１０６】
重合触媒として用いた乳酸キレートチタン化合物（フェニルホスホン酸混合）の合成方法は、以下の通りである。
【０１０７】
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（２１８ｇ、３．５１モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応混合物を１５分間撹拌し、そしてその反応フラスコに乳酸アンモニウム（２５２ｇ、２．００モル）の８５重量／重量％水溶液を加えると、透明な淡黄色の生成物（Ｔｉ含有量６．５４重量％）を得た。この混合溶液に対し、フェニルホスホン酸（１５８ｇ、１．００モル）を加えることで、リン化合物を含有するチタン化合物を得た（Ｐ含有量４．２３重量％）。なお、重縮合反応の開始時点ではリン化合物を追加添加しなかった。
【０１０８】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．２ｄｔｅｘ、伸度が２７．６％、沸騰水収縮率が６．８％、伸縮復元率が３９．９％、捲縮伸長率が２１．７％の仮撚加工糸を得た。
【０１０９】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３８．８、光沢感は４級であり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．６％と良好であり、毛羽発生数も０．１４個／２０００ｍと合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は良好であり、製品評価は４級であった。
【０１１０】
実施例１０
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒に乳酸キレートチタン化合物（フェニルホスホン酸、リン酸混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１１１】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は９ｐｐｍであり、Ｔｉ／Ｐ＝０．７であった。
【０１１２】
重合触媒として用いた乳酸キレートチタン化合物（フェニルホスホン酸、リン酸混合）の合成方法は、以下の通りである。
【０１１３】
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（２１８ｇ、３．５１モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応混合物を１５分間撹拌し、そしてその反応フラスコに乳酸アンモニウム（２５２ｇ、２．００モル）の８５重量／重量％水溶液を加えると、透明な淡黄色の生成物（Ｔｉ含有量６．５４重量％）を得た。この混合溶液に対し、フェニルホスホン酸（１５８ｇ、１．００モル）及びリン酸の８５重量／重量％水溶液（３９．９ｇ、０．３５モル）を加えることで、リン化合物を含有するチタン化合物を得た（Ｐ含有量５．７１重量％）。なお、重縮合反応の開始時点ではリン化合物を追加添加しなかった。
【０１１４】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．１％、沸騰水収縮率が６．７％、伸縮復元率が４０．２％、捲縮伸長率が２１．７％の仮撚加工糸を得た。
【０１１５】
未延伸糸の異形度は１．８７であった。仮撚加工糸の光沢度は３９．６、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９９．４％、毛羽発生数は０．０６個／２０００ｍであり、非常に良好であった。また、織布および編成工程においても仮撚加工糸要因での停台は発生せず、操業性に優れ、織物、編物の光沢感は良好であり、製品評価は５級であった。
【０１１６】
実施例１１
重合触媒にテトライソプロポキシチタン化合物を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１１７】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【０１１８】
重合触媒として用いたテトラプロポキシチタン化合物の合成方法は、以下の通りである。
【０１１９】
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（４９６ｇ、８．００モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応フラスコに、ＮａＯＨ（１２５ｇ、１．００モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えて透明な黄色の液体を得た（Ｔｉ含有量４．４４重量％）。
【０１２０】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２６．９％、沸騰水収縮率が６．６％、伸縮復元率が３９．８％、捲縮伸長率が２１．６％の仮撚加工糸を得た。
【０１２１】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３８．４、光沢感は４級であり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．４％、毛羽発生数は０．１８個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【０１２２】
実施例１２
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒にテトラプロポキシチタン化合物（リン酸混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１２３】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【０１２４】
重合触媒として用いたテトラプロポキシチタン化合物（リン酸混合）の合成方法は、以下の通りである。
【０１２５】
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（４９６ｇ、８．００モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応フラスコに、ＮａＯＨ（１２５ｇ、１．００モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えて透明な黄色の液体を得た（Ｔｉ含有量４．４４重量％）。この混合溶液に対し、リン酸の８５重量／重量％水溶液（１１４ｇ、１．００モル）を加えた（Ｐ含有量２．８７重量％）。
【０１２６】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．０％、沸騰水収縮率が６．７％、伸縮復元率が４０．０％、捲縮伸長率が２１．９％の仮撚加工糸を得た。
【０１２７】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３８．０、光沢感は４級であり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．４％、毛羽発生数は０．１８個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【０１２８】
実施例１３
重縮合反応の開始時点でリン化合物を追加添加しないことと重合触媒にテトラプロポキシチタン化合物（ジエチルホスホノ酢酸エチル混合）を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１２９】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【０１３０】
重合触媒として用いたチタンアルコシド化合物（ジエチルホスホノ酢酸エチル混合）の合成方法は、以下の通りである。
【０１３１】
撹拌機、凝縮器及び温度計を備えた２Ｌのフラスコ中に撹拌されているチタンテトライソプロポキシド（２８５ｇ、１．００モル）に滴下漏斗からエチレングリコール（４９６ｇ、８．００モル）を加えた。添加速度は、反応熱がフラスコ内容物を約５０℃に加温するように調節された。その反応フラスコに、ＮａＯＨ（１２５ｇ、１．００モル）の３２重量／重量％水溶液を滴下漏斗によりゆっくり加えて透明な黄色の液体を得た（Ｔｉ含有量４．４４重量％）。この混合溶液に対し、ジエチルホスホノ酢酸エチル（２２４ｇ、１．００モル）を加えることで、リン化合物を含有するチタン化合物を得た（Ｐ含有量２．８７重量％）。
【０１３２】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２７．０％、沸騰水収縮率が６．７％、伸縮復元率が３９．９％、捲縮伸長率が２１．６％の仮撚加工糸を得た。
【０１３３】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３８．２、光沢感は４級であり、良好な光沢感を有する仮撚加工糸であった。仮撚加工性は９８．４％、毛羽発生数は０．２０個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【０１３４】
実施例１４
重合触媒にアコーディス社製のチタン及びケイ素からなる複合酸化物を用いること以外は実施例１と同様な方法でポリエステル組成物を得た。
【０１３５】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であった。
【０１３６】
重合触媒として用いたアコーディス社製のチタン及びケイ素からなる複合酸化物（商品名：Ｃ−９４、以降Ｔｉ／Ｓｉ複合酸化物と記す）の０．１５重量％エチレングリコール溶液を得られるポリマーに対してチタン原子換算で１０ｐｐｍとなるように添加し、５分後、フェニルホスホン酸ジメチルエステルの１０重量％エチレングリコール溶液を得られるポリマーに対してリン原子換算で６ｐｐｍとなるように添加した。
【０１３７】
上記ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２６．８％、沸騰水収縮率が６．７％、伸縮復元率が３９．８％、捲縮伸長率が２１．９％の仮撚加工糸を得た。
【０１３８】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３７．１、光沢感は３級であり、光沢感は合格レベルであった。仮撚加工性は９８．２％毛羽発生数は０．３２個／２０００ｍであり、ともに合格レベルであった。また、織布および編成工程の操業性や織物、編物の光沢感は合格レベルであり、製品評価は３〜４級であった。
【０１３９】
実施例１５
実施例１と同様な方法でポリエステル組成物を得た。得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であり、アンチモン原糸の含有量は０ｐｐｍであった。
【０１４０】
上記ポリエステル組成物を未延伸糸の異形度を低下させるために口金吐出孔のスリット長、スリット幅を変更すること以外は実施例１と同様な方法で仮撚加工を行った。未延伸糸の異形度は１．５３であった。得られた仮撚加工糸のマルチフィラメント繊度は５９．０ｄｔｅｘ、伸度は２８．４％、沸騰水収縮率は６．７％、伸縮復元率は４０．５％、捲縮伸長率は２２．７％であった。
【０１４１】
仮撚加工糸の光沢度は、３６．４、光沢感は３級であり、光沢感は合格レベルであった。仮撚加工性は９９．６％、毛羽発生数は０．０６個／２０００ｍと非常に良好であった。また、織布および編成工程の操業性は良好で、織物、編物の光沢感は合格レベルであり、製品評価は３級であった。
【０１４２】
実施例１６
実施例１と同様な方法でポリエステル組成物を得た。得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であり、アンチモン原糸の含有量は０ｐｐｍであった。
【０１４３】
上記ポリエステル組成物を未延伸糸の異形度を増加させるために口金吐出孔のスリット長、スリット幅を変更すること以外は実施例１と同様な方法で仮撚加工を行った。未延伸糸の異形度は２．２６であった。得られた仮撚加工糸のマルチフィラメント繊度は５９．０ｄｔｅｘ、伸度は２６．８％、沸騰水収縮率は６．７％、伸縮復元率は３９．６％、捲縮伸長率は２１．７％であった。
【０１４４】
仮撚加工糸の光沢度は、４２．６、光沢感は５級であり、優れた光沢感を有する仮撚加工糸であった。仮撚加工性は９８．０％、毛羽発生数は０．４２個／２０００ｍであり合格レベルであった。また、織布および編成工程の操業性は合格レベルで、織物、編物の光沢感は良好であり、製品評価は３級であった。
【０１４５】
比較例１
重合触媒に三酸化アンチモン（住友金属鉱山社製）を、得られるポリマーに対してアンチモン原子換算で４００ｐｐｍ添加したこと以外は実施例１と同様な方法でポリエステル組成物を得た。重合触媒に三酸化アンチモンを用いても重合反応性は良好に推移した。
【０１４６】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃、溶液ヘイズは２．３５％であった。
【０１４７】
次いで、該ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２３．１％、沸騰水収縮率が６．５％、伸縮復元率が３６．４％、捲縮伸長率が２０．９％の仮撚加工糸を得た。
【０１４８】
未延伸糸の異形度は１．８５であった。仮撚加工糸の光沢度は３４．６、光沢感は１級であり、光沢感に乏しい仮撚加工糸であった。仮撚加工性は８７．６％、毛羽発生数は２．１０個／２０００ｍであり、仮撚加工性、毛羽ともに不良であった。また、得られるポリエステル組成物の溶液ヘイズが２．３５％と高いため、溶融紡糸時に口金面の汚れが著しかった。さらに、織布および編成工程において仮撚加工糸要因の糸切れが多発し、停台が頻繁に発生した。製品評価は１級であり、操業性、光沢感ともに不良であった。
比較例２
重合触媒に酸化ゲルマニウム（住友金属鉱山社製）を、得られるポリマーに対してゲルマニウム原子換算で１５０ｐｐｍ添加したこと以外は実施例１と同様にな方法でポリエステル組成物を得た。重合触媒に酸化ゲルマニウムを用いても重合反応性は良好に推移した。
【０１４９】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃、溶液ヘイズは２．０８％であった。
【０１５０】
次いで、該ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２３．３％、沸騰水収縮率が６．５％、伸縮復元率が３６．７％、捲縮伸長率が２０．９％の仮撚加工糸を得た。
【０１５１】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３５．８、光沢感は２級であり、光沢感に乏しい仮撚加工糸であった。仮撚加工性は８９．０％、毛羽発生数は１．４６個／２０００ｍであり、仮撚加工性、毛羽ともに不調であった。また、織布および編成工程において仮撚加工糸要因の糸切れが多発し、停台が頻繁に発生した。製品評価は２級であり、操業性、光沢感ともに不調であった。
【０１５２】
比較例３
触媒に酢酸アンチモン（住友金属鉱山社製）を、得られるポリマーに対してアンチモン原子換算で４００ｐｐｍ添加したこと以外は実施例１と同様にしてポリエステル組成物を得た。重合触媒に酢酸アンチモンを用いても重合反応性は良好に推移した。
【０１５３】
得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃、溶液ヘイズは２．１８％であった。
【０１５４】
次いで、該ポリエステル組成物を用いて、実施例１と同様な方法で仮撚加工を行い、マルチフィラメント繊度が５９．１ｄｔｅｘ、伸度が２３．２％、沸騰水収縮率が６．５％、伸縮復元率が３６．６％、捲縮伸長率が２１．０％の仮撚加工糸を得た。
【０１５５】
未延伸糸の異形度は１．８６であった。仮撚加工糸の光沢度は３４．８、光沢感は２級であり、光沢感に乏しい仮撚加工糸であった。仮撚加工性は８８．２％、毛羽発生数は１．３２個／２０００ｍであり、仮撚加工性、毛羽ともに不調であった。また、織布および編成工程において仮撚加工糸要因の糸切れが多発し、停台が頻繁に発生した。製品評価は２級であり、操業性、光沢感ともに不調であった。
【０１５６】
比較例４
実施例１と同様な方法でポリエステル組成物を得た。得られたポリエステル組成物のＩＶは０．６６、ポリマーの融点は２５９℃であった。また、ポリマーから測定したチタン触媒由来のチタン原子の含有量は１０ｐｐｍ、リン原子の含有量は６ｐｐｍであり、Ｔｉ／Ｐ＝１．０であり、アンチモン原糸の含有量は０ｐｐｍであった。
【０１５７】
上記ポリエステル組成物を円形の口金吐出孔を用いること以外は実施例１と同様な方法で仮撚加工を行った。得られた仮撚加工糸のマルチフィラメント繊度は５９．０ｄｔｅｘ、伸度は２８．８％、沸騰水収縮率は６．７％、伸縮復元率は３９．９％、捲縮伸長率は２１．８％であった。
【０１５８】
仮撚加工糸の光沢度は、３３．２、光沢感は１級であり、光沢感に乏しい仮撚加工糸であった。仮撚加工性は９９．６％、毛羽発生数は０．０４個／２０００ｍであった。また、織布および編成工程の操業性は合格レベルであったが、織物、編物の光沢感が不良であり、製品評価は１級であった。
【０１５９】
【表１】

【０１６０】
【表２】

【０１６１】
【発明の効果】
本発明の仮撚加工糸を用いることにより、光沢感に優れた布帛を提供することができ、かつ、織布工程や編成工程などでの毛羽や断糸の発生が少なく、織機や編機の停台が少ないので、安定した生産性で布帛を提供することができる。
【図面の簡単な説明】
【図１】本発明での仮撚工程の一例を示す概略図である。
【符号の説明】
１：未延伸糸
２：糸条解舒ガイド
３：供給ロール
４：仮撚ヒーター
５：仮撚具
６：引取ローラー
７：第２引取ローラー
８：仮撚糸チーズ[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyester false twisted yarn produced using a specific polyester polymerization catalyst, and in particular, has excellent glossiness comprising a polyester composition containing a novel polyester polymerization catalyst having good color tone and heat resistance. The present invention relates to a polyester false twisted yarn capable of providing a woven or knitted fabric.
[0002]
[Prior art]
Polyesters are widely used in various fields including fibers, films, and bottles because of their excellent properties. Among them, polyethylene terephthalate is widely used in various fields including general clothing fields due to its various excellent properties including mechanical properties, chemical properties, and dimensional stability. In garment applications, the quality has been improved using natural fibers as a target, and in particular, in order to give the drawn yarns insufficient bulkiness, false twisting is performed at the same time as drawing to obtain a bulky texture.
[0003]
On the other hand, with the diversification of consumer sensitivity, demands for false twisted yarns having sharp and sharp luster have been increasing. However, since the false twisted yarn is heated and twisted under high temperature and high tension in order to obtain a feeling of bulkiness, there is a problem that the filament cross section is flattened and glossiness is reduced. In general, polyethylene terephthalate is produced from terephthalic acid or its ester-forming derivative and ethylene glycol. In a commercial process for producing a polymer having a high molecular weight, an antimony compound is widely used as a polycondensation catalyst. However, when the antimony compound is added to such an extent that a commercial polymerization rate is exhibited, the antimony catalyst residue after polycondensation, that is, the precipitation of antimony metal, causes darkening and foreign matters in the polyester composition, resulting in a dull gloss. Problem. In addition, polymers containing antimony compounds have some undesirable properties as described below.
[0004]
For example, it is known that when a polymer obtained using an antimony catalyst is melt-spun into fibers, residues of the antimony catalyst accumulate around the mouth of the mouthpiece. If this accumulation progresses, a yarn bending phenomenon at the die discharge hole or a spike of the discharge yarn occurs, which causes yarn spots and breakage of the yarn. The deposition of the antimony catalyst residue occurs because the antimony compound in the polymer is metamorphosed near the base discharge hole, and after a part of the antimony compound is vaporized and dissipated, the component mainly composed of antimony remains around the base discharge hole. It is considered.
[0005]
In addition, the antimony catalyst residue in the polymer tends to be relatively large particles and becomes a foreign substance, which causes an increase in the filtration pressure of the filter in the pack during melt spinning, thereby shortening the replacement cycle of the pack and causing an increase in cost. .
[0006]
Furthermore, the contamination of foreign matter mainly composed of antimony deposited around the nozzle discharge hole into the fiber and the residue of antimony catalyst in the polymer, that is, metal antimony, not only cause the occurrence of thread breakage during melt spinning, but also during false twisting. It causes fluff and yarn breakage, and eventually causes loom and knitting machines to stop due to fluff and breakage of false twisted yarns in the weaving process and knitting process.
[0007]
Means for improving the glossiness of the false twisted yarn include reducing the amount of inorganic oxide particles used as a matting agent in the polymer, but the lower limit of the amount added is limited from the viewpoint of yarn-making properties. You. It is also effective to increase the degree of irregularity of the filament cross section. However, if the degree of irregularity is too high, the operability at the time of spinning is reduced, the spots of dyeing due to cooling spots between the single yarns, and the fluff at the time of false twisting are generated. This causes a deterioration in quality.
[0008]
In view of the above background, polyesters having a low or no antimony content have been demanded in order to prevent a decrease in glossiness due to the occurrence of darkening or foreign matters of the polyester composition caused by antimony catalyst residues. Therefore, when a role of the polycondensation catalyst is required for a compound other than the antimony-based compound, a germanium compound is known. However, a germanium compound is hardly available as a rare compound and is difficult to be used for general purposes.
[0009]
Therefore, in the present invention, the above problems have been improved, and as a result of intensive studies on polyester false twisted yarn having excellent heat resistance, color tone and excellent gloss, the object of the present invention is to use a titanium compound as a polymerization catalyst. The knowledge that can be achieved was obtained.
[0010]
On the other hand, it has been proposed to use a titanium complex comprising a titanium compound and a phosphorus compound as a polymerization catalyst as a polyester polymerization catalyst (see Patent Documents 1 to 3). According to this method, although foreign substances caused by the catalyst can be reduced, the color tone of the obtained polymer is not sufficient. Therefore, further improvement of titanium compounds is required.
[0011]
Therefore, in the present invention, as a result of intensive studies on improving the production and quality defects of the polyester false twisted yarn, a polyester produced using a titanium compound (excluding titanium dioxide particles) as a main catalyst and an antimony compound It has been found that the object of the present invention can be achieved by containing no or at 30 ppm or less in terms of antimony atoms relative to polyester.
[0012]
[Patent Document 1]
JP 2001-524536 A (page 1)
[0013]
[Patent Document 2]
JP-T-2002-512267 (page 1)
[0014]
[Patent Document 3]
JP-A-2002-293909 (page 1)
[0015]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyester composition containing a novel polyester polymerization catalyst having good color tone and heat resistance, excellent glossiness, stable production without generation of fluff and breakage, and woven fabric. It is an object of the present invention to provide a stable false twisted yarn having a small number of stops of a loom or a knitting machine in a process or a knitting process.
[0016]
[Means for Solving the Problems]
An object of the present invention is to provide a polyester produced using a titanium compound (excluding titanium dioxide particles) as a main catalyst and containing no antimony compound or containing 30 ppm or less in terms of antimony atom based on the polyester. Achieved by a polyester false twisted yarn characterized in that the content of the inorganic oxide particles used as a matting agent is 0.04% by weight or less and the cross section of the undrawn yarn before false twisting is irregular. it can.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail.
[0018]
The polyester composition used for the polyester false twisting yarn in the present invention is a polymer synthesized from dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. Those which can be used as molded articles such as fibers, films, bottles and the like are preferable.
[0019]
Specific examples of such a polyester composition include, for example, polyethylene terephthalate, polytrimethylene terephthalate, polytetramethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene-2,6-naphthalenedicarboxylate, polyethylene-1, 2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylate and the like. The present invention is particularly suitable for the most widely used polyethylene terephthalate or polyester copolymer containing mainly ethylene terephthalate units.
[0020]
Further, in these polyester compositions, adipic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, dicarboxylic acids such as cyclohexanedicarboxylic acid, etc. Ester-forming derivatives thereof, dioxy compounds such as polyethylene glycol, hexamethylene glycol, neopentyl glycol, polypropylene glycol, and cyclohexane dimethanol; oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid; and ester-forming derivatives thereof. May be copolymerized.
[0021]
In the polyester composition used for the polyester false twisting yarn of the present invention, the titanium compound that can be used as a catalyst is selected from the group consisting of functional groups represented by the following general formulas 1 to 6 in which the substituents of the titanium compound are represented by the following general formulas: At least one kind of titanium compound, titanium oxide and the like can be mentioned.
[0022]
Embedded image

[0023]
(In Formulas 1 to 6, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group having 1 to 30 carbon atoms.)
Formula 1 of the present invention includes an alkoxy group such as ethoxide, propoxide, isopropoxide, butoxide, and 2-ethylhexoxide, and a hydroxy polycarboxylic acid compound such as lactic acid, malic acid, tartaric acid, and citric acid. Functional groups.
[0024]
Formula 2 includes a functional group composed of a β-diketone compound such as acetylacetone and a ketoester compound such as methyl acetoacetate and ethyl acetoacetate.
[0025]
Formula 3 includes a functional group composed of phenoxy, cresylate, salicylic acid, and the like.
[0026]
Formula 4 includes an acylate group such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemi-mellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, and sebacine. Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or anhydride thereof, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And a functional group comprising a nitrogen-containing polycarboxylic acid such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.
[0027]
Formula 5 includes a functional group composed of aniline, phenylamine, diphenylamine, and the like.
[0028]
Above all, it is preferable to include Formula 1 and / or Formula 4 from the viewpoint of the thermal stability and color tone of the polymer.
[0029]
Examples of the titanium compound include titanium diisopropoxybisacetylacetonate and titanium triethanolaminate isopropoxide containing two or more of these substituents of formulas 1 to 6.
[0030]
Examples of the titanium oxide include a composite oxide in which a main metal element is composed of titanium and silicon.
[0031]
The catalyst of the present invention refers to all or some of the following reactions (1) to (3) in a polymer synthesized from dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative. Refers to a compound that substantially contributes to the promotion of the reaction.
(1) Esterification reaction which is a reaction between a dicarboxylic acid component and a diol component (2) Ester exchange reaction which is a reaction between an ester-forming derivative component of a dicarboxylic acid and a diol component (3) Substantially esterification or transesterification The reaction is completed, and the resulting polyethylene terephthalate low polymer is subjected to a polycondensation reaction to increase the degree of polymerization by a dediol reaction.Accordingly, titanium dioxide particles generally used as inorganic particles in a fiber matting agent and the like are: It has substantially no catalytic action on the above reaction, and is different from the titanium compound that can be used as the catalyst of the present invention.
[0032]
The method for producing the composite oxide in which the main metal element is composed of titanium and silicon is not particularly limited.For example, in a method of producing a titanium oxide by using a alkoxide compound as a raw material by a hydrolysis reaction, the hydrolysis rate is controlled. Obtained by Specifically, for example, a small amount of another metal alkoxide compound such as silicon or zirconium or a polyhydric alcohol compound is allowed to coexist with a titanium alkoxide compound as a main raw material, and a coprecipitation method, a partial hydrolysis method, It can be synthesized by a chemical sol-gel method. Here, the coprecipitation method is a method in which a solution having a predetermined composition containing two or more components is prepared, and the hydrolysis reaction proceeds with the composition. The partial hydrolysis method is a method in which one component is previously hydrolyzed, the other component is added thereto, and the hydrolysis is further advanced. The coordination chemical sol-gel method is a method in which a titanium alkoxide raw material and a polyhydric alcohol compound having a plurality of functional groups in a molecule coexist, and a reactant is formed between the two in advance, thereby performing a subsequent hydrolysis. It is intended to control the rate of the reaction. For example, Ueno et al., “Preparation of Catalyst Using Metal Alkoxide”, page 321, line 1 to page 353, line 16, (IPC, published August 10, 1993) And so on.
[0033]
The titanium compound (excluding titanium dioxide particles) in the present invention is preferably contained in an amount of 0.5 to 150 ppm in terms of titanium atoms with respect to the obtained polymer. If it is 1 to 100 ppm, the thermal stability and color tone of the polymer are good, and the amount of change in the intrinsic viscosity of the carbo terminal group and the polymer from the end of the polymerization reaction to the formation of chips is small, so that polyester false twist with excellent leveling properties It is preferably a processed yarn, and more preferably 3 to 50 ppm.
[0034]
The polyester composition of the present invention preferably contains 0.1 to 400 ppm of phosphorus together with the titanium compound in terms of phosphorus atom based on the polyester. The phosphorus content is preferably from 1 to 200 ppm, more preferably from 3 to 100 ppm, from the viewpoint of the thermal stability and the color tone of the polyester composition during spinning.
[0035]
The phosphorus contained in the polyester composition of the present invention is added as a phosphorus compound in the process of producing the polyester composition. Such a phosphorus compound is any one or two of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinous acid, and phosphine. Is preferred. Specifically, for example, phosphoric acids, such as phosphoric acid, trimethyl phosphate, triethyl phosphate, and triphenyl phosphate, and phosphorous acids, such as phosphorous acid, trimethyl phosphite, triethyl phosphite, and triphenyl phosphite. Phosphoric acid, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, anthryl Phosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5-dicarboxy Phenylphosphonic acid, 2,6-dicarboxy Nylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2,3,5-tricarboxyphenylphosphonic acid, 2,3 2,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl ester, ethylphosphonic acid dimethyl ester, ethyl Phosphonic acid diethyl ester, Phenylphosphonic acid dimethyl ester, Phenylphosphonic acid diethyl ester, Phenylphosphonic acid diphenyl ester, Benzylphosphonic acid dimethyl ester, Benzylphosphonic acid diethyl ester, Benzylphosphonic acid diester Phenyl ester, lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), magnesium bis (3, Ethyl 5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), diethylphosphonoacetic acid, methyl diethylphosphonoacetate, Phosphonic acid compounds such as ethyl diethylphosphonoacetate, hypophosphorous acid, sodium hypophosphite, methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, tolylphosphinic acid , Xylylphosphinic acid, Biphenylylphosphinic acid, diphenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid, diisopropylphosphinic acid, dibutylphosphinic acid, ditolylphosphinic acid, dixylylphosphinic acid, dibiphenylylphosphinic acid, naphthylphosphinic acid, Anthrylphosphinic acid, 2-carboxyphenylphosphinic acid, 3-carboxyphenylphosphinic acid, 4-carboxyphenylphosphinic acid, 2,3-dicarboxyphenylphosphinic acid, 2,4-dicarboxyphenylphosphinic acid, 2,5- Dicarboxyphenylphosphinic acid, 2,6-dicarboxyphenylphosphinic acid, 3,4-dicarboxyphenylphosphinic acid, 3,5-dicarboxyphenylphosphinic acid, 2,3,4-trica Boxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2,4,6-tricarboxy Phenylphosphinic acid, bis (2-carboxyphenyl) phosphinic acid, bis (3-carboxyphenyl) phosphinic acid, bis (4-carboxyphenyl) phosphinic acid, bis (2,3-dicarboxylphenyl) phosphinic acid, bis ( 2,4-dicarboxyphenyl) phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, Bis (3,5-dicarboxyphenyl) phosphinic acid, bis (2,3 4-tricarboxyphenyl) phosphinic acid, bis (2,3,5-tricarboxyphenyl) phosphinic acid, bis (2,3,6-tricarboxyphenyl) phosphinic acid, bis (2,4,5-tricarboxyphenyl) ) Phosphinic acid, and bis (2,4,6-tricarboxyphenyl) phosphinic acid, methyl phosphinic acid methyl ester, dimethyl phosphinic acid methyl ester, methyl phosphinic acid ethyl ester, dimethyl phosphinic acid ethyl ester, ethyl phosphinic acid methyl ester, Methyl diethylphosphinic acid ester, ethylphosphinic acid ethylester, diethylphosphinic acid ethylester, phenylphosphinic acid methylester, phenylphosphinic acid ethylester, phenylphosphinic acid phenylester, diphenyl Nylphosphinic acid methyl ester, diphenylphosphinic acid ethyl ester, diphenylphosphinic acid phenyl ester, benzylphosphinic acid methyl ester, benzylphosphinic acid ethyl ester, benzylphosphinic acid phenyl ester, bisbenzylphosphinic acid methyl ester, bisbenzylphosphinic acid ethyl ester, Phosphinic acids such as bisbenzylphosphinic acid phenyl ester, phosphine oxides such as trimethyl phosphine oxide, triethyl phosphine oxide, tripropyl phosphine oxide, triisopropyl phosphine oxide, tributyl phosphine oxide, and triphenyl phosphine oxide; methyl phosphonous acid; ethyl Phosphonous acid, propyl phosphonous acid, isopropyl Phosphonic acids such as phonic acid, butyl phosphonous acid, phenyl phosphonous acid, methyl phosphinous acid, ethyl phosphinous acid, propyl phosphinous acid, isopropyl phosphinous acid, butyl phosphinous acid, phenyl phosphinous acid, dimethyl Phosphinous acid, diethyl phosphinous acid, dipropyl phosphinic acid, diisopropyl phosphinous acid, dibutyl phosphinous acid, phosphinous acid systems such as diphenyl phosphinous acid, methyl phosphine, dimethyl phosphine, trimethyl phosphine, meer phosphine, diethyl phosphine, Examples thereof include phosphine compounds such as triethylphosphine, phenylphosphine, diphenylphosphine, and triphenylphosphine, and one or two of these are preferable. In particular, from the viewpoints of thermal stability and color tone improvement, phosphoric acid and / or phosphonic acid are preferred.
[0036]
It is necessary that the polyester composition of the present invention does not contain an antimony compound or contains 30 ppm or less in terms of antimony atom based on polyester. When the content is in this range, it is possible to suppress the occurrence of darkening and foreign matter of the polyester composition due to the antimony catalyst residue, and it is possible to improve the glossiness. In addition, since there is little accumulation of antimony catalyst residue around the nozzle discharge hole during melt spinning, it is possible to prevent a yarn bending phenomenon at the nozzle discharge hole and yarn spots and breakage due to spikes in the discharge yarn, and also to prevent foreign substances mainly composed of antimony. Since the amount of antimony mixed in the fibers and the amount of the antimony catalyst residue in the polymer, that is, the amount of antimony metal, is small, fluff and breakage during false twisting can be prevented. Furthermore, relatively inexpensive polymers can be obtained. The content of the antimony compound is more preferably 10 ppm or less, and further preferably substantially no content.
[0037]
In the polyester composition of the present invention, the content of the inorganic oxide particles used as the matting agent needs to be 0.04% by weight or less. When the content of the inorganic oxide particles used as the matting agent is 0.04% by weight or less, irregular reflection of light by the particles can be suppressed, and a decrease in glossiness can be prevented. In order to further improve the glossiness, the content is preferably not more than 0.02% by weight.
[0038]
The polyester false twisted yarn of the present invention is necessary for a woven or knitted fabric having a good glossiness to have an irregular fiber cross section of the undrawn yarn before polyester false twisting. If the cross section of the fiber is circular, superior glossiness cannot be obtained as compared with conventional materials. An irregular cross-section refers to a cross-section other than a circle, and includes, for example, multi-lobed, flat, C-shaped, V-shaped, and W-shaped, but is not limited thereto. Considering the spinning properties and glossiness, a trilobal section is preferred. Further, the shape of the undrawn yarn represented by the following formula is preferably 1.5 to less than 2.3.
[0039]
R = r2 / r1
[Wherein, r1: the diameter of the inscribed circle of the fiber cross section, r2: the diameter of the circumscribed circle of the fiber cross section]
Further, when the molar ratio of Ti / P is 0.1 to 20 as a phosphorus atom with respect to a titanium atom of the titanium compound, thermal stability and color tone of the polyester composition are improved, which is preferable. More preferably, Ti / P is 0.2 to 10, and further preferably, Ti / P is 0.3 to 5.
[0040]
The titanium compound and the phosphorus compound used in the present invention may be added as they are to the reaction system of the polyester composition.However, the titanium compound and the phosphorus compound are mixed in advance with a solvent containing a diol component forming the polyester composition such as ethylene glycol or propylene glycol. Alternatively, it is preferable to add a slurry to the reaction system after removing low-boiling components such as alcohol used in synthesizing the titanium compound or the phosphorus compound as necessary, since the generation of foreign substances in the polymer is further suppressed. As for the timing of addition, as an esterification reaction catalyst or a transesterification reaction catalyst, there are a method of adding the catalyst immediately after the addition of the raw material and a method of adding the catalyst together with the raw material. Further, when added as a polycondensation reaction catalyst, it may be substantially before the start of the polycondensation reaction, before the esterification reaction or transesterification reaction, or after the end of the reaction, before the start of the polycondensation reaction catalyst. May be added. In this case, in order to suppress the deactivation of the catalyst due to contact between the titanium compound and the phosphorus compound, a method of adding the titanium compound and the phosphorus compound to different reaction tanks, or the addition interval of the titanium compound and the phosphorus compound in the same reaction tank is 1 to 15 minutes. And a method of separating the addition position.
[0041]
In the present invention, a catalyst obtained by reacting a titanium compound with a phosphorus compound in advance can be used as a catalyst. In this case, (1) a titanium compound is mixed with a solvent and a part or the whole thereof is dissolved in the solvent, and the phosphorus compound is dissolved and diluted in a stock solution or a solvent and added dropwise to the mixed solution. (2) When using a ligand of a titanium compound such as a hydroxycarboxylic acid-based compound or a polycarboxylic acid-based compound, the titanium compound or the ligand compound is mixed with a solvent, and a part or all of the mixture is placed in the solvent. After dissolution, the ligand compound or titanium compound is dissolved and diluted in a stock solution or a solvent, and the mixture is added dropwise. Further, it is preferable to further dissolve and dilute the phosphorus compound in a stock solution or a solvent and then add the phosphorus compound to the mixed solution, from the viewpoint of improving thermal stability and color tone. The above reaction conditions are carried out by heating at a temperature of 0 to 200 ° C for 1 minute or more, preferably at a temperature of 20 to 100 ° C for 2 to 100 minutes. The reaction pressure at this time is not particularly limited, and may be normal pressure. The solvent used here can be selected from those capable of dissolving part or all of the titanium compound, the phosphorus compound and the carbonyl group-containing compound, but is preferably water, methanol, ethanol, ethylene glycol, or propane. It is selected from diol, butanediol, benzene, and xylene.
[0042]
In the method for producing a polyester composition used for the polyester false twisting yarn of the present invention, the manganese compound is contained at any time in an amount of 1 to 400 ppm in terms of manganese atom with respect to the polyester, and the ratio of the manganese compound to the phosphorus compound is manganese atom and phosphorus atom. When Mn / P is added in such a manner that the molar ratio of Mn / P becomes 0.1 to 200, a decrease in polymerization activity can be suppressed, and the color tone of the obtained polymer becomes favorable, which is preferable. The manganese compound used in this case is not particularly limited, but specifically, for example, manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, manganese acetate tetrahydrate, manganese acetate dihydrate And the like.
[0043]
In the method for producing a polyester composition used for the polyester false twisting yarn of the present invention, it is preferable to further add a cobalt compound at an arbitrary time point, since the color tone of the obtained polymer becomes good. The cobalt compound used in this case is not particularly limited, but specific examples thereof include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.
[0044]
Further, an alkali metal compound, an alkaline earth metal compound, an aluminum compound, a zinc compound, a tin compound, or the like may be added for the purpose of improving the color tone of the obtained polymer or the heat resistance of the polymer.
[0045]
Furthermore, in addition to particles such as titanium dioxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin, and carbon black, additives such as coloring inhibitors, stabilizers, and antioxidants may be contained. .
[0046]
The method for producing the polyester composition used in the polyester false twisted yarn of the present invention will be described. An example of polyethylene terephthalate will be described as a specific example, but the present invention is not limited to this.
[0047]
Polyethylene terephthalate is usually produced by one of the following processes. That is, (1) a process of obtaining a low polymer by a direct esterification reaction using terephthalic acid and ethylene glycol as raw materials and further obtaining a high molecular weight polymer by a subsequent polycondensation reaction, and (2) a process of using dimethyl terephthalate and ethylene glycol as raw materials. In this process, a low polymer is obtained by a transesterification reaction, and a high molecular weight polymer is obtained by a subsequent polycondensation reaction. Here, the esterification reaction proceeds without a catalyst, but a titanium compound may be added as a catalyst. Further, in the transesterification reaction, the reaction is carried out using a compound such as manganese, calcium, magnesium, zinc, lithium or the above-mentioned titanium compound as a catalyst, and after the transesterification reaction is substantially completed, the catalyst used in the reaction is used. In order to inactivate, a phosphorus compound is added.
[0048]
The production method of the present invention comprises the step of adding a matting agent to the low polymer obtained at any stage of the series of reactions (1) or (2), preferably in the first half of the series of reactions (1) or (2). After adding an additive such as titanium dioxide particles or a cobalt compound, the above-mentioned titanium compound is added as a polycondensation catalyst and a polycondensation reaction is performed to obtain a high molecular weight polyethylene terephthalate.
[0049]
The above reaction can be applied to a batch system, a semi-batch system or a continuous system.
[0050]
The method for producing a polyester false twisted yarn of the present invention is, specifically, a melt spinning method of a polyester undrawn yarn to be subjected to false twisting, for example, a pressure melter method or an extruder method, and the spinning speed is also temporary. Spinning speed suitable for twisting can be adopted.
[0051]
Specifically, the method for producing a polyester false twisting yarn of the present invention can use a friction-type friction false-twisting device or a belt nip-type friction false-twisting device. The false twisting speed is 350 to 1500 m / min. The twisting magnification is 1.4 to 2.0 times, the false twist heater temperature is 130 to 250 ° C, the D / Y ratio is 1.30 to 2.50, and the number of twists is 1500 to 7500 t / m. it can. Here, the D / Y ratio is a ratio between the peripheral speed (D) of the false twisting tool such as a friction disk and a belt and the false twisting speed (Y).
[0052]
Specifically, the polyester false twisted yarn of the present invention has a multifilament fineness of 10 to 660 dtex, an elongation of 15 to 50%, a boiling water shrinkage of 2 to 15%, an elasticity recovery of 10 to 60%, The crimp elongation is 2 to 50%, preferably, the multifilament fineness is 22 to 600 dtex, the elongation is 15 to 45%, the boiling water shrinkage is 4 to 12%, and the elastic recovery is 20 to 55%. The crimp elongation is 15 to 40%, and more preferably, the multifilament fineness is 28 to 500 dtex, the elongation is 20 to 40%, the boiling water shrinkage is 5 to 7%, and the elastic recovery is 30 to 50%. The crimp elongation is 20 to 35%. The measuring methods of the multifilament fineness, elongation, boiling water shrinkage, expansion / recovery, and crimp elongation are as follows.
(1) Multifilament fineness (referred to as D (dtex))
Initial tension: (0.088 x multifilament fineness (dtex)) using a measuring machine with a frame circumference of 1 m, winding 100 turns (100 m) with cN, and measuring the mass of the shackle winding: M (g) with an electronic balance. Then, the multifilament fineness is calculated from the multifilament fineness: D = 100 × M.
(2) Elongation (referred to as E (%))
The sample length: 20 cm, tensile speed: 20 cm / min, recording paper speed: 30 cm / min, initial tension: (0.088 × multifilament fineness (dtex)) cN are stretched using ORIENTEC's RTC-121OA model. Using the sample length at break: L (cm), the elongation (E (%)) is calculated by the following equation.
[0053]
E (%) = 3.33 × L
(3) Boiling water shrinkage (referred to as Ws (%))
Initial tension: (0.088 x multifilament fineness (dtex)) using a scale measuring machine with a frame circumference of 1 m, a skein with a length of 50 cm and 10 turns made of cN, load: (1.767 x multifilament fineness) (Dtex)) The sample length: a is measured with cN applied. Thereafter, a boiling water treatment was performed at 100 ° C. for 15 minutes, and after air drying, a sample length: b was measured under a load of (1.767 × multifilament fineness (dtex)) cN, and boiling water shrinkage was calculated by the following equation. Calculate the ratio: Ws (%).
[0054]
Ws (%) = ((ab) / a) × 100
(4) Expansion / contraction restoration rate (referred to as CR (%))
Initial tension: (0.088 × multifilament fineness (dtex)) cN, using a measuring machine with a frame circumference of 1 m, make a skein of 50 cm in length and 10 turns, and put this in hot water at 90 ° C. After immersion for 20 minutes, drain the water with a blotter or a cloth and air dry naturally. The skein is placed in water at room temperature, and a sample length: a is measured in a state where a prescribed initial load and a constant load are applied. Next, the constant load is removed, the sample is left in water for 3 minutes with only the initial load applied, the sample length: b after 3 minutes is measured, and the expansion / contraction restoration rate CR (%) is calculated by the following equation. . The initial load and the constant load use those determined by the following formula.
[0055]
CR (%) = ((ab) / a) × 100
Initial load (cN) = (multifilament fineness (dtex) /1.111) × 0.002 × 0.9807 × number of windings × 2
Constant load (cN) = (multifilament fineness (dtex) /1.111) × 0.1 × 0.9807 × number of windings × 2
(5) Crimp elongation rate (referred to as TR (%))
Initial tension: (0.088 x multifilament fineness (dtex)) Using a scale measuring machine with a frame circumference of 1 m, make a skein of 50 cm in length and 20 turns with cN, apply initial load, and apply 150 ± 2 ° C. Heat dry for 5 minutes. After the dry heat treatment, a sample length: a under an initial load is measured. Next, the initial load is removed, and the sample length: b under a constant load is measured, and the crimp elongation rate TR (%) is calculated by the following equation. The initial load and the constant load use those determined by the following formula.
[0056]
TR (%) = ((ba−a) / b) × 100
Initial load (cN) = (multifilament fineness (dtex) /1.111) × 0.00166 × 0.9807 × number of windings × 2
Constant load (cN) = (multifilament fineness (dtex) /1.111) × 0.1 × 0.9807 × number of windings × 2
[0057]
【Example】
Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples of the present invention. In addition, the following methods were used for the evaluation method and the measurement method in the examples. The evaluation results and the measurement results are as shown in Tables 1 and 2.
(1) Content of titanium element, phosphorus element, antimony element, germanium element, and manganese element in polyester The content was determined using a fluorescent X-ray element analyzer (MESA-500W type, manufactured by Horiba, Ltd.). In addition, when titanium dioxide particles were contained in the polyester, the following pretreatment was performed and then the fluorescent X-ray analysis was performed. That is, the polyester is dissolved in orthochlorophenol (5 g of the polymer with respect to 100 g of the solvent), and the same amount of dichloromethane as the polymer solution is added to adjust the viscosity of the solution. Then, the centrifuge (18,000 rpm, 1 hour) To settle the particles. Thereafter, only the supernatant was recovered by a gradient method, and the same amount of acetone as that of the supernatant was added to reprecipitate the polymer. Thereafter, the polymer was filtered through a 3G3 glass filter (manufactured by IWAKI), and the filtered material was further filtered. After washing with acetone, acetone was removed by vacuum drying at room temperature for 12 hours. The polymer obtained by performing the above pretreatment was analyzed for a titanium element, a phosphorus element, an antimony element, a germanium element, and a manganese element.
[0058]
On the other hand, when the titanium dioxide particles are not contained, it is not necessary to perform the pretreatment, and the polymer may be analyzed as it is.
(2) Intrinsic viscosity of polymer [η]
The measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(3) 10 mg of a sample to be measured for melting point is precisely weighed, sealed using an aluminum oven pan and a pan cover, and heated from 20 ° C. under a nitrogen stream using a differential scanning calorimeter (manufactured by PerkinElmer, Model DSC7). The temperature was raised to 285 ° C. at a rate of 16 ° C./min, and the melting point peak temperature observed on the way was defined as the melting point.
(4) 2.0 g of a sample to be measured for solution haze was dissolved in 20 ml of orthochlorophenol, and the sample was analyzed by a haze meter (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP type) by an integrating sphere photoelectricity method. .
(5) Deformity (R)
The degree of deformation of the single yarn is calculated by the following equation, and the average value is defined as the degree of irregularity (R).
[0059]
R = r2 / r1
[Wherein, r1: the diameter of the inscribed circle of the fiber cross section, r2: the diameter of the circumscribed circle of the fiber cross section]
(6) Glossiness A knitted fabric for measuring glossiness (length 5 cm x width 5 cm) is fixed to a special sample fixing frame, and two light sources are obtained by a 45 ° diffusion method using an SM color computer manufactured by Suga Test Instruments Co., Ltd. From the light receiving part installed below the sample fixing frame, and the gloss was defined as a ratio when the luminous intensity when the standard plate was measured under the same conditions was set to 100.
[0060]
The dyeing color of the knitted fabric for measuring gloss was blue.
(7) Glossiness evaluation The false twisted yarns obtained in the working examples and the comparative examples were formed into a 35-cm-long tubular knitting machine using a single-necked tubular knitting machine (gauge number: 20) manufactured by Koike Machinery Co., Ltd. Dyeing, washing with water and drying were carried out by a conventional method using a machine. With respect to the cloth obtained by the above method, the glossiness was sensory-evaluated in 1st to 5th grades, and 3rd grade or more was regarded as acceptable.
(8) False twisting properties When 500 untwisted yarns are used to obtain 5.0 kg of false twisting threads, the proportion of false twisting threads in which no yarn breakage or fluff is generated is determined by the false twisting properties ( %), And 98.0% or more was regarded as acceptable.
(9) Number of fluffs The number of fluffs was measured for 5 minutes while running at a yarn speed of 400 m / min using MULTI POINT FLAY COUNTER model MFC-1110 manufactured by Toray Engineering Co., Ltd. did. The number of fluffs generated was 0.50 pieces / 2000m or less.
(10) Product evaluation Using the false twisted yarns obtained in Examples and Comparative Examples, woven and knitted fabrics were produced by the following method, and dyed, washed with water and dried by ordinary methods. With respect to the fabric obtained by the above method, the operability in the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were comprehensively evaluated in the first to fifth grades, and the third grade or more was evaluated as acceptable.
[0061]
A. Woven fabric method A false twisted yarn of 56 dtex, 36 filaments obtained by false twisting an undrawn yarn having a round cross section before false twisting is used as a warp. The false twisted yarn is driven into a woven fabric with a width of 1.7 m, a woven density of 90 yarns / inch, and a loom rotation speed of 800 cpm.
[0062]
B. Using the 360 false twisted yarns obtained in the knitting method examples and comparative examples, warping is performed at a warping speed of 400 m / min, and the obtained beam is formed into a half structure using a 28-gauge single tricot knitting machine. Knitted.
[0063]
Example 1
A slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals, Inc.) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) is charged in advance with about 123 kg of bis (hydroxyethyl) terephthalate at a temperature of 250 ° C. and a pressure of 1.2 × 10 ⁵ Pa. The mixture was sequentially supplied to the held esterification reaction tank over 4 hours, and after the supply was completed, the esterification reaction was further performed for 1 hour, and 123 kg of the esterification reaction product was transferred to the polycondensation tank.
[0064]
Subsequently, 0.025% by weight based on the polymer from which an ethylene glycol slurry of titanium oxide particles was obtained was added to the polycondensation reaction tank into which the esterification reaction product was transferred. After stirring for 5 minutes, an ethylene glycol solution of cobalt acetate and manganese acetate was added to the obtained polymer so as to be 30 ppm in terms of cobalt atoms and 15 ppm in terms of manganese atoms. After stirring for another 5 minutes, a 2% by weight ethylene glycol solution of the titanium citrate chelate compound was added to the obtained polymer so as to be 10 ppm in terms of titanium atoms, and after 5 minutes, 10% by weight of dimethyl phenylphosphonate was added. % Ethylene glycol solution is added so as to be 6 ppm in terms of phosphorus atom with respect to the obtained polymer. Then, while stirring the low polymer at 30 rpm, the temperature of the reaction system is gradually raised from 250 ° C. to 285 ° C. , And the pressure was reduced to 40 Pa. The time required to reach the final temperature and the final pressure was 60 minutes. When the stirring torque reached a predetermined value, the reaction system was purged with nitrogen and returned to normal pressure to stop the polycondensation reaction, discharged into cold water in a strand form, and immediately cut to obtain polymer pellets. The time from the start of the pressure reduction to the arrival of the predetermined stirring torque was 3 hours.
[0065]
The method for synthesizing the titanium citrate chelate compound used as the polymerization catalyst is as follows.
[0066]
Citric acid monohydrate (532 g, 2.52 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetraisopropoxide (288 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated at reflux for 1 hour to form a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The product obtained is filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove the isopropanol / water and give a slightly cloudy pale yellow product (Ti content 3 .85% by weight).
[0067]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. The content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, Ti / P = 1.0, and the content of antimony raw yarn was 0 ppm. confirmed.
[0068]
After drying the polyester composition, melt spinning was performed at a spinning temperature of 289 ° C. and a spinning speed of 2600 m / min, and an undrawn yarn (POY) having a 108.0 dtex, 36-filament fiber cross section having a trilobal cross section was wound up. The degree of irregularity of the undrawn yarn was 1.86. Next, the unstretched yarn was tentatively processed at a temperature of 220 ° C. of the false twisting heater 4, a stretching ratio of 1.89 times, a processing speed of 600 m / min, and a D / Y ratio of 1.64 using the false twisting device shown in FIG. Twist processing was performed. The multifilament fineness of the obtained false twisted yarn is 59.0 dtex, the elongation is 27.5%, the boiling water shrinkage is 6.7%, the elasticity recovery is 40.3%, and the crimp elongation is 22. 4%.
[0069]
The false twisted yarn had a glossiness of 38.6 and a glossiness of 4th grade, and was a false twisted yarn having good glossiness. The false twisting property was as good as 98.6%, and the number of fluffs generated was at an acceptable level of 0.18 / 2000 m. Further, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were good, and the product evaluation was grade 4.
[0070]
Example 2
A polyester composition was obtained in the same manner as in Example 1, except that the amount of the ethylene glycol slurry of titanium oxide particles to be added as a matting agent was 0.040% by weight based on the obtained polymer.
[0071]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0072]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.3%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 40.4% and a crimp elongation of 22.3% was obtained.
[0073]
The degree of irregularity of the undrawn yarn was 1.85. The glossiness of the false twisted yarn is 37.8, the glossiness is 3rd to 4th grade, and the glossiness decreases as the amount of the ethylene glycol slurry of titanium oxide particles added as a matting agent increases, It was a pass level and was a false twisted yarn having a good glossiness. The false twisting property was as good as 98.8%, and the number of fluffs generated was at an acceptable level of 0.14 / 2000 m. Further, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were good, and the product evaluation was grade 4.
[0074]
Example 3
A polyester composition was obtained in the same manner as in Example 1, except that antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was added as a polymerization catalyst to the obtained polymer in an amount of 20 ppm in terms of antimony atoms. Even when antimony trioxide was used as the polymerization catalyst, the polymerization reactivity changed favorably.
[0075]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.00.
[0076]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.0 dtex, the elongation was 27.2%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 40.4% and a crimp elongation of 22.3% was obtained.
[0077]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn has a glossiness of 38.0 and a glossiness of 3rd to 4th grade, and the glossiness is reduced by the amount of antimony trioxide used as the polymerization catalyst, but is at an acceptable level, and the glossiness is good. It was a false twisted yarn. The false twisting property was as good as 98.6%, and the number of fluffs generated was at an acceptable level of 0.20 pieces / 2000 m. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0078]
Example 4
A 2% by weight ethylene glycol solution of a titanium citrate chelate compound is added to the obtained polymer so as to be 3 ppm in terms of titanium atom. After 5 minutes, a 10% by weight ethylene glycol solution of dimethyl phenylphosphonic acid is obtained. A polyester composition was obtained in the same manner as in Example 1, except that it was added to the polymer so as to be 2 ppm in terms of phosphorus atoms.
[0079]
The IV of the obtained polyester composition was 0.64 because the polymerization activity was low due to the small addition amount of the 2% by weight ethylene glycol solution of the titanium citrate chelate compound. there were. The melting point of the polymer was 259 ° C. The content of titanium atoms derived from the titanium catalyst measured from the polymer was 1 ppm, the content of phosphorus atoms was 0.8 ppm, and Ti / P was 1.0.
[0080]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 26.3%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 38.4% and a crimp elongation of 21.3% was obtained.
[0081]
The degree of irregularity of the undrawn yarn was 1.85. The false twisted yarn had a glossiness of 40.5 and a glossiness of 5th grade, and was a false twisted yarn having excellent glossiness. The false twisting property was 98.2%, and the number of fluffs generated was 0.27 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0082]
Example 5
A 2% by weight ethylene glycol solution of a titanium citrate chelate compound is added to the polymer to obtain 50 ppm in terms of titanium atom with respect to the polymer to be obtained. After 5 minutes, a 10% by weight ethylene glycol solution of dimethyl phenylphosphonic acid is obtained. A polyester composition was obtained in the same manner as in Example 1, except that it was added so as to be 40 ppm in terms of phosphorus atom with respect to the polymer.
[0083]
IV of the obtained polyester composition was 0.66. The melting point of the polymer was 259 ° C. The content of titanium atoms derived from the titanium catalyst measured from the polymer was 50 ppm, the content of phosphorus atoms was 40 ppm, and Ti / P was 0.8.
[0084]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 26.3%, the boiling water shrinkage was 6.5%, and the elasticity was restored. A false twisted yarn having a rate of 39.4% and a crimp elongation of 21.8% was obtained.
[0085]
The degree of irregularity of the undrawn yarn was 1.86. The glossiness of the false twisted yarn was 36.8, and the glossiness was tertiary, and the glossiness was reduced by the high content of titanium atoms and phosphorus atoms derived from the titanium catalyst, but was at an acceptable level. The false twisting property was 98.0%, and the number of fluffs generated was 0.35 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grade 3.
[0086]
Example 6
A polyester composition was obtained in the same manner as in Example 1, except that no additional phosphorus compound was added at the start of the polycondensation reaction, and that a titanium citrate chelate compound (phenylphosphonic acid mixture) was used as the polymerization catalyst.
[0087]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0088]
The method for synthesizing the citric acid chelate titanium compound (phenylphosphonic acid mixture) used as the polymerization catalyst is as follows.
[0089]
Citric acid monohydrate (532 g, 2.52 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetraisopropoxide (288 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated at reflux for 1 hour to form a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The product obtained is filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove the isopropanol / water and give a slightly cloudy pale yellow product (Ti content 3 .85% by weight). Phenylphosphonic acid (158 g, 1.00 mol) was added to the mixed solution to obtain a titanium compound containing a phosphorus compound (P content: 2.49% by weight).
[0090]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.4%, the boiling water shrinkage was 6.6%, and the elasticity was restored. A false twisted yarn having a rate of 40.2% and a crimp elongation of 22.1% was obtained.
[0091]
The degree of irregularity of the undrawn yarn was 1.86. The glossiness of the false twisted yarn was 39.1 and the glossiness was 5th grade, and the false twisted yarn had excellent glossiness. The false twisting property was as good as 99.0%, and the number of fluffs generated was at an acceptable level of 0.16 pieces / 2000 m. Further, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were good, and the product evaluation was grade 4.
[0092]
Example 7
A polyester composition was obtained in the same manner as in Example 1, except that no additional phosphorus compound was added at the start of the polycondensation reaction, and a titanium citrate chelate titanium compound (phenylphosphonic acid, phosphoric acid mixture) was used as the polymerization catalyst. Was.
[0093]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 9 ppm, and Ti / P was 0.7.
[0094]
A method for synthesizing a citric acid chelate titanium compound (mixed phenylphosphonic acid and phosphoric acid) used as a polymerization catalyst is as follows.
[0095]
Citric acid monohydrate (532 g, 2.52 mol) was dissolved in warm water (371 g) in a 3 L flask equipped with a stirrer, condenser and thermometer. Titanium tetraisopropoxide (288 g, 1.00 mol) was slowly added to the stirred solution from a dropping funnel. The mixture was heated at reflux for 1 hour to form a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to below 70 ° C., and to the stirring solution was slowly added a 32% w / w aqueous solution of NaOH (380 g, 3.04 mol) via dropping funnel. The product obtained is filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove the isopropanol / water and give a slightly cloudy pale yellow product (Ti content 3 .85% by weight). By adding phenylphosphonic acid (158 g, 1.00 mol) and an 85% w / w aqueous solution of phosphoric acid (39.9 g, 0.35 mol) to the mixed solution, the titanium compound containing the phosphorus compound was added. Was obtained (P content: 3.36% by weight).
[0096]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.4%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 40.1% and a crimp elongation of 22.2% was obtained.
[0097]
The degree of irregularity of the undrawn yarn was 1.87. The false twisted yarn had a glossiness of 40.2 and a glossiness of 5th grade, and was a false twisted yarn having excellent glossiness. The false twisting property was 99.4%, and the number of fluffs generated was 0.08 / 2000 m, which was very good. Also, in the woven fabric and knitting process, there was no stop due to the false twisting yarn factor, the operability was excellent, the glossiness of the woven fabric and the knitted fabric was good, and the product evaluation was grade 5.
[0098]
Example 8
A polyester composition was obtained in the same manner as in Example 1, except that a titanium lactate compound was used as the polymerization catalyst.
[0099]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0100]
The synthesis method of the titanium lactate chelate compound used as the polymerization catalyst is as follows.
[0101]
Ethylene glycol (218 g, 3.51 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 1 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. The reaction mixture was stirred for 15 minutes, and an 85% w / w aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear, pale yellow product (Ti content 6.54%). %).
[0102]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.0%, the boiling water shrinkage was 6.8%, and the elasticity was restored. A false twisted yarn having a rate of 40.1% and a crimp elongation of 22.0% was obtained.
[0103]
The degree of irregularity of the undrawn yarn was 1.86. The glossiness of the false twisted yarn was 39.2, and the glossiness was class 5, which was a false twisted yarn having excellent glossiness. The false twisting property was as good as 98.8%, and the number of fluffs generated was at an acceptable level of 0.16 / 2000 m. Further, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were good, and the product evaluation was grade 4.
[0104]
Example 9
A polyester composition was obtained in the same manner as in Example 1, except that no additional phosphorus compound was added at the start of the polycondensation reaction and a titanium lactate chelate (mixed with phenylphosphonic acid) was used as the polymerization catalyst.
[0105]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.1.
[0106]
The method for synthesizing the titanium lactate chelate compound (phenylphosphonic acid mixture) used as the polymerization catalyst is as follows.
[0107]
Ethylene glycol (218 g, 3.51 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. The reaction mixture was stirred for 15 minutes, and an 85% w / w aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear, pale yellow product (Ti content 6.54%). %). Phenylphosphonic acid (158 g, 1.00 mol) was added to the mixed solution to obtain a phosphorus compound-containing titanium compound (P content: 4.23% by weight). At the start of the polycondensation reaction, no additional phosphorus compound was added.
[0108]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.2 dtex, the elongation was 27.6%, the boiling water shrinkage was 6.8%, and the elasticity was restored. A false twisted yarn having a rate of 39.9% and a crimp elongation of 21.7% was obtained.
[0109]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 38.8 and a glossiness of 4th grade, and was a false twisted yarn having a good glossiness. The false twisting property was as good as 98.6%, and the number of fluffs generated was at an acceptable level of 0.14 / 2000 m. Further, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were good, and the product evaluation was grade 4.
[0110]
Example 10
A polyester composition was obtained in the same manner as in Example 1, except that no additional phosphorus compound was added at the start of the polycondensation reaction, and a titanium lactate chelate compound (phenylphosphonic acid, phosphoric acid mixture) was used as a polymerization catalyst. .
[0111]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 9 ppm, and Ti / P was 0.7.
[0112]
A method for synthesizing a titanium lactate chelate compound (mixed phenylphosphonic acid and phosphoric acid) used as a polymerization catalyst is as follows.
[0113]
Ethylene glycol (218 g, 3.51 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. The reaction mixture was stirred for 15 minutes, and an 85% w / w aqueous solution of ammonium lactate (252 g, 2.00 mol) was added to the reaction flask to give a clear, pale yellow product (Ti content 6.54%). %). By adding phenylphosphonic acid (158 g, 1.00 mol) and an 85% w / w aqueous solution of phosphoric acid (39.9 g, 0.35 mol) to the mixed solution, the titanium compound containing the phosphorus compound was added. Was obtained (P content: 5.71% by weight). At the start of the polycondensation reaction, no additional phosphorus compound was added.
[0114]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.1%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 40.2% and a crimp elongation of 21.7% was obtained.
[0115]
The degree of irregularity of the undrawn yarn was 1.87. The false twisted yarn had a glossiness of 39.6 and a glossiness of 5th grade, and was a false twisted yarn having excellent glossiness. The false twisting property was 99.4%, and the number of fluffs generated was 0.06 / 2000 m, which was very good. Also, in the woven fabric and knitting process, there was no stop due to the false twisting yarn factor, the operability was excellent, the glossiness of the woven fabric and the knitted fabric was good, and the product evaluation was grade 5.
[0116]
Example 11
A polyester composition was obtained in the same manner as in Example 1 except that a tetraisopropoxy titanium compound was used as a polymerization catalyst.
[0117]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0118]
The method for synthesizing the tetrapropoxy titanium compound used as the polymerization catalyst is as follows.
[0119]
Ethylene glycol (496 g, 8.00 mol) was added from a dropping funnel to tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. A 32% w / w aqueous solution of NaOH (125 g, 1.00 mol) was slowly added to the reaction flask via a dropping funnel to give a clear yellow liquid (Ti content 4.44% w / w).
[0120]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 26.9%, the boiling water shrinkage was 6.6%, and the elasticity was restored. A false twisted yarn having a rate of 39.8% and a crimp elongation of 21.6% was obtained.
[0121]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 38.4 and a glossiness of the fourth grade, and was a false twisted yarn having good glossiness. The false twisting property was 98.4%, and the number of fluffs generated was 0.18 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0122]
Example 12
A polyester composition was obtained in the same manner as in Example 1 except that no additional phosphorus compound was added at the start of the polycondensation reaction and a tetrapropoxytitanium compound (mixed with phosphoric acid) was used as a polymerization catalyst.
[0123]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0124]
The method for synthesizing the tetrapropoxy titanium compound (mixed with phosphoric acid) used as the polymerization catalyst is as follows.
[0125]
Ethylene glycol (496 g, 8.00 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. A 32% w / w aqueous solution of NaOH (125 g, 1.00 mol) was slowly added to the reaction flask via a dropping funnel to give a clear yellow liquid (Ti content 4.44% w / w). To this mixed solution was added a 85% by weight / weight aqueous solution of phosphoric acid (114 g, 1.00 mol) (P content: 2.87% by weight).
[0126]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.0%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 40.0% and a crimp elongation of 21.9% was obtained.
[0127]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 38.0 and a glossiness of 4th grade, and was a false twisted yarn having good glossiness. The false twisting property was 98.4%, and the number of fluffs generated was 0.18 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0128]
Example 13
A polyester composition was obtained in the same manner as in Example 1, except that no additional phosphorus compound was added at the start of the polycondensation reaction and a tetrapropoxytitanium compound (ethyl diethylphosphonoacetate mixture) was used as a polymerization catalyst.
[0129]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0130]
The method for synthesizing the titanium alkoxide compound (ethyl diethylphosphonoacetate mixed) used as the polymerization catalyst is as follows.
[0131]
Ethylene glycol (496 g, 8.00 mol) was added from a dropping funnel to titanium tetraisopropoxide (285 g, 1.00 mol) stirred in a 2 L flask equipped with a stirrer, condenser and thermometer. . The rate of addition was adjusted so that the heat of reaction warmed the contents of the flask to about 50 ° C. A 32% w / w aqueous solution of NaOH (125 g, 1.00 mol) was slowly added to the reaction flask via a dropping funnel to give a clear yellow liquid (Ti content 4.44% w / w). Ethyl diethyl phosphonoacetate (224 g, 1.00 mol) was added to the mixed solution to obtain a titanium compound containing a phosphorus compound (P content: 2.87% by weight).
[0132]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 27.0%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 39.9% and a crimp elongation of 21.6% was obtained.
[0133]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 38.2 and a glossiness of 4th grade, and was a false twisted yarn having a good glossiness. The false twisting property was 98.4%, and the number of fluffs generated was 0.20 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0134]
Example 14
A polyester composition was obtained in the same manner as in Example 1, except that a composite oxide composed of titanium and silicon manufactured by Accordis was used as a polymerization catalyst.
[0135]
The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, and Ti / P was 1.0.
[0136]
A polymer obtained from a 0.15% by weight ethylene glycol solution of a composite oxide composed of titanium and silicon (trade name: C-94, hereinafter referred to as Ti / Si composite oxide) manufactured by Accordis, which was used as a polymerization catalyst. After 5 minutes, the solution was added so as to be 6 ppm in terms of phosphorus atoms with respect to the polymer from which a 10% by weight solution of phenylphosphonic acid dimethyl ester in ethylene glycol was obtained.
[0137]
Using the above polyester composition, false twisting was performed in the same manner as in Example 1, and the multifilament fineness was 59.1 dtex, the elongation was 26.8%, the boiling water shrinkage was 6.7%, and the elasticity was restored. A false twisted yarn having a rate of 39.8% and a crimp elongation of 21.9% was obtained.
[0138]
The degree of irregularity of the undrawn yarn was 1.86. The glossiness of the false twisted yarn was 37.1, the glossiness was grade 3, and the glossiness was at an acceptable level. The false twisting property was 98.2%, and the number of fluffs generated was 0.32 pieces / 2000 m, both of which were acceptable levels. In addition, the operability of the woven fabric and the knitting process and the glossiness of the woven fabric and the knitted fabric were acceptable, and the product evaluation was grades 3 and 4.
[0139]
Example 15
A polyester composition was obtained in the same manner as in Example 1. The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, Ti / P = 1.0, and the content of antimony raw thread was 0 ppm.
[0140]
The above-mentioned polyester composition was subjected to false twisting in the same manner as in Example 1 except that the slit length and slit width of the nozzle discharge hole were changed in order to reduce the irregularity of the undrawn yarn. The degree of irregularity of the undrawn yarn was 1.53. The multifilament fineness of the obtained false twisted yarn is 59.0 dtex, the elongation is 28.4%, the boiling water shrinkage is 6.7%, the elasticity recovery is 40.5%, and the crimp elongation is 22. 7%.
[0141]
The glossiness of the false twisted yarn was 36.4, the glossiness was grade 3, and the glossiness was at an acceptable level. The false twisting property was 99.6%, and the number of fluffs generated was very good at 0.06 pieces / 2000 m. Further, the operability of the woven fabric and the knitting process was good, the glossiness of the woven fabric and the knitted fabric was at an acceptable level, and the product evaluation was grade 3.
[0142]
Example 16
A polyester composition was obtained in the same manner as in Example 1. The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, Ti / P = 1.0, and the content of antimony raw thread was 0 ppm.
[0143]
The above polyester composition was subjected to false twisting in the same manner as in Example 1 except that the slit length and slit width of the nozzle discharge hole were changed in order to increase the degree of irregularity of the undrawn yarn. The degree of irregularity of the undrawn yarn was 2.26. The multifilament fineness of the obtained false twisted yarn is 59.0 dtex, the elongation is 26.8%, the boiling water shrinkage is 6.7%, the elastic recovery is 39.6%, and the crimp elongation is 21. 7%.
[0144]
The false twisted yarn had a glossiness of 42.6 and a glossiness of 5th grade, and was a false twisted yarn having excellent glossiness. False twistability was 98.0%, and the number of fluffs generated was 0.42 / 2000 m, which was an acceptable level. In addition, the operability of the woven fabric and the knitting process was at an acceptable level, the glossiness of the woven fabric and the knitted fabric was good, and the product evaluation was grade 3.
[0145]
Comparative Example 1
A polyester composition was obtained in the same manner as in Example 1, except that antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was added as a polymerization catalyst to the obtained polymer in an amount of 400 ppm in terms of antimony atoms. Even when antimony trioxide was used as the polymerization catalyst, the polymerization reactivity changed favorably.
[0146]
The IV of the obtained polyester composition was 0.66, the melting point of the polymer was 259 ° C., and the solution haze was 2.35%.
[0147]
Next, using the polyester composition, false twisting is performed in the same manner as in Example 1, and the multifilament fineness is 59.1 dtex, the elongation is 23.1%, the boiling water shrinkage is 6.5%, A false twisted yarn having an elastic recovery ratio of 36.4% and a crimp elongation ratio of 20.9% was obtained.
[0148]
The degree of irregularity of the undrawn yarn was 1.85. The false twisted yarn had a glossiness of 34.6 and a glossiness of first class, and was a poorly twisted yarn. The false twisting property was 87.6%, the number of fluffs generated was 2.10 / 2000m, and both the false twisting property and the fluff were poor. Further, since the solution haze of the obtained polyester composition was as high as 2.35%, stains on the die surface were remarkable during melt spinning. Furthermore, in the woven fabric and the knitting process, yarn breakage due to false twisting yarn occurred frequently, and frequent stopping occurred. The product was rated first, and both the operability and glossiness were poor.
Comparative Example 2
A polyester composition was obtained in the same manner as in Example 1 except that germanium oxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was added as a polymerization catalyst to the obtained polymer at 150 ppm in terms of germanium atoms. Even when germanium oxide was used as the polymerization catalyst, the polymerization reactivity changed favorably.
[0149]
The IV of the obtained polyester composition was 0.66, the melting point of the polymer was 259 ° C., and the solution haze was 2.08%.
[0150]
Next, using the polyester composition, false twisting is performed in the same manner as in Example 1, and the multifilament fineness is 59.1 dtex, the elongation is 23.3%, the boiling water shrinkage is 6.5%, A false twisted yarn having an elastic recovery ratio of 36.7% and a crimp elongation ratio of 20.9% was obtained.
[0151]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 35.8 and a glossiness of second grade, and was a poorly twisted yarn. The false twisting property was 89.0%, the number of fluffs generated was 1.46 pieces / 2000 m, and both the false twisting property and fluff were poor. Further, in the woven fabric and the knitting process, yarn breakage caused by false twisting yarn occurred frequently, and frequent stopping occurred. The product was rated second, and both the operability and the glossiness were poor.
[0152]
Comparative Example 3
A polyester composition was obtained in the same manner as in Example 1, except that antimony acetate (manufactured by Sumitomo Metal Mining Co., Ltd.) was added to the resulting polymer in an amount of 400 ppm in terms of antimony atoms. Even when antimony acetate was used as the polymerization catalyst, the polymerization reactivity changed favorably.
[0153]
The IV of the obtained polyester composition was 0.66, the melting point of the polymer was 259 ° C., and the solution haze was 2.18%.
[0154]
Next, using the polyester composition, false twisting is performed in the same manner as in Example 1, and the multifilament fineness is 59.1 dtex, the elongation is 23.2%, the boiling water shrinkage is 6.5%, A false twisted yarn having an elastic restoration ratio of 36.6% and a crimp elongation ratio of 21.0% was obtained.
[0155]
The degree of irregularity of the undrawn yarn was 1.86. The false twisted yarn had a glossiness of 34.8 and a glossiness of second grade, and was a poorly twisted yarn. The false twisting property was 88.2%, the number of fluffs generated was 1.32 pieces / 2000 m, and both the false twisting property and fluff were poor. Further, in the woven fabric and the knitting process, yarn breakage caused by false twisting yarn occurred frequently, and frequent stopping occurred. The product was rated second, and both the operability and the glossiness were poor.
[0156]
Comparative Example 4
A polyester composition was obtained in the same manner as in Example 1. The IV of the obtained polyester composition was 0.66, and the melting point of the polymer was 259 ° C. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer was 10 ppm, the content of phosphorus atoms was 6 ppm, Ti / P = 1.0, and the content of antimony raw thread was 0 ppm.
[0157]
False twisting was performed on the polyester composition in the same manner as in Example 1 except that a circular die discharge hole was used. The multifilament fineness of the obtained false twisted yarn is 59.0 dtex, the elongation is 28.8%, the boiling water shrinkage is 6.7%, the elasticity recovery is 39.9%, and the crimp elongation is 21. 8%.
[0158]
The false twisted yarn had a glossiness of 33.2 and a glossiness of the first grade, and was a poorly twisted yarn. The false twisting property was 99.6%, and the number of fluffs generated was 0.04 pieces / 2000 m. The operability of the woven fabric and the knitting process was acceptable, but the glossiness of the woven fabric and knitted fabric was poor, and the product evaluation was first class.
[0159]
[Table 1]

[0160]
[Table 2]

[0161]
【The invention's effect】
By using the false twisted yarn of the present invention, a fabric excellent in glossiness can be provided, and the generation of fluff and breakage in a woven fabric process or a knitting process is small, and a loom or knitting machine is used. Since there are few stops, the fabric can be provided with stable productivity.
[Brief description of the drawings]
FIG. 1 is a schematic view showing an example of a false twisting step in the present invention.
[Explanation of symbols]
1: undrawn yarn 2: yarn unwinding guide 3: supply roll 4: false twist heater 5: false twisting tool 6: take-up roller 7: second take-up roller 8: false twisted yarn cheese

Claims (14)

A polyester produced by using a titanium compound (excluding titanium dioxide particles) as a main catalyst, and containing no antimony compound or containing 30 ppm or less in terms of antimony atoms based on the polyester, A polyester false twisted yarn, wherein the content of inorganic oxide particles used as a matting agent is 0.04% by weight or less, and the cross-section of an undrawn yarn before false twisting is irregular. The titanium compound (excluding titanium dioxide particles) is contained in an amount of 0.5 to 150 ppm in terms of titanium atoms relative to polyester, and the phosphorus compound is contained in an amount of 0.1 to 400 ppm in terms of phosphorus atoms relative to polyester. Polyester false twisted yarn comprising a polyester composition. 3. The polyester composition according to claim 1, wherein the ratio of the titanium compound (excluding titanium dioxide particles) to the phosphorus compound is Ti / P = 0.1 to 20 as a molar ratio of titanium atoms to phosphorus atoms. 4. Polyester false twisted yarn. The manganese compound is contained in an amount of 1 to 400 ppm in terms of manganese atom with respect to the polyester, and the ratio of the manganese compound to the phosphorus compound is Mn / P = 0.1 to 200 as a molar ratio of the manganese atom to the phosphorus atom. Item 5. A polyester false twisted yarn comprising the polyester composition according to any one of Items 1 to 3. The phosphorus compound is a phosphoric acid type, a phosphorous acid type, a phosphonic acid type, a phosphinic acid type, a phosphine oxide type, a phosphonous acid type, a phosphinous acid type, or a phosphine type. A polyester false twisted yarn comprising the polyester composition according to claim 1. The polyester false twisted yarn comprising the polyester composition according to claim 5, wherein the phosphoric acid-based phosphorus compound is a phosphoric acid and / or a phosphoric ester compound. The polyester false twisted yarn comprising the polyester composition according to claim 5, wherein the phosphonic acid-based phosphorus compound is a phosphonic acid and / or a phosphonate ester compound. The polyester false twisted yarn comprising the polyester composition according to any one of claims 1 to 7, wherein the titanium compound is an oxide. The polyester false-twisted yarn comprising the polyester composition according to claim 8, wherein the titanium compound is a composite oxide in which a main metal element comprises titanium and silicon. The polyester compound according to any one of claims 1 to 7, wherein the substituent of the titanium compound is at least one selected from the group consisting of functional groups represented by the following formulas (1) to (6). Polyester false twisted yarn.

(In Formulas 1 to 6, R _{1 to} R ₃ each independently have hydrogen, a hydrocarbon group having 1 to 30 carbon atoms, an alkoxy group, a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, an ester group, or an amino group. Represents a hydrocarbon group having 1 to 30 carbon atoms.) Polyester false twisted yarn comprising a polyester composition according to claim 10, wherein a hydrocarbon group of Formulas 1 to 3 of R ₁ to R ₃ hydrogen or C1-30 to each independently. In Formulas 1 to 3, at least one of R _{1 to} R ₃ is a hydrocarbon group having 1 to 30 carbon atoms having a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group, or an ester group. Item 11. A polyester false twisted yarn comprising the polyester composition according to Item 10. The polyester false twist made of the polyester composition according to claim 12, wherein at least one of R _{1 to} R _{3 in} the formula 1 is a hydrocarbon group having a carboxyl group or an ester group and having 1 to 30 carbon atoms. Processing thread. R _{1 in the} formula 4 is a hydrocarbon group having 1 to 30 carbon atoms, or a hydrocarbon group having 1 to 30 carbon atoms having a hydroxyl group, a carbonyl group, an acetyl group, a carboxyl group or an ester group. A polyester false twisted yarn comprising the polyester composition according to 10.

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