JP2005042218A - Superfine polyester multifilament - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a superfine polyester multifilament which has more excellent heat resistance and Uster irregularity than those of conventional superfine polyester multifilaments. <P>SOLUTION: This superfine polyester multifilament produced in the presence of a catalyst consisting mainly of a titanium compound (excluding titanium dioxide particles) and having a single filament fineness of ≤1.5 dtex comprises a polyester characterized by containing the titanium compound in an amount of 0.5 to 150 ppm converted into titanium atom on the basis of the polyester, a phosphorus compound in an amount of 0.1 to 400 ppm converted into phosphorus atom on the basis of the polyester, and not containing an antimony compound or containing the antimony compound in an amount of ≤30 ppm converted into antimony atom on the basis of the polyester. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

【００２７】
（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。
【００２８】
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。
【００２９】
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。
【００３０】
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。
【００３１】
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。
【００３２】
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およびウースター斑改善の点から好ましい。
【００３３】
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。
【００３４】
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。
【００３５】
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。
【００３６】
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。
【００３７】
なお、本発明に用いるポリエステルに含有されるリンは、ポリエステル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、例えばリン酸系としては、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。亜リン酸系としては、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。ホスホン酸系としては、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。ホスフィン酸系としては、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。ホスフィンオキサイド系としては、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。亜ホスホン酸系としては、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。亜ホスフィン酸系としては、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。ホスフィン系としては、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。
【００３８】
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の熱安定性やウースター斑改善の点から好ましい。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。
【００３９】
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。
【００４０】
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。
【００４１】
本発明のポリエステル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エステルを用いた極細ポリエステルマルチフィラメントのウースター斑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。
【００４２】
また、本発明のポリエステル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エステルを用いた極細ポリエステルマルチフィラメントのウースター斑が一層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。
【００４３】
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。
【００４４】
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。
【００４５】
本発明に用いるポリエステル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。
【００４６】
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、前述の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。
【００４７】
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。
【００４８】
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。
【００４９】
次に本発明の極細ポリエステルマルチフィラメント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を用いた極細ポリエステルマルチフィラメントの例を記載するがこれに限定されるものではない。
【００５０】
極細ポリエステルマルチフィラメントは通常、（１）ポリエステルを溶融し、計量し、濾過した後に吐出するプロセス、（２）吐出されたポリエステルフィラメントを冷却風により冷却した後引き取るプロセス、（３）引き取られたポリエステルフィラメントを巻き取るプロセスおよび（４）巻き取られたポリエステルマルチフィラメントをさらに熱延伸し極細ポリエステルマルチフィラメントを得るプロセスにより得られる。また上記（３）のプロセスにおいて直接極細ポリエステルマルチフィラメントを得ることも可能であり、また上記（２）のプロセスにおいて冷却風による冷却に引き続いて加熱域で延伸し、次いで（３）のプロセスを経て極細ポリエステルマルチフィラメントを得ることも可能である。また（３）のプロセスにおいて引き取ったポリエステルマルチフィラメントを一旦巻き取ることなく加熱ローラーで延伸、熱処理した後巻き取る方法によっても極細ポリエステルマルチフィラメントを得ることが可能である。
【００５１】
本発明の極細ポリエステルマルチフィラメントの単糸繊度は１．５ｄｔｅｘ以下とする必要がある。単糸繊度が１．５ｄｔｅｘより大きい場合、従来の極細ポリエステルマルチフィラメントの欠点であるウースター斑がそれほど悪くないため、本発明の効果が小さなものとなる。ウースター斑が大きく改善され、本発明の効果がより大きくなる点から、単糸繊度は１．０ｄｔｅｘ以下とすることがより好ましく、０．７ｄｔｅｘ以下とすることがさらに好ましい。
【００５２】
【実施例】
以下実施例により本発明をさらに詳細に説明する。なお、実施例中の物性値は以下に述べる方法で測定した。
（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、マンガン元素およびコバルト元素の含有量
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、アンチモン元素及びマンガン元素の分析を行った。
【００５３】
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ＩＶ
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プ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）ウースター斑
ｚｅｌｌｗｅｇｅｒ社製ウスター糸斑測定機を用い、糸速度２００ｍ／分、撚り数１２０００Ｔ／ｍで１分間測定する間の平均値を算出しウースター斑とした。
（６）加工糸切れ判定
３０ｄｔｅｘ１２フィラメントで、１００℃、３０分の沸水処理における収縮率が３０％であるフィラメントとの複合仮撚を、延伸倍率１．２倍、加工速度７００ｍ／分の条件で１０８錘で同時に実施した際の糸切れ回数を測定し、１回以下なら◎、２〜３回なら○、４〜５回なら△、６回以上なら×とした。
【００５４】
実施例１
Ａ．ポリエチレンテレフタレートの製造方法
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。
【００５５】
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０．３重量％添加した。５分間撹拌した後、塩化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２０ｐｐｍ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０．５ｐｐｍとなるように添加し、５分後、リン酸の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１０ｐｐｍ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。
【００５６】
得られたポリマーのＩＶは０．６６、ポリマーの融点は２５９℃、溶液ヘイズは０．７％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０．５ｐｐｍ、リン原子の含有量は１０ｐｐｍであり、Ｔｉ／Ｐ＝０．０３であり、アンチモン原子の含有量は０ｐｐｍであることを確認した。
【００５７】
また、このポリエステルを乾燥後、紡糸機に供し、メルターにて溶融した後、計量し紡糸口金から吐出し、１８５０ｍ／分の速度で引取った。得られた未延伸糸を８８℃で２．８倍に延伸した後、ホットプレート（１３０℃）で熱セットし、５０デシテックス７２フィラメントの延伸糸を得た。ウースター斑は０．８７であり、糸切れ判定は△、加工糸切れ判定は△となった。
【００５８】
なお、以下に触媒の合成方法を記す。
【００５９】
触媒Ａ．クエン酸キレートチタン化合物の合成方法
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。
【００６０】
触媒Ｂ．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
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％）。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。
【００６１】
触媒Ｃ．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
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％）。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。
【００６２】
触媒Ｄ．乳酸キレートチタン化合物の合成方法
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。得られたチタン化合物は実施例１と同様、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、リン酸の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１０ｐｐｍとなるように添加し、重合を行った。
【００６３】
触媒Ｅ．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
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。
【００６４】
触媒Ｆ．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
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。
【００６５】
触媒Ｇ．チタンアルコキシド化合物の合成方法
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％）。得られたチタン化合物は実施例１と同様、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３０ｐｐｍとなるように添加し、５分後、ジエチルホスホノ酢酸エチルの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１０ｐｐｍとなるように添加し、重合を行った。
【００６６】
触媒Ｈ．チタンアルコキシド化合物（リン酸混合）の合成方法
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％）。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。
【００６７】
触媒Ｉ．チタンアルコキシド化合物（ジエチルホスホノ酢酸エチル混合）の合成方法
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％）。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。
【００６８】
触媒Ｊ．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
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１０ｐｐｍとなるように添加した。
【００６９】
実施例２〜７、比較例１、２
触媒として用いたクエン酸キレートチタン化合物の添加量を得られるポリマーに対してチタン原子換算で１．２、３、３０、５０、１００、１５０、０．３、２００ｐｐｍ（それぞれ実施例２、３、４、５、６、７、比較例１、２）とした以外は実施例１と同様の方法で重合し、溶融紡糸し、延伸を行った。チタン化合物量を変更しても重合反応性は良好に推移するが、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑は表１に示した結果となり、実施例２〜７についてはいずれも良好な結果となったが比較例１、２はウースター斑が悪化し、糸切れは△または×判定、加工糸切れは×判定となった。
【００７０】
実施例８
触媒として用いたクエン酸キレートチタン化合物の添加量を得られるポリマーに対してチタン原子換算で２０ｐｐｍとし、リン酸の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０．１ｐｐｍとなるように添加した以外は実施例１と同様の方法で重合し、溶融紡糸し、延伸を行った。チタン化合物量を変更しても重合反応性は良好に推移し、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑は表１に示したとおり良好な結果となった。
【００７１】
実施例９〜１５、比較例３、４
リン酸の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１、３、５０、１００、１５０、２００、４００、０．０７、５００ｐｐｍ（それぞれ実施例９、１０、１１、１２、１３、１４、１５）となるように添加した以外は実施例８と同様の方法で重合し、溶融紡糸し、延伸を行った。リン化合物量を変更しても重合反応性は良好に推移したが、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑は表１に示したとおりであり、実施例９〜１５については良好な結果を得たが、比較例３および４では糸切れが多発し、ウースター斑も悪化し、加工糸切れも多発した。
【００７２】
実施例１６、１７、比較例５
触媒としてチタン化合物の他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１０、３０、４０ｐｐｍ添加したこと以外は実施例４と同様にして重合し、溶融紡糸し、延伸を行った。三酸化アンチモン量を変更しても重合反応性は良好に推移したが、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑は表１に示したとおりであり、実施例１６、１７については良好な結果が得られたが、比較例５では糸切れが多発し、ウースター斑も悪化した。また加工糸切れも多発した。
【００７３】
実施例１８〜２３
エチレングリコール溶液として加える酢酸マンガンを、得られるポリマーに対してマンガン原子換算でそれぞれ０．７、１、１００、２５０、４００、５００ｐｐｍ（それぞれ実施例１８、１９、２０、２１、２２、２３）となるように加えたこと以外は実施例４と同様にして重合し、溶融紡糸し、延伸を行った。マンガン化合物量を変更しても重合反応性は良好に推移し、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑についても表２に示したとおり良好な結果を得た。
【００７４】
実施例２４
エチレングリコール溶液として加える酢酸マンガンを、得られるポリマーに対してマンガン原子換算でそれぞれ５００ｐｐｍとなるように、またリン酸の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となるように添加した以外は実施例４と同様にして重合し、溶融紡糸し、延伸を行った。マンガン化合物量およびリン化合物量を変更しても重合反応性は良好に推移し、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑についても表２に示したとおり良好な結果を得た。
【００７５】
実施例２５〜３３
触媒として用いるチタン化合物をそれぞれ触媒Ｂ、Ｃ、Ｄ、Ｅ、Ｆ、Ｇ、Ｈ、Ｉ、Ｊ（それぞれ実施例２５、２６、２７、２８、２９、３０、３１、３２、３３）とした以外は実施例４と同様にして重合し、溶融紡糸し、延伸を行った。チタン化合物の種類を変更しても重合反応性は良好に推移し、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑についても表２に示したとおり良好な結果を得た。
【００７６】
実施例３４、３５
エチレングリコール溶液として加える塩化コバルトを酢酸コバルト（実施例３４）、なし（実施例３５）とした以外は実施例４と同様にして重合し、溶融紡糸し、延伸を行った。チタン化合物の種類を変更しても重合反応性は良好に推移し、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑についても表２に示したとおり良好な結果を得た。
【００７７】
実施例３６、３７
実施例４と同様の方法で重合した後、溶融紡糸する際、吐出量のみを変更し、得られるポリエステルマルチフィラメントを８４デシテックス７２フィラメント（実施例３６）、１０８デシテックス７２フィラメント（実施例３７）とした以外は実施例４と同様にして溶融紡糸し、延伸を行った。単糸繊度を大きくしたが、溶融紡糸時の糸切れおよび得られるポリエステルマルチフィラメントのウースター斑についても表２に示したとおり良好な結果を得た。
【００７８】
比較例６
触媒にチタン化合物を用いず、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３００ｐｐｍ添加したこと以外は実施例１と同様にして重合し、溶融紡糸を行った。触媒を変更しても重合反応性は良好に推移するが、得られるポリマーの溶液ヘイズは２．４％と高く、また表２に示したとおり、溶融紡糸時に糸切れが多発し、ウースター斑も大幅に悪化した。また加工糸切れも多発した。
【００７９】
【表１】

【００８０】
【表２】

【００８１】
【発明の効果】
本発明の極細ポリエステルマルチフィラメントは、耐熱性およびウースター斑が大きく改善されることにより、そのソフト感および均一性を特徴とする織物、編物に好適に用いることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an ultrafine polyester multifilament that has been excellent in heat resistance and Worcester spots.
[0002]
[Prior art]
Polyester multifilaments represented by polyethylene terephthalate are fibers with high strength, high Young's modulus, and excellent thermal dimensional stability, and are widely used for clothing and industrial materials. Further, among clothing, those having a single yarn fineness of 1.5 dtex or less are generally regarded as ultrafine yarns, and such multifilaments having a single yarn fineness are used in various applications due to their soft feeling. Yes. For example, by applying false twisting after mixing with high-shrinkage yarn, the high-shrinkage yarn becomes the core side and the ultrafine yarn becomes the sheath side. Fiber can be provided.
[0003]
However, while the ultrafine polyester multifilament has the above-mentioned excellent characteristics, it has various problems in its quality because of its fine single yarn fineness.
[0004]
The first point is that Worcester spots, stained spots, etc. may be deteriorated by minute foreign matters resulting from catalyst residues in the polymer. It is believed that foreign matter in the polymer deteriorates Wooster spots and the like because it affects the structure formation during melt spinning of the filament.
[0005]
The second point is that the uniformity of the surface is impaired by the foreign matter, and the frictional characteristics of the multifilament may be uneven. Although the mechanism is not clear, it is considered that when the amount of foreign matter generated is large, the amount of foreign matter exposed on the surface increases and the friction characteristics change.
[0006]
In order to solve such problems, various proposals such as spinning temperature, cooling conditions after melt discharge, and optimization of the spinneret have been made, but these alone are not effective for improvement and constitute a fundamental solution. Absent. In the process of producing a polyester multifilament by reheating and non-contact stretching after cooling once after melt discharge, a solution to the above problem has been proposed by defining the distance from the spinneret to the reheating non-contact stretching region. The effect is not sufficient (see Patent Document 1).
[0007]
There are also attempts to solve this problem by improving the polymer.
Attempts have been made to solve various problems such as clogging of the spinneret and yarn breakage at the time of melt spinning by using an aluminum compound, a phosphorus compound and a phenolic compound in combination as a polymerization catalyst. Patent Document 2). However, the aluminum compound has low activity as a polymerization catalyst and the polymerization time is prolonged, resulting in a decrease in productivity, and the color of the resulting polymer is more yellowish than the polymer obtained by the conventional antimony catalyst, and also has heat resistance. However, it has not been put into practical use. In addition, a method for suppressing the formation of foreign substances in the polymer by using a composite oxide of titanium and silicon as a catalyst has been studied. However, the polyester polymer obtained by this method is not sufficient for suppressing the generation of foreign substances, and the ultrafine polyester Not suitable for filaments (see Patent Document 3).
[0008]
On the other hand, the proposal which uses the titanium complex which consists of a titanium compound and a phosphorus compound as a polymerization catalyst as a catalyst for polyester polymerization is made (refer patent documents 4-6). Although this method can reduce foreign matters caused by the catalyst, the effect is not sufficient. Accordingly, there is a need for further improvements in titanium compounds.
[0009]
As described above, in the current state of the art, it has not been realized to improve the heat resistance and Wooster spots of ultrafine polyester multifilaments by modifying polymers.
[0010]
[Patent Document 1]
JP 61-215714 A (first page)
[0011]
[Patent Document 2]
JP 2002-227033 A (first page)
[0012]
[Patent Document 3]
JP 2001-348728 A (first page)
[0013]
[Patent Document 4]
JP 2001-524536 A (1st page)
[0014]
[Patent Document 5]
Japanese translation of PCT publication No. 2002-512267 (first page)
[0015]
[Patent Document 6]
JP 2002-293909 A (first page)
[0016]
[Problems to be solved by the invention]
The inventors of the present invention have fundamentally studied from a polymer in order to obtain ultrafine polyester multifilaments having superior heat resistance and improved Wooster spots, and have reached the ultrafine polyester multifilaments of the present invention. It is a thing.
[0017]
[Means for Solving the Problems]
An object of the present invention described above is a polyester produced using a titanium compound (excluding titanium dioxide particles) as a main catalyst, containing 0.5 to 150 ppm of the titanium compound in terms of titanium atom relative to the polyester, and a phosphorus compound as the polyester. 0.1 to 400 ppm in terms of phosphorus atoms, and no polyester or 30 ppm or less in terms of antimony atoms in terms of polyester, ultrafine polyester multis composed of filaments having a single yarn of 1.5 dtex or less Can be achieved with filaments.
[0018]
DETAILED DESCRIPTION OF THE INVENTION
The titanium compound catalyst for producing the polyester used in the present invention needs to be 0.5 to 150 ppm in terms of titanium atom relative to the polyester. When the amount is less than 0.5 ppm, the polymerization activity is not sufficient, so that it is necessary to lengthen the polymerization time, which is not suitable for commercial production. On the other hand, when the content is more than 150 ppm, the polymerization activity is sufficient, but the resulting polyester has an insufficient color tone. From these viewpoints, the amount of the titanium compound catalyst for producing the polyester used in the present invention is preferably 1 to 100 ppm, more preferably 3 to 50 ppm.
[0019]
The phosphorus compound for producing the polyester used in the present invention needs to be 0.1 to 400 ppm in terms of phosphorus atom relative to the polyester. When the amount is less than 0.1 ppm, the production of foreign matter is not sufficiently suppressed and the effect of the present invention is not sufficient. On the other hand, if it exceeds 400 ppm, the polymerization activity is not sufficient, so that it is necessary to lengthen the polymerization time, which is not suitable for commercial production. From this point, 1 to 200 ppm is preferable, and 3 to 100 ppm is more preferable.
[0020]
The antimony compound as a polymerization catalyst for producing the polyester used in the present invention needs to be 30 ppm or less in terms of antimony atoms relative to the polyester. When it is more than 30 ppm, the improvement of Wooster spots, which is a feature of the present invention, is insufficient. From the viewpoint of improving Wooster spots, it is preferably 10 ppm or less, and further preferably not contained.
[0021]
In the method for producing a polyester multifilament of the present invention, the polyester may be melted and discharged from a spinneret, taken up, and then wound up, and then drawn, or may be drawn after being taken up. Alternatively, it may be cooled once after melting and discharging, and then directly wound at a speed of 5500 m / min or more, or may be taken up after being led to a non-contact heating and stretching region after cooling and then taken up.
[0022]
The polyester of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. What can be used as molded articles, such as a fiber, a film, and a bottle, is preferable.
[0023]
Specific examples of such polyesters include polyethylene terephthalate, polypropylene 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 suitable for polyethylene terephthalate or polyester copolymers mainly containing ethylene terephthalate units, which are most commonly used.
[0024]
In addition to diethylene glycol, these polyesters include dicarboxylic acids such as adipic acid, isophthalic acid, sebacic acid, phthalic acid, naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and cyclohexanedicarboxylic acid, and esters thereof. Formable derivatives, dioxy compounds such as polyethylene glycol, hexamethylene glycol, neopentyl glycol, polypropylene glycol and cyclohexanedimethanol, oxycarboxylic acids such as p- (β-oxyethoxy) benzoic acid and ester-forming derivatives thereof It may be polymerized.
[0025]
In the polyester of the present invention, examples of the titanium compound that can be used as a catalyst include titanium compounds in which the substituent of the titanium compound is at least one selected from the group consisting of functional groups represented by the following general formulas 1 to 6. It is done.
[0026]
[Chemical 2]

[0027]
(In Formula 1 to Formula 6, R ₁ ~ R ₃ Each independently represents 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, and a hydrocarbon group having 1 to 30 carbon atoms. )
Formula 1 of the present invention comprises an alkoxy group such as ethoxide, propoxide, isopropoxide, butoxide, 2-ethylhexoxide, or the like, or a hydroxy polyvalent carboxylic acid compound such as lactic acid, malic acid, tartaric acid, citric acid, etc. A functional group is mentioned.
[0028]
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.
[0029]
Moreover, as Formula 3, the functional group which consists of phenoxy, cresylate, salicylic acid, etc. is mentioned.
[0030]
Formula 4 includes acylate groups such as lactate and stearate, phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacin Polycarboxylic acid compounds such as acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or their anhydrides, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid And functional groups composed of nitrogen-containing polyvalent carboxylic acids such as triethylenetetraminohexaacetic acid, iminodiacetic acid, iminodipropionic acid, hydroxyethyliminodiacetic acid, hydroxyethyliminodipropionic acid, and methoxyethyliminodiacetic acid.
[0031]
Formula 5 includes functional groups composed of aniline, phenylamine, diphenylamine, and the like.
[0032]
Among these, it is preferable that Formula 1 and / or Formula 4 is included from the viewpoint of thermal stability of the polymer and improvement of Wooster spots.
[0033]
Examples of the titanium compound include titanium diisopropoxybisacetylacetonate and titanium triethanolamate isopropoxide containing two or more of the substituents represented by formulas 1 to 6.
[0034]
In addition, examples of the titanium oxide include composite oxides whose main metal elements are titanium and silicon.
[0035]
The catalyst of the present invention is a polymer synthesized from a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof. All or some of the following reactions (1) to (3) Refers to a compound that substantially contributes to the promotion of the reaction.
(1) Esterification reaction that is a reaction between a dicarboxylic acid component and a diol component
(2) Transesterification reaction, which is a reaction between an ester-forming derivative component of dicarboxylic acid and a diol component
(3) A polycondensation reaction in which the ester reaction or transesterification reaction is substantially completed, and the resulting polyethylene terephthalate low polymer is highly polymerized by a dediol reaction.
Therefore, titanium dioxide particles generally used as inorganic particles in fiber matting agents and the like have substantially no catalytic effect on the above reaction and can be used as the catalyst of the present invention. Different from titanium compounds.
[0036]
A method for producing a 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 by a hydrolysis reaction using an alkoxide compound of titanium as a raw material, by controlling the rate of hydrolysis, can get. Specifically, for example, a titanium alkoxide compound as a main raw material is allowed to coexist with a small amount of another metal alkoxide compound such as silicon or zirconium or a polyhydric alcohol compound, and both coprecipitation method, partial hydrolysis method, distribution It can be synthesized by a coordinate chemical sol-gel method or the like. 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 preliminarily hydrolyzed, and the other component is added thereto to further proceed hydrolysis. The coordination chemical sol-gel method is a method in which a polyhydric alcohol compound having a plurality of functional groups in the molecule is coexisted together with a titanium alkoxide raw material, and a reaction product is formed between the two in advance, thereby allowing subsequent hydrolysis. It is intended to control the rate of reaction. For example, Ueno et al., “Catalyst Preparation Using Metal Alkoxide”, page 321 line 1 to page 353 line 16 (IPC, issued on August 10, 1993). Etc. are described.
[0037]
In addition, the phosphorus contained in the polyester used for this invention is added as a phosphorus compound in the manufacturing process of polyester. Examples of such phosphorus compounds include one or two of phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinic acid, and phosphine compounds. It is preferable. Specifically, for example, phosphoric acid, phosphoric acid, trimethyl phosphate, triethyl phosphate, triphenyl phosphate and the like. Examples of the phosphorous acid system include phosphorous acid, trimethyl phosphite, triethyl phosphite, and triphenyl phosphite. Examples of phosphonic acids include methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, isopropylphosphonic acid, butylphosphonic acid, phenylphosphonic acid, benzylphosphonic acid, tolylphosphonic acid, xylylphosphonic acid, biphenylphosphonic acid, naphthylphosphonic acid, Anthrylphosphonic acid, 2-carboxyphenylphosphonic acid, 3-carboxyphenylphosphonic acid, 4-carboxyphenylphosphonic acid, 2,3-dicarboxyphenylphosphonic acid, 2,4-dicarboxyphenylphosphonic acid, 2,5- Dicarboxyphenylphosphonic acid, 2,6-dicarboxyphenylphosphonic acid, 3,4-dicarboxyphenylphosphonic acid, 3,5-dicarboxyphenylphosphonic acid, 2,3,4-tricarboxyphenylphosphonic acid, 2, 3,5-tri Ruboxyphenylphosphonic acid, 2,3,6-tricarboxyphenylphosphonic acid, 2,4,5-tricarboxyphenylphosphonic acid, 2,4,6-tricarboxyphenylphosphonic acid, methylphosphonic acid dimethyl ester, methylphosphonic acid diethyl Ester, ethylphosphonic acid dimethyl ester, ethylphosphonic 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 diphenyl ester, Lithium (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), sodium (3,5-di-tert-butyl-4-hydroxyben Ethyl phosphonate), magnesium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), calcium bis (ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), diethyl Phosphonoacetic acid, diethyl phosphonoacetate methyl, diethyl phosphonoacetate ethyl and the like. As the phosphinic acid system, 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, dixylphosphinic 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-tricarboxyphenylphosphinic acid, 2,3,5-tricarboxyphenylphosphinic acid, 2,3,6-tricarboxyphenylphosphinic acid, 2,4,5-tricarboxyphenylphosphinic acid, 2, 4,6-tricarboxyphenylphosphinic 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-dicarboxypheny) ) Phosphinic acid, bis (2,5-dicarboxyphenyl) phosphinic acid, bis (2,6-dicarboxyphenyl) phosphinic acid, bis (3,4-dicarboxyphenyl) phosphinic acid, bis (3,5-di) Carboxyphenyl) 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, methylphosphinic acid methyl ester, dimethylphosphinic acid methyl ester, methylphosphinic acid ethyl ester, Dimethylphosphinic acid ethyl ester, ethylphosphinic acid methyl ester Steal, diethylphosphinic acid methyl ester, ethylphosphinic acid ethyl ester, diethylphosphinic acid ethyl ester, phenylphosphinic acid methyl ester, phenylphosphinic acid ethyl ester, phenylphosphinic acid phenyl ester, diphenylphosphinic 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, bisbenzylphosphinic acid phenyl ester and the like. Examples of the phosphine oxide include trimethylphosphine oxide, triethylphosphine oxide, tripropylphosphine oxide, triisopropylphosphine oxide, tributylphosphine oxide, and triphenylphosphine oxide. Examples of the phosphonous acid system include methylphosphonous acid, ethylphosphonous acid, propylphosphonous acid, isopropylphosphonous acid, butylphosphonous acid, and phenylphosphonous acid. The phosphinic acid system includes methylphosphinic acid, ethylphosphinic acid, propylphosphinic acid, isopropylphosphinic acid, butylphosphinic acid, phenylphosphinic acid, dimethylphosphinic acid, diethylphosphinic acid, dipropylphosphinic acid Acids, diisopropylphosphinic acid, dibutylphosphinic acid, diphenylphosphinic acid and the like. Examples of the phosphine group include methylphosphine, dimethylphosphine, trimethylphosphine, melephosphine, diethylphosphine, triethylphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, and the like. preferable. In particular, from the viewpoints of thermal stability and color tone improvement, phosphoric acid and / or phosphonic acid are preferable.
[0038]
Moreover, it is preferable from the point of the thermal stability of polyester and the Wooster spot improvement that it is Ti / P = 0.1-20 by the molar ratio as a phosphorus atom with respect to the titanium atom of a titanium compound. More preferably, it is Ti / P = 0.2-10, More preferably, Ti / P = 0.3-5.
[0039]
The titanium compound and phosphorus compound used in the present invention may be added to the polyester reaction system as they are, but are mixed in advance with a solvent containing a diol component that forms a polyester such as ethylene glycol or propylene glycol to form a solution or slurry. If necessary, it is preferable to remove low-boiling components such as alcohol used in the synthesis of the titanium compound or phosphorus compound and then add to the reaction system, since foreign matter formation in the polymer is further suppressed. The addition time includes an esterification reaction catalyst and a transesterification reaction catalyst, a method of adding the catalyst immediately after the addition of the raw material, and a method of adding it 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 completion of the reaction, before the polycondensation reaction catalyst is started. It may be added. In this case, in order to suppress the deactivation of the catalyst due to the contact between the titanium compound and the phosphorus compound, a method of adding to a different reaction tank, 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.
[0040]
In the present invention, a titanium compound previously reacted with a phosphorus compound can also be used as a catalyst. In this case, (1) a titanium compound is mixed with a solvent, a part or all of the titanium compound is dissolved in the solvent, and the phosphorus compound is dissolved and diluted in the stock solution or the solvent and added dropwise to the mixed solution. (2) In the case of using a ligand of a titanium compound such as a hydroxycarboxylic acid compound or a polyvalent carboxylic acid compound, the titanium compound or the ligand compound is mixed in a solvent, and a part or all thereof is mixed in the solvent. Dissolve, and dissolve and dilute the ligand compound or titanium compound in the stock solution or solvent in this mixed solution. Moreover, it is preferable from the viewpoint of thermal stability and color tone improvement that a phosphorus compound is further dissolved and diluted in a stock solution or a solvent and added dropwise to the mixed solution. Said reaction conditions are performed by heating at the temperature of 0-200 degreeC for 1 minute or more, Preferably it is 2-100 minutes at the temperature of 20-100 degreeC. 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 a part or all of the titanium compound, phosphorus compound and carbonyl group-containing compound, preferably water, methanol, ethanol, ethylene glycol, propane. It is selected from diol, butanediol, benzene and xylene.
[0041]
In the method for producing the polyester of the present invention, the manganese compound is contained at 1 to 400 ppm in terms of manganese atom relative to the polyester at an arbitrary time, and the ratio of manganese compound to phosphorus compound is Mn / P = 0. When it is added so as to be 1 to 200, the decrease in polymerization activity can be suppressed, and the Wooster spots of the ultrafine polyester multifilament using the polyester obtained thereby are preferable. The manganese compound used in this case is not particularly limited. Specifically, for example, manganese chloride, manganese bromide, manganese nitrate, manganese carbonate, manganese acetylacetonate, manganese acetate tetrahydrate, manganese acetate dihydrate Etc.
[0042]
Further, in the method for producing a polyester of the present invention, Worcester spots of ultrafine polyester multifilaments using a polyester obtained by further adding a cobalt compound at an arbitrary time are preferable. The cobalt compound used in this case is not particularly limited, and specific examples include cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt acetylacetonate, cobalt naphthenate, and cobalt acetate tetrahydrate.
[0043]
Moreover, you may add an alkali metal compound, an alkaline-earth metal compound, an aluminum compound, a zinc compound, a tin compound, etc. in order to improve the color tone of the polymer obtained, and the heat resistance of a polymer.
[0044]
In addition to particles such as titanium dioxide, silicon oxide, calcium carbonate, silicon nitride, clay, talc, kaolin and carbon black, additives such as anti-coloring agents, stabilizers and antioxidants may be included. .
[0045]
A method for producing the polyester used in the present invention will be described. Although the example of a polyethylene terephthalate is described as a specific example, it is not limited to this.
[0046]
Polyethylene terephthalate is usually produced by one of the following processes. (1) A process in which terephthalic acid and ethylene glycol are used as raw materials, a low polymer is obtained by direct esterification reaction, and a high molecular weight polymer is obtained by subsequent polycondensation reaction, and (2) dimethyl terephthalate and ethylene glycol are used 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 even without a catalyst, but the aforementioned titanium compound may be added as a catalyst. In the transesterification reaction, a catalyst such as manganese, calcium, magnesium, zinc, lithium or the above titanium compound is used as a catalyst, and the catalyst used in the reaction after the transesterification reaction is substantially completed. In order to inactivate, a phosphorus compound is added.
[0047]
The production method of the present invention comprises a matting agent applied to a low polymer obtained in 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-described titanium compound is added as a polycondensation catalyst and a polycondensation reaction is performed to obtain a high molecular weight polyethylene terephthalate.
[0048]
Further, the above reaction can be applied to a batch, semi-batch, or continuous system.
[0049]
Next, the manufacturing method of the ultra fine polyester multifilament of this invention is demonstrated. Although the example of the ultrafine polyester multifilament using a polyethylene terephthalate is described as a specific example, it is not limited to this.
[0050]
Ultra fine polyester multifilaments are usually (1) a process in which the polyester is melted, weighed, filtered, and discharged, (2) a process in which the discharged polyester filament is cooled by cooling air, and then (3) the taken polyester It is obtained by a process of winding a filament and (4) a process of further drawing the wound polyester multifilament to obtain an ultrafine polyester multifilament. It is also possible to directly obtain ultra-fine polyester multifilaments in the process (3), and in the process (2), the film is stretched in the heating area following the cooling by the cooling air, and then passed through the process (3). It is also possible to obtain ultrafine polyester multifilaments. In addition, the polyester multifilament taken up in the process (3) can be obtained by a method of drawing and heat-treating the polyester multifilament with a heating roller without winding it once and then winding it.
[0051]
The single yarn fineness of the ultrafine polyester multifilament of the present invention needs to be 1.5 dtex or less. When the single yarn fineness is larger than 1.5 dtex, Worcester spots, which are disadvantages of the conventional ultrafine polyester multifilament, are not so bad, and the effect of the present invention is small. From the point that Wooster spots are greatly improved and the effect of the present invention is further increased, the single yarn fineness is more preferably 1.0 dtex or less, and further preferably 0.7 dtex or less.
[0052]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. In addition, the physical-property value in an Example was measured by the method described below.
(1) Content of titanium element, phosphorus element, antimony element, manganese element and cobalt element in polyester
It calculated | required with the fluorescent-X-ray elemental-analysis apparatus (The Horiba Ltd. make, MESA-500W type | mold). When the polyester contains titanium dioxide particles, fluorescent X-ray analysis was performed after the following pretreatment. That is, polyester is dissolved in orthochlorophenol (5 g of polymer per 100 g of solvent), and after adding the same amount of dichloromethane as this polymer solution to adjust the viscosity of the solution, a centrifuge (rotation speed 18000 rpm, 1 hour) To settle the particles. Thereafter, only the supernatant liquid is collected by a gradient method, and the polymer is reprecipitated by adding the same amount of acetone as the supernatant liquid, and then filtered through a 3G3 glass filter (manufactured by IWAKI). After washing with acetone, the acetone was removed by vacuum drying at room temperature for 12 hours. The polymer obtained by performing the above pretreatment was analyzed for titanium element, phosphorus element, antimony element and manganese element.
[0053]
On the other hand, when the titanium dioxide particles are not contained, it is not necessary to perform a pretreatment, and the polymer may be analyzed as it is.
(2) Intrinsic viscosity of polymer IV
Measurement was performed at 25 ° C. using orthochlorophenol as a solvent.
(3) Melting point
10 mg of the sample to be measured is precisely weighed, sealed using an aluminum open pan and pan cover, and 16 from 20 ° C. to 285 ° C. under a nitrogen stream using a differential scanning calorimeter (Perkin Elmer, DSC7 type). The temperature was raised at a rate of ° C./min, and the melting point peak temperature observed in the middle was taken as the melting point.
(4) Solution haze
2.0 g of the sample to be measured was dissolved in 20 mL of orthochlorophenol and analyzed by an integrating sphere photoelectric photometry method using a haze meter (manufactured by Suga Test Instruments Co., Ltd., HGM-2DP type).
(5) Wooster spots
An average value during measurement for 1 minute at a yarn speed of 200 m / min and a twist number of 12000 T / m was calculated using a Worcter yarn spot measuring machine manufactured by Zellweger, and used as Wooster blotch.
(6) Processing thread breakage judgment
When simultaneous false twisting with 30 dtex 12 filaments and filaments with a shrinkage rate of 30% at 30 ° C. for 30 minutes in boiling water treatment was performed at 108 spindles at a draw ratio of 1.2 times and a processing speed of 700 m / min. The number of yarn breaks was measured, and it was ◎ if it was 1 or less, ○ if it was 2 to 3 times, Δ if it was 4 to 5 times, and × if it was 6 times or more.
[0054]
Example 1
A. Method for producing polyethylene terephthalate
A slurry of 100 kg of high-purity terephthalic acid (manufactured by Mitsui Chemicals) and 45 kg of ethylene glycol (manufactured by Nippon Shokubai Co., Ltd.) was previously charged with about 123 kg of bis (hydroxyethyl) terephthalate, temperature 250 ° C., pressure 1.2 × 10 ⁵ The esterification reaction tank maintained at Pa was sequentially supplied over 4 hours, and after the completion of the supply, the esterification reaction was further performed over 1 hour, and 123 kg of this esterification reaction product was transferred to the polycondensation tank.
[0055]
Subsequently, 0.3% by weight was added to the polycondensation reaction tank to which the esterification reaction product had been transferred with respect to the polymer from which an ethylene glycol slurry of titanium oxide particles was obtained. After stirring for 5 minutes, 30 ppm in terms of cobalt atom and 20 ppm in terms of manganese atom were added to the polymer from which an ethylene glycol solution of cobalt chloride and manganese acetate was obtained. After further stirring for 5 minutes, a 2 wt% ethylene glycol solution of a citrate chelate titanium compound was added to the polymer to give 0.5 ppm in terms of titanium atom, and after 5 minutes, 10 wt% of phosphoric acid. An ethylene glycol solution is added to the polymer that can be obtained in terms of phosphorus atoms to 10 ppm, and then the reaction system is gradually heated from 250 ° C. to 285 ° C. while stirring the low polymer at 30 rpm, The pressure was reduced to 40 Pa. The time to reach the final temperature and final pressure was both 60 minutes. When the predetermined stirring torque was reached, the reaction system was purged with nitrogen, returned to normal pressure, the polycondensation reaction was stopped, discharged into cold water in a strand form, and immediately cut to obtain polymer pellets. The time from the start of decompression to the arrival of the predetermined stirring torque was 3 hours.
[0056]
The obtained polymer had an IV of 0.66, a melting point of 259 ° C., and a solution haze of 0.7%. Further, the content of titanium atoms derived from the titanium catalyst measured from the polymer is 0.5 ppm, the content of phosphorus atoms is 10 ppm, Ti / P = 0.03, and the content of antimony atoms is 0 ppm. It was confirmed.
[0057]
Further, this polyester was dried, subjected to a spinning machine, melted in a melter, weighed, discharged from a spinneret, and taken up at a speed of 1850 m / min. The obtained undrawn yarn was drawn 2.8 times at 88 ° C. and then heat-set with a hot plate (130 ° C.) to obtain a drawn yarn of 50 dtex 72 filaments. Wooster spot was 0.87, the yarn breakage judgment was Δ, and the processed yarn breakage judgment was Δ.
[0058]
The method for synthesizing the catalyst is described below.
[0059]
Catalyst A. Method for synthesizing citrate chelate titanium compound
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. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 .85% by weight).
[0060]
Catalyst B. Method for synthesizing citrate chelate titanium compound (mixed with phenylphosphonic acid)
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. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 .85% by weight). To this mixed solution, phenylphosphonic acid (158 g, 1.00 mol) was added to obtain a titanium compound containing a phosphorus compound (P content: 2.49 wt%). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0061]
Catalyst C. Citrate chelate titanium compound (phenylphosphonic acid, phosphoric acid mixed) synthesis method
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. To this stirred solution was slowly added titanium tetraisopropoxide (288 g, 1.00 mol) from the addition funnel. The mixture was heated to reflux for 1 hour to produce a cloudy solution from which the isopropanol / water mixture was distilled under vacuum. The product was cooled to a temperature below 70 ° C., and a 32 wt / wt% aqueous solution of NaOH (380 g, 3.04 mol) was slowly added via a dropping funnel to the stirred solution. The resulting product was filtered and then mixed with ethylene glycol (504 g, 80 mol) and heated under vacuum to remove isopropanol / water and a slightly cloudy light yellow product (Ti content 3 .85% by weight). To this mixed solution, phenylphosphonic acid (158 g, 1.00 mol) and an aqueous 85 wt / wt% phosphoric acid solution (39.9 g, 0.35 mol) were added to obtain a titanium compound containing a phosphorus compound. Obtained (P content 3.36% by weight). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0062]
Catalyst D. Method for synthesizing lactate chelate titanium compounds
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 flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% 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 wt. %). The obtained titanium compound was added so as to be 10 ppm in terms of titanium atom with respect to the polymer from which a 2 wt% ethylene glycol solution of the titanium compound was obtained in the same manner as in Example 1, and after 5 minutes, 10 wt% of phosphoric acid. Polymerization was performed by adding 10 ppm in terms of phosphorus atom to the polymer from which an ethylene glycol solution was obtained.
[0063]
Catalyst E. Synthesis method of lactate chelate titanium compound (mixed with phenylphosphonic acid)
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 flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% 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 wt. %). By adding phenylphosphonic acid (158 g, 1.00 mol) to this mixed solution, a titanium compound containing a phosphorus compound was obtained (P content 4.23 wt%). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0064]
Catalyst F. Method for synthesizing lactate chelate titanium compound (mixture of phenylphosphonic acid and phosphoric acid)
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 flask contents to about 50 ° C. The reaction mixture was stirred for 15 minutes and an 85 wt / wt% 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 wt. %). To this mixed solution, phenylphosphonic acid (158 g, 1.00 mol) and an aqueous 85 wt / wt% phosphoric acid solution (39.9 g, 0.35 mol) were added to obtain a titanium compound containing a phosphorus compound. Obtained (P content 5.71% by weight). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0065]
Catalyst G. Method for synthesizing titanium alkoxide compound
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 flask contents to about 50 ° C. To the reaction flask, a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added via a dropping funnel to give a clear yellow liquid (Ti content 4.44 wt%). The obtained titanium compound was added in the same manner as in Example 1 so as to be 30 ppm in terms of titanium atom with respect to the polymer from which a 2% by weight ethylene glycol solution of the titanium compound was obtained. Polymerization was carried out by adding to the polymer from which a 10 wt% ethylene glycol solution was obtained in an amount of 10 ppm in terms of phosphorus atoms.
[0066]
Catalyst H. Method for synthesizing titanium alkoxide compound (mixed phosphoric acid)
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 flask contents to about 50 ° C. To the reaction flask, a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added via a dropping funnel to give a clear yellow liquid (Ti content 4.44 wt%). To this mixed solution, an 85 wt / wt% aqueous solution of phosphoric acid (114 g, 1.00 mol) was added (P content 2.87 wt%). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0067]
Catalyst I. Method for synthesizing titanium alkoxide compound (mixed with ethyl diethylphosphonoacetate)
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 flask contents to about 50 ° C. To the reaction flask, a 32 wt / wt% aqueous solution of NaOH (125 g, 1.00 mol) was slowly added via a dropping funnel to give a clear yellow liquid (Ti content 4.44 wt%). To this mixed solution, ethyl diethylphosphonoacetate (224 g, 1.00 mol) was added to obtain a titanium compound containing a phosphorus compound (P content: 2.87 wt%). No additional phosphorus compound was added at the start of the polycondensation reaction.
[0068]
Catalyst J. Composite oxide made of Accordis made of titanium and silicon
Titanium and silicon composite oxide (trade name: C-94, hereinafter referred to as Ti / Si composite oxide) manufactured by Accords, Inc. in terms of titanium atoms with respect to a polymer from which a 0.15 wt% ethylene glycol solution can be obtained. It added so that it might become 10 ppm, and it added so that it might become 10 ppm in conversion of a phosphorus atom with respect to the polymer which can obtain the 10 weight% ethylene glycol solution of phenylphosphonic acid dimethyl ester after 5 minutes.
[0069]
Examples 2 to 7, Comparative Examples 1 and 2
1.2, 3, 30, 50, 100, 150, 0.3, 200 ppm in terms of titanium atom based on the polymer capable of obtaining the addition amount of the citric acid chelate titanium compound used as the catalyst (Examples 2, 3, respectively) Polymerization, melt spinning, and stretching were carried out in the same manner as in Example 1 except that 4, 5, 6, 7, and Comparative Examples 1 and 2). Even if the amount of the titanium compound is changed, the polymerization reactivity remains favorable. However, the yarn breakage during melt spinning and the Wooster spots of the obtained polyester multifilament are the results shown in Table 1. For Examples 2 to 7, In Comparative Examples 1 and 2, Wooster spots were deteriorated, the thread breakage was judged as Δ or x, and the processed thread breakage was judged as x.
[0070]
Example 8
The amount of addition of the citric acid chelate titanium compound used as the catalyst is 20 ppm in terms of titanium atom with respect to the polymer, and 0.1 ppm in terms of phosphorus atom with respect to the polymer from which a 10 wt% ethylene glycol solution of phosphoric acid is obtained. Polymerization was performed in the same manner as in Example 1 except that the addition was performed, melt spinning, and stretching. Even when the amount of the titanium compound was changed, the polymerization reactivity continued to be good, and the yarn breakage during melt spinning and the Worcester spots of the resulting polyester multifilament showed good results as shown in Table 1.
[0071]
Examples 9 to 15 and Comparative Examples 3 and 4
1, 3, 50, 100, 150, 200, 400, 0.07, 500 ppm (respectively, Examples 9, 10, 11, 12 in terms of phosphorus atoms) with respect to the polymer from which a 10 wt% ethylene glycol solution of phosphoric acid is obtained. , 13, 14, and 15) except that the polymer was polymerized, melt-spun and stretched in the same manner as in Example 8. Even though the amount of the phosphorus compound was changed, the polymerization reactivity continued to be favorable, but the yarn breakage during melt spinning and the Wooster spots of the resulting polyester multifilament were as shown in Table 1, and for Examples 9 to 15 Although good results were obtained, in Comparative Examples 3 and 4, thread breakage occurred frequently, Wooster spots also deteriorated, and processed thread breakage occurred frequently.
[0072]
Examples 16, 17 and Comparative Example 5
In addition to the titanium compound as a catalyst, antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was polymerized and melted in the same manner as in Example 4 except that 10, 30, and 40 ppm in terms of antimony atoms were added to the resulting polymer. Spin and stretch. Even though the amount of antimony trioxide was changed, the polymerization reactivity continued to be good, but the yarn breakage during melt spinning and the Worcester spots of the resulting polyester multifilament were as shown in Table 1. Examples 16 and 17 Good results were obtained, but in Comparative Example 5, thread breakage occurred frequently, and Wooster spots also deteriorated. In addition, thread breakage occurred frequently.
[0073]
Examples 18-23
Manganese acetate added as an ethylene glycol solution was 0.7, 1, 100, 250, 400, 500 ppm (respectively, Examples 18, 19, 20, 21, 22, 23) in terms of manganese atoms with respect to the obtained polymer. Polymerization, melt spinning, and stretching were carried out in the same manner as in Example 4 except that it was added as described above. Even when the amount of the manganese compound was changed, the polymerization reactivity remained favorable, and good results were obtained as shown in Table 2 for yarn breakage during melt spinning and Worcester spots of the resulting polyester multifilament.
[0074]
Example 24
Manganese acetate added as an ethylene glycol solution is 500 ppm in terms of manganese atoms with respect to the obtained polymer, and 2 ppm in terms of phosphorus atoms with respect to the polymer from which a 10 wt% ethylene glycol solution of phosphoric acid is obtained. Polymerization, melt spinning, and stretching were carried out in the same manner as in Example 4 except that the addition was performed as described above. Even when the amount of the manganese compound and the amount of the phosphorus compound were changed, the polymerization reactivity remained favorable, and good results were obtained as shown in Table 2 for yarn breakage during melt spinning and Worcester spots of the resulting polyester multifilament. .
[0075]
Examples 25-33
Except that the titanium compounds used as the catalysts were catalysts B, C, D, E, F, G, H, I, J (Examples 25, 26, 27, 28, 29, 30, 31, 32, 33, respectively). Was polymerized, melt spun and stretched in the same manner as in Example 4. Even when the type of the titanium compound was changed, the polymerization reactivity remained favorable, and good results were obtained as shown in Table 2 for yarn breakage during melt spinning and wooster spots of the resulting polyester multifilament.
[0076]
Examples 34 and 35
Polymerization, melt spinning, and stretching were carried out in the same manner as in Example 4 except that cobalt acetate added as an ethylene glycol solution was changed to cobalt acetate (Example 34) and none (Example 35). Even when the type of the titanium compound was changed, the polymerization reactivity remained favorable, and good results were obtained as shown in Table 2 for yarn breakage during melt spinning and wooster spots of the resulting polyester multifilament.
[0077]
Examples 36 and 37
After polymerizing in the same manner as in Example 4, when melt spinning, only the discharge rate was changed, and the resulting polyester multifilaments were 84 dtex 72 filaments (Example 36), 108 dtex 72 filaments (Example 37). Except that, melt spinning was carried out in the same manner as in Example 4 to perform stretching. Although the single yarn fineness was increased, good results were obtained as shown in Table 2 with respect to yarn breakage during melt spinning and Worcester spots of the resulting polyester multifilament.
[0078]
Comparative Example 6
Without using a titanium compound as a catalyst, antimony trioxide (manufactured by Sumitomo Metal Mining Co., Ltd.) was polymerized in the same manner as in Example 1 except that 300 ppm in terms of antimony atoms was added to the obtained polymer, and melt spinning was performed. It was. Even if the catalyst is changed, the polymerization reactivity remains favorable, but the solution haze of the resulting polymer is as high as 2.4%, and as shown in Table 2, yarn breakage frequently occurs during melt spinning, and Wooster spots are also observed. Deteriorated significantly. In addition, thread breakage occurred frequently.
[0079]
[Table 1]

[0080]
[Table 2]

[0081]
【The invention's effect】
The ultrafine polyester multifilament of the present invention can be suitably used for woven fabrics and knitted fabrics characterized by its soft feeling and uniformity by greatly improving heat resistance and Wooster spots.

Claims (13)

A polyester produced using a titanium compound (excluding titanium dioxide particles) as a main catalyst, containing 0.5 to 150 ppm of the titanium compound in terms of titanium atom relative to the polyester, and 0.1% in terms of phosphorus atom relative to the polyester of the phosphorus compound. An ultrafine polyester multifilament composed of a filament having a single yarn of 1.5 dtex or less, which is made of polyester, characterized by comprising -400 ppm, containing no antimony compound, or containing 30 ppm or less in terms of antimony atoms relative to the polyester. 2. The ultrafine polyester multifilament according to claim 1, wherein the ratio of titanium compound (excluding titanium dioxide particles) and phosphorus compound is Ti / P = 0.1-20 as a molar ratio of titanium atom to phosphorus atom. . A manganese compound is contained as a catalyst in an amount of 1 to 400 ppm in terms of manganese atom relative to polyester, and the ratio of the manganese compound to the phosphorus compound is Mn / P = 0.1 to 200 as the molar ratio of the manganese atom to the phosphorus atom. The ultrafine polyester multifilament according to claim 1 or 2. The phosphorous compound is phosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid, phosphine oxide, phosphonous acid, phosphinic acid, or phosphine. 2. The ultra-fine polyester multifilament according to claim 1. The ultrafine polyester multifilament according to claim 4, wherein the phosphorous-based phosphorus compound is phosphoric acid and / or a phosphoric ester compound. The ultrafine polyester multifilament according to claim 4, wherein the phosphonic phosphorus compound is phosphonic acid and / or a phosphonic acid ester compound. The ultrafine polyester multifilament according to any one of claims 1 to 6, wherein the titanium compound is an oxide. The ultrafine polyester multifilament according to any one of claims 1 to 6, wherein the titanium compound is a composite oxide in which main metal elements are titanium and silicon. The ultrafine polyester multi according to any one of claims 1 to 6, wherein the substituent of the titanium compound is at least one selected from the group consisting of functional groups represented by the following general formulas 1 to 6. filament.

(In Formula 1 to Formula 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.) The ultrafine polyester multifilament according to claim 9, wherein R _{1 to} R _{3 in} Formulas 1 to ₃ are each independently hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. 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 10. The ultrafine polyester multifilament according to Item 9. The ultrafine polyester multifilament according to claim 11, wherein at least one of R _{1 to} R _{3 in} Formula 1 is a hydrocarbon group having 1 to 30 carbon atoms having a carboxyl group or an ester group. R _{1 in} 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. 9. The ultrafine polyester multifilament according to 9.