JP2004051883A - Polyester compositon - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester composition having minute pores when given a fiber or film shape, and having abrasion resistance, and showing improved color deepness and clearness when it is dyed. <P>SOLUTION: This polyester composition contains a calcium phosphate fine particle having an average diameter of 0.01-0.1 μm and represented by the formula: Ca<SB>a</SB>H<SB>b</SB>P<SB>c</SB>O<SB>d</SB>(wherein a is a real number of 1-10, b is a real number of 0-10, c is a real number of 1-6, and d is a real number of 1-10) in a range of 0.03-5 wt%. <P>COPYRIGHT: (C)2004,JPO

Description

【０００９】
しかしながら、本製造方法においては反応中に不溶性粒子をポリエステル中に均一な超微粒子分散状態で生成せしめるものの、剤添加時の温度や添加剤の添加速度等添加条件のきわめてわずかな差によっても粗大結晶核を生成し、一旦粗大粒子を生成してしまうと消失することがないため、重合工程でのフィルター詰まり、紡糸工程でのパック圧上昇や断糸を誘発し、連続生産を続けることが極めて困難であるという問題点を抱えていた。
【００１０】
本願発明の目的の一つは、染色した際に改善された色の深みと鮮明性とを呈するようにできるポリエステル組成物を提供することにある。本願発明のさらに他の目的および利点は、以下の説明から明らかになるであろう。
【００１１】
【課題を解決するための手段】
本発明の第一の態様によれば、ポリエステルと、
平均粒子径が０．０１〜０．１μｍの範囲にあるＣａ_ａＨ_ｂＰ_ｃＯ_ｄ（ここで、ａは１〜１０の実数、ｂは０〜１０の実数、ｃは１〜６の実数、ｄは１〜１０の実数を表す）で表されるリン酸カルシウム微粒子とを含有し、
当該リン酸カルシウム微粒子の含有率が０．０３〜５重量％の範囲にある
ポリエステル組成物が提供される。
【００１２】
前記リン酸カルシウム微粒子が第一リン酸カルシウム、第ニリン酸カルシウム、第三リン酸カルシウムおよびまたはその混合物からなる群のうちの少なくとも一種を含むこと、前記ポリエステルの繰り返し単位の少なくとも８０モル％がエチレンテレフタレート単位であること、内直径６４ｍｍの、ＪＩＳ　Ｇ３５５６に準拠する公称目開き基準寸法０．０２６ｍｍ（すなわち５００メッシュ相当）の平織り金網からなるフィルターを直交して２枚重ね、温度２９０℃、３３．３ｇ／分の濾過速度で当該ポリエステル組成物を濾過した場合、１２０時間経過時点で測定した濾過昇圧が５ＭＰａ／日未満であること、形状としては、繊維状またはフィルム状であること、塩基性化合物と接触させて減量し、表面に微細孔を有するようにすること等が好ましい。染色した際に改善された色の深みと鮮明性とを呈する効果が得やすいからである。２重量％以上減量することが好ましい。なお、ここで、上記フィルターを直交して２枚重ねるとは、それぞれの金網を構成する縦方向または横方向の鋼線が互いに直交するように重ねることを意味する。
【００１３】
【発明の実施の形態】
以下に、本願発明の実施の形態を実施例等を使用して説明する。なお、これらの実施例等および説明は本願発明を例示するものであり、本願発明の範囲を制限するものではない。本願発明の趣旨に合致する限り他の実施の形態も本願発明の範疇に属し得ることは言うまでもない。なお、本明細書においては繊維を中心にして説明するが、その他の形状、たとえばフィルム状で使用する場合にも、同様の効果を得ることができることは言うまでもない。たとえば「繊維表面での光の乱反射」を「フィルム表面での光の乱反射」と読み替えることが可能である。
【００１４】
本発明においては、平均粒子径が０．０１〜０．１μｍの範囲にあるＣａ_ａＨ_ｂＰ_ｃＯ_ｄ（ここで、ａは１〜１０の実数、ｂは０〜１０の実数、ｃは１〜６の実数、ｄは１〜１０の実数を表す）で表されるリン酸カルシウム微粒子がポリエステル組成物に含有されていることが必要である。
【００１５】
平均粒径が０．０１μｍ未満であると、繊維化したときの形成孔の径が小さいため、繊維表面での光の乱反射をともなわず、染色したときの色の深みに欠けるものとなり好ましくない。０．１μｍを超えると形成孔が大きくなるため、染色したときの色の深みに欠けるほか、重合反応中や製糸工程で一部が凝集しやすく、粗大粒子化し、ポリマーフィルターを昇圧させたり、紡糸工程でのパック圧上昇、断糸を誘発しやすくなるため好ましくない。なおこの平均粒子径は、ＪＩＳＺ８８２３−１による方法で測定することができる。
【００１６】
本発明に用いられるリン酸カルシウム微粒子は、Ｃａ_ａＨ_ｂＰ_ｃＯ_ｄで表されるが、ａ，ｂ，ｃ，ｄは組成を表示しており、必ずしも整数でなくてもよい。ａが１未満であると微細孔を形成せず、１０を超えると粗大粒子化またはゲル化を起こしやすくなり好ましくない。ｂが１０を超えると、ポリエステル組成物の熱安定性が劣るようになるため好ましくない。ｃが１未満では微細孔形成能を有さず、１０を超えるとリン酸の影響で系の酸性度が変わり、重合時にＣａ_ａＨ_ｂＰ_ｃＯ_ｄを添加した場合に、ポリエステルの固有粘度が上昇しにくくなるため好ましくない。ｄが１未満であると微細孔形成性粒子とならず、１０を超えるとポリエステルの色相が劣るようになる。適正な微細孔を形成させる点から検討の結果、ａ／ｃは、１．３〜１．７がより好ましい。なお、ここでいう微細孔とは、たとえば繊維状に成形した場合、繊維表面の繊維軸方向に多数配列した、短径が０．１〜２．０μｍ、長径が０．１〜５．０μｍ程度の微細な孔を意味する微粒子である。
【００１７】
このようなリン酸カルシウム微粒子を形成するリン酸カルシウム化合物としては、Ｃａ（Ｈ_２ＰＯ_４）_２、ＣａＨＰＯ_４、Ｃａ（ＰＯ_４）_２、アパタイト、ヒドロキシアパタイト、酸性ピロリン酸カルシウム、ピロリン酸カルシウム等が挙げられる。これらを単一で含有してもよいし、複数を混合して含有してもよい。中でも、安価で粒子の粉砕処理が容易である点で、第一リン酸カルシウム、第ニリン酸カルシウム、第三リン酸カルシウムが好ましく用いられる。
【００１８】
本発明におけるリン酸カルシウム微粒子の含有量は０．０３〜５重量％の範囲であることが必要である。０．０３重量％未満であると繊維としたときの微細孔の数が少なくなり、５重量％を超えると凝集粒子を生成しやすくなったり、重合時にＣａ_ａＨ_ｂＰ_ｃＯ_ｄを添加した場合に、ポリエステルの固有粘度が十分上昇しにくくなるので好ましくない。ただし、場合によっては、５重量％を超える濃度のリン酸カルシウム微粒子を含有するポリエステル組成物を作製し、これを希釈して０．０３〜５重量％の範囲にすることも本発明の範疇に属する。
【００１９】
本発明においてポリエステルとは、ジカルボン酸および／またはそのエステル形成性誘導体（以下、エステル形成性酸成分ともいう）ならびにジオールおよび／またはそのエステル形成性誘導体（以下、エステル形成性ジオール成分ともいう）とから合成される線状飽和ポリエステルであって、汎用樹脂としての物性を失わない範囲で目的に応じて他の成分が共重合されていてもよい。
【００２０】
エステル形成性酸成分として、テレフタル酸、２，６−ナフタレンジカルボン酸、イソフタル酸、１，４−シクロヘキシルジカルボン酸、アジピン酸、セバシン酸、フタル酸、無水フタル酸、５−ナトリウムスルホイソフタル酸、５−テトラブチルホスホニウムスルホイソフタル酸、ｐ−ヒドロキシ安息香酸、テレフタル酸ジメチル、２，６−ナフタレンジカルボン酸ジメチル、イソフタル酸ジメチル、１，４−シクロヘキサンジカルボン酸、アジピン酸ジメチル、セバシン酸ジメチル、フタル酸ジメチル、５−ナトリウムスルホイソフタル酸ジメチル、５−テトラブチルホスホニウムスルホイソフタル酸ジメチル等を挙げることができる。特に、テレフタル酸、２，６−ナフタレンジカルボン酸、テレフタル酸ジメチル、２，６−ナフタレンジカルボン酸ジメチルを用いることが好ましい。
【００２１】
また、エステル形成性ジオール成分として、エチレングリコール、１，４−ブタンジオール、ジエチレングリコール、プロピレングリコール、２，２−ジメチル−１，３−プロパンジオール、ジプロピレングリコール、１，６−ヘキサンジオール、１，４−ヘキサンジメタノール、ジメチロールプロピオン酸、ポリ（エチレンオキシド）グリコール、ポリ（テトラメチレンオキシド）グリコール等を挙げることができる。特に、エチレングリコール、１，４−ブタンジオールを用いることが好ましい。
【００２２】
エステル形成性酸成分とエステル形成性ジオール成分との組み合わせとしては、ポリエステルの繰り返し単位の８０モル％以上がエチレンテレフタレート単位であることが好ましい。優れた物性が実現できるからである。
【００２３】
これらのエステル形成性酸成分とエステル形成性ジオール成分とはそれぞれ１種ずつを単独で用いても、２種以上を併用してもどちらでもよい。
【００２４】
なお、本発明におけるポリエステルには、トリメリット酸、トリメシン酸、無水トリメリット酸、ピロメリット酸、トリメリット酸モノカリウム塩などの多価カルボン酸、グリセリン、ジメチロールエチルスルホン酸ナトリウム、ジメチロールプロピオン酸カリウム等の多価ヒドロキシ化合物を、本発明の目的を達成する範囲内であれば共重合してもよい。
【００２５】
本発明の樹脂組成物は要件を備えたリン酸カルシウムを乾式処理、湿式処理により、所定の平均粒径になるように調製し、水および／または沸点が５０〜２４０℃の範囲にある有機化合物を分散媒とするスラリーとしてポリエステルの製造中に添加することで容易に製造することができる。なお、重合反応の完結したポリエステルまたはポリエステル組成物を押出機または混練機に供給し、該リン酸カルシウム微粒子のスラリーを、または該リン酸カルシウム微粒子をそのまま、添加し、混練することで製造することもできる。上記所定の平均粒径としては、０．０１〜０．１μｍの範囲にあれば良い。
【００２６】
上記分散媒としての有機化合物としては、メタノール、エタノール、１，４−ブタンジオール等のアルコール類、ベンゼン、トルエン、キシレン等の芳香族炭化水素化合物、テトラヒドロフラン、１，３−ジオキソラン、２−メチル−１，３−ジオキソラン等のエーテル類、その他エステル類、ケトン類、アミン類等を挙げることができる。スラリーの分散媒は、水を含めて、一種を単独で用いても、二種以上の混合分散媒を用いてもよい。
【００２７】
さらに、リン酸カルシウム微粒子が均一に分散しているスラリーを得るために、本発明の目的を奏する範囲内であれば各種の添加剤を用いてもよい。該添加剤としては、ポリスチレンスルホン酸ソーダ、カルボキシメチルセルロース、ポリビニルアルコール等の保護剤、水酸化ナトリウム、ヘキサメタリン酸ナトリウム等のナトリウム塩、テトラメチルアンモニウムクロライド、テトラエチルアンモニウムヒドロキサイド等のオニウム化合物、ドデシルベンゼンスルホン酸ナトリウム、ラウリル硫酸ナトリウム等のアニオン系界面活性剤、ポリオキシエチレンノニルフェニルエーテル、ポリエチレングリコールモノステアレート等のノニオン系界面活性剤等を挙げることができる。
【００２８】
なお、乾式で粉砕または解砕し、さらに分級処理を加えるか、粉砕または解砕単独の処理を行うか、分級処理単独の処理を行った後、水および／または沸点が５０〜２４０℃の範囲にある有機化合物とのスラリーとしてもよい。
【００２９】
あるいは、乾式と湿式とを適宜組み合わせてもよく、たとえば、乾式で粉砕した粒子をスラリー化した後、湿式にて分級処理を行う、乾式にて解砕および／または分級処理を行った後に湿式にて粉砕処理を行う等の方法を任意に採用すればよい。
【００３０】
乾式の粉砕または解砕処理としては、高速回転衝撃式粉砕機、気流式粉砕機等による粉砕を挙げることができる。分級処理としては、風力分級装置による分級を挙げることができる。湿式の粉砕または解砕処理としては、ビーズによる粉砕を挙げることができる。分級処理としては、遠心沈降式分級器による分級を挙げることができる。
【００３１】
スラリー濃度については、特に制限されないが、最終的には溶媒を除去することから、可能な限り高濃度とすることが好ましく、スラリーの全重量を基準として５〜５０重量％の範囲にあることが好ましい。上記の範囲内にあるときには該ポリエステル組成物を製造する際のスラリー添加量を少なくすることができるので、ポリエステルの分解劣化を抑制することができるとともに、スラリーのハンドリング性も良好なものとなることが多い。
【００３２】
本発明のポリエステル組成物にはポリエステルの製造時に通常用いられるリチウム、ナトリウム、カルシウム、マグネシウム、マンガン、亜鉛、アンチモン、ゲルマニウム、チタン等の化合物の金属化合物触媒、着色防止剤としてのリン化合物、その他ポリエステルの改質に用いられる不活性粒子や有機化合物等を本発明の目的を奏する範囲内で含んでいてもよい。
【００３３】
本発明に係るポリエステル組成物は凝集異物が少なく、さらに、６４ｍｍ直径の、ＪＩＳ　Ｇ３５５６に準拠する公称目開き基準寸法０．０２６ｍｍの平織り金網からなるフィルターを直交して２枚重ね、温度２９０℃、流量３３．３ｇ／分で濾過したとき、５ＭＰａ／日未満と、粒子含有ポリエステルとしては非常に低い昇圧で済み、さらに１２０時間経過時点で同様の昇圧評価しても依然５ＭＰａ／日未満の昇圧にとどまる特徴を有するようにすることができ、従って、溶融処理時におけるフィルター詰まりやパック圧上昇が少なく、断糸、断膜等の工程上の不具合が少ないという効果を実現することができる。なお、１２０時間経過時点での昇圧とは、１２０時間経過時点から１４４時間経過時点までの圧力上昇値を意味する。
【００３４】
本発明におけるポリエステル組成物は、そのまま紡糸しても、あるいはいわゆるマスターバッチにして、紡糸工程または別の成形工程にて比較的低濃度にポリマー希釈してから使用することもできる。
【００３５】
このようにして得られたポリエステル組成物を溶融紡糸として繊維にする場合を説明すれば、紡糸に特別な方法を採用する必要はなく、通常のポリエステル繊維の溶融紡糸方法が任意に採用できる。ここで紡出する繊維は中空部を有しない中実繊維であっても中空部を有する中空繊維であってもよい。また紡出する繊維の横断面における外形や中空部の形状は、円形であっても異形であってもよい。さらに紡糸するに際して、上記のリン酸カルシウム微粒子を含有する組成物と含有しないポリエステルやポリエステル組成物とを使用し、芯鞘型複合繊維にしても、２層ないしそれ以上の多層構造を有するサイド・バイ・サイド型複合繊維にしてもよい。
【００３６】
このようにして得られる繊維状のポリエステル組成物の表面に微細孔を与えると、染色した際に改善された色の深みと鮮明性とを呈するようになる。摩耗耐久性も満足させることが可能である。このような微細孔を与える手段としては、物理的、化学的方法等どのようなものでもよいが、繊維状のポリエステル組成物を塩基性化合物と接触させ、減量する方法が好ましい。この塩基性化合物との接触は、繊維を必要に応じて延伸加熱処理または仮撚加工等の処理に供した後、または更に布帛にした後、たとえば塩基性化合物の水溶液で処理することにより容易に行うことができる。
【００３７】
ここで使用する塩基性化合物としては、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、炭酸ナトリウム、炭酸カリウム等を挙げることができる。なかでも水酸化ナトリウム、水酸化カリウムが特に好ましい。
【００３８】
この塩基性化合物の水溶液の濃度は、塩基性化合物の種類、処理条件等によって異なるが、特に０．１〜３０重量％の範囲が好ましい。処理温度は常温〜１００℃の範囲であることが好ましい。処理時間は通常１分〜４時間の範囲で行われる。
【００３９】
また、この塩基性化合物の水溶液の処理によって減量する量は、繊維重量に対して２重量％以上の範囲にすることが好ましい。このように塩基性化合物の水溶液で処理することによって、繊維軸方向に配列した微細孔を繊維表面およびその近傍に多数形成せしめることができ、染色した際により優れた色の深みを呈するようになる。なお、減量の上限については特に制限がないが、減量が過ぎると物性が低下したり、フィブリル化しやすくなるので、配慮が必要となる場合が多い。上限として３０重量％が好ましい場合が多い。
【００４０】
【実施例】
以下、実施例を挙げて本発明をさらに具体的に説明する。なお、実施例中における各特性の測定は以下の方法により行った。実施例中、「部」は重量部を意味する。
【００４１】
（平均粒径）
堀場製ＣＡＰＡ−５００を用いて、ＪＩＳ　Ｚ８８２３−１による方法で測定した。
【００４２】
なお、本発明に係るリン酸カルシウム微粒子の平均粒径は、ポリエステル組成物に添加する前に測定したものであるが、ポリエステル組成物中でも同程度の平均粒径を維持できることが、別途確認されている。
【００４３】
（固有粘度（［η］））
１，１，２，２−テトラクロロエタン４０重量部とフェノール６０重量部との混合溶媒中に試料を溶解して３５℃にて測定した。
【００４４】
（ポリエステル組成物の濾過昇圧）
ポリエステル組成物の濾過時の昇圧を評価するため、下記のように濾過昇圧速度を評価した。
【００４５】
小型１軸スクリュータイプ押出機の溶融ポリマー出側にポリマー定量供給装置を取り付け、更にその出側に内直径６４ｍｍの、ＪＩＳ　Ｇ３５５６に準拠する公称目開き基準寸法０．０２６ｍｍの平織り金網からなるフイルターを直交して２枚重ねて装着した。次いで、溶融ポリマーの温度を２９０℃一定となるようにコントロールし、ポリマー流量が３３．３ｇ／分の速度となるようにポリマーを２４時間連続して濾過した。そして、この濾過フイルター入側の圧力上昇値をもって、濾過圧力上昇速度１とした。次いでさらに濾過操作を続行し、１２０時間時点から１４４時間時点までの圧力上昇値をもって濾過圧力上昇速度２とした。濾過圧力上昇速度２は本発明に係る「濾過昇圧」に該当する。
【００４６】
（色の深み）
色の深みを示す尺度として、深色度（Ｋ／Ｓ）を用いた。この値はサンプル布帛の分光反射率を島津製ＲＣ−３３０型自記分光光度計にて測定し、下記のクベルカ・ムンクの式より求めた。この値が大きいほど深色効果が大きいことを示す。
【００４７】
Ｋ／Ｓ＝（１−Ｒ）^２／２Ｒ
なお、Ｒは反射率、Ｋは吸収係数、Ｓは散乱係数を示す。
【００４８】
（耐摩擦変色性）
摩擦堅牢度試験用の学振型平面摩耗機を使用し、摩擦布としてポリエチレンテレフタレート１００％からなるジョーゼットを用いて試験布５００ｇの加重下で所定回数平面摩耗して、変色の程度を変退色用グレースケールで判定した。摩耗性が極めて低い場合を１級とし、極めて高い場合を３級とした。１級のみが実用に供されるレベルである。
【００４９】
［参考例１］
（リン酸カルシウム微粒子スラリーの調製）
太平化学（株）製の第三リン酸カルシウムを２０重量％のエチレングリコールスラリーとし、０．８ｍｍ径のジルコニアビーズを粉砕材として、五十嵐機械製サンドグラインダーで平均粒径を０．０８μｍに調製した。
【００５０】
［実施例１］
（ポリエステルの製造）
ジメチルテレフタレート１００重量部とエチレングリコール７０重量部とを用い、酢酸マンガン・４水和物０．０３８重量部を触媒として常法に従ってエステル交換反応により生成したオリゴマーに、参照例１で作製したスラリーを、第三リン酸カルシウム量が、最終生成組成物を基準として２．５重量％となるように添加し、１５分間反応を継続した後三酸化アンチモン０．０４５重量部を添加し、更に５分間反応させてから、減圧下２９０℃まで昇温し、０．０３ｋＰａ以下の高真空下にて重縮合反応を行って固有粘度０．６４のポリエステルペレットを得た。
【００５１】
このペレットを１４０℃にて６ｈｒ乾燥し、孔径０．３ｍｍの円形紡糸孔を３６個穿設した紡糸口金を使用して２９０℃で溶融紡糸した。紡糸は１２０時間実施した。ついで３．５倍に延伸して、８３ｄｔｅｘ／３６ｆｉｌの延伸糸を得た。この原糸にＳ撚２５００Ｔ／ｍおよびＺ撚２５００Ｔ／ｍの強撚を施し、続いて該強撚糸を８０℃で３０分蒸熱処理して撚止めを行った。紡糸中における圧上昇は、１ＭＰａ／日であり、紡糸、延伸における断糸率はそれぞれ１％にとどまった。これらは、いずれも、本発明に係るリン酸カルシウム微粒子を含まないポリエステルを紡糸、延伸したときと同程度の値であった。
【００５２】
なお、断糸率は、紡糸断糸率については、人為的または機械的要因に起因する断糸を除き、紡糸機運転中に発生した紡糸断糸回数を記録し、下記式で紡糸断糸率（％）を計算したものである。
【００５３】
紡糸断糸率（％）＝［断糸回数／（稼働ワインダー数×ドッフ数）］×１００（ここで、ドッフ数とは未延伸糸パッケージを規定量（１０ｋｇ）まで巻き取った回数をいう。）
また、延伸断糸率については、人為的または機械的要因に起因する断糸を除き、延伸機運転中に発生した延伸断糸回数を記録し、下記式で延伸断糸率（％）を計算したものである。
【００５４】
延伸断糸率（％）＝［断糸回数／（稼働錘数×ドッフ数）］×１００（ここで、ドッフ数とは仮撚加工糸パッケージを規定量（２．５ｋｇ）まで巻き取った回数をいう。）
該撚止め強撚糸を経密度４７本／ｃｍ、緯密度３２本／ｃｍでＳ，Ｚを２本交互に配して梨地ジョーゼット織物を製織した。
【００５５】
得られた生機をロータリーワッシャーにて沸騰温度で２０分間リラックス処理し、シボ立てを行い、常法によりプリセット後、沸騰温度の３．５重量％の水酸化ナトリウム水溶液で処理し、減量率が２０％の布帛を得た。この減量した布帛の表面には、繊維軸方向に配列した、短径が０．１〜０．５μｍ、長径が０．１〜０．８μｍの微細孔が繊維表面に多数形成されていることを電子顕微鏡で確認した。
【００５６】
これらのアルカリ処理後の布帛をＤｉａｎｏｉｘ　Ｂｌａｃｋ　ＨＧ−ＦＳ（三菱化学製）１５％ｏｗｆで１３０℃６０分間染色後、水酸化ナトリウム１ｇ／Ｌおよびハイドロサルファイト１ｇ／Ｌを含む水溶液にて７０℃で２０分間還元洗浄して黒染布を得た。これらの黒色布の色の深みおよび摩耗２００回の耐磨耗変色性を表１に示した。
【００５７】
なお、上記とは別に、上記の「ポリエステル組成物の濾過昇圧」試験を行い、濾過圧力上昇速度１と濾過圧力上昇速度２とを測定した。この結果も表１に示す。
【００５８】
［実施例２］
リン酸カルシウム微粒子の含有量を表１に示す通りに変更した以外は、実施例１と同様に実施した。結果を表１に示す。紡糸中における圧上昇や、紡糸、延伸における断糸率は実施例１と同程度であった。
【００５９】
［実施例３］
リン酸カルシウム微粒子の平均粒径を表１に示す通りに変更した以外は実施例１と同様に実施した。結果を表１に示す。紡糸中における圧上昇や、紡糸、延伸における断糸率は実施例１と同程度であった。
【００６０】
［実施例４］
粒子の種類を表１に示す通りに変更した以外は実施例３と同様に実施した。結果を表１に示す。紡糸中における圧上昇や、紡糸、延伸における断糸率は実施例１と同程度であった。
【００６１】
［比較例１］
第三リン酸カルシウム微粒子の代わりに平均粒径０．０３μｍのシリカ粒子を使用する以外は、微細化処理も含めて、実施例１と同様に行った。結果を表１に示す。この減量した布帛の表面には、０．２〜０．７μｍの不規則な凹凸があり、この凹凸内に０．０５〜０．２μｍの微細な凹凸が存在していた。
【００６２】
【表１】

【００６３】
【発明の効果】
本発明によれば、繊維やフィルムの形状を付与したときに微細孔を有し、染色した際に改善された色の深みと鮮明性とを呈するようにできるポリエステル組成物が提供される。摩耗耐久性も満足させることが可能である。この組成物は異物量が少なく、従って、ブレンド、製糸、成膜等の溶融処理時におけるフィルター詰まりやパック圧上昇が少なく、断糸、断膜等の工程上の不具合が少ない。[0001]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD The present invention relates to a polyester composition, and more particularly, to a polyester composition having fine pores when imparting the shape of a fiber or film, and exhibiting improved color depth and sharpness when dyed. About.
[0002]
[Prior art]
Polyesters are widely used as synthetic fibers because of their many excellent properties. However, compared to natural fibers such as wool and silk, fibrous fibers such as rayon and acetate, and acrylic fibers, polyester fibers are inferior in coloring and clarity because they have no depth in color when colored. There are drawbacks.
[0003]
[Problems to be solved by the invention]
Conventionally, attempts have been made to improve dyes and to chemically modify polyesters in order to solve this drawback, but none of them has been able to provide a sufficient effect.
[0004]
On the other hand, as an attempt to give depth to the color when the surface of the polyester fiber is colored by imparting irregularities, a fiber made of polyester containing polyoxyethylene glycol and / or a sulfonic acid compound is treated with an aqueous alkali solution. By doing so, there has been proposed a method for producing a hygroscopic fiber in which wrinkled micropores arranged in the fiber axis direction are formed.
[0005]
However, the fibers obtained by these methods have no effect of improving the color depth, but rather have a decrease in luminous density. That is, when the treatment with the aqueous alkali solution is not sufficient in these methods, the effect of improving the color depth is not recognized at all because the irregularities only occur on the very surface of the fiber, and the treatment with the aqueous alkaline solution is not sufficient. Sometimes, instead of improving the color depth, perhaps due to irregular reflection of light, the luminous density is reduced, it becomes whitish even if it is colored deeply, and the strength of the obtained fiber is significantly reduced, It becomes fibrillated easily and does not withstand use.
[0006]
In addition, polyester containing inorganic fine particles such as silica having a particle diameter of 80 nm or less is reduced in alkali to give irregularities of 0.2 to 0.7 μm on the fiber surface, and 0.05 to There has been proposed a method of improving the color depth by providing fine irregularities of 0.2 μm (see Japanese Patent Application Laid-Open No. 55-120728). However, the effect of improving the color depth is not enough even by this method, and furthermore, there is a disadvantage that it is likely to be fibrillated probably because of such an extremely complicated uneven shape.
[0007]
In order to eliminate the above-mentioned disadvantages, the following formula (1) (where R is ₁ And R ₂ Is a monovalent organic group and R ₁ And R ₂ M may be the same or different, and m is 1 when M is an alkali metal, and ｍ when M is an alkaline earth metal) and the metal-containing phosphorus compound (a) 0.5 to 1.2 times the molar amount of the alkaline earth metal (b) with respect to the compound is added without previously reacting (a) and (b), and then the synthesis of the polyester is completed. A method for producing synthetic fibers having fine pores, characterized in that the obtained polyester is melt-spun and then treated with an aqueous solution of a basic compound to reduce the weight by 2% by weight or more.
[0008]
Embedded image

[0009]
However, in this production method, insoluble particles are generated in a uniform dispersion state of ultrafine particles in the polyester during the reaction, but coarse crystals are formed even by a very small difference in the addition conditions such as the temperature at the time of addition of the agent and the addition speed of the additive. Since nuclei are generated and coarse particles are not lost once they are generated, filter clogging in the polymerization process, pack pressure increase and spinning in the spinning process are induced, and continuous production is extremely difficult. Had the problem of being
[0010]
One of the objects of the present invention is to provide a polyester composition which can exhibit improved color depth and sharpness when dyed. Still other objects and advantages of the present invention will become apparent from the following description.
[0011]
[Means for Solving the Problems]
According to a first aspect of the present invention, a polyester,
Ca having an average particle size in the range of 0.01 to 0.1 μm _a H _b P _c O _d (Where a is a real number of 1 to 10, b is a real number of 0 to 10, c is a real number of 1 to 6, and d is a real number of 1 to 10).
The content of the calcium phosphate fine particles is in the range of 0.03 to 5% by weight.
A polyester composition is provided.
[0012]
Wherein the calcium phosphate fine particles contain at least one member selected from the group consisting of monocalcium phosphate, dibasic calcium phosphate, tribasic calcium phosphate and / or a mixture thereof, wherein at least 80 mol% of the repeating units of the polyester are ethylene terephthalate units. Two filters each composed of a flat woven wire mesh having a diameter of 64 mm and a nominal mesh size of 0.026 mm according to JIS G3556 (that is, equivalent to 500 mesh) are superposed at right angles, and at a temperature of 290 ° C. and a filtration rate of 33.3 g / min. When the polyester composition is filtered, the pressure increase in filtration measured at the elapse of 120 hours is less than 5 MPa / day, the shape is fibrous or film-like, the weight is reduced by contact with a basic compound, Having micropores on the surface, etc. Is preferred. This is because the effect of exhibiting improved color depth and sharpness when dyed is easily obtained. It is preferable to reduce the weight by 2% by weight or more. Here, to overlap two filters at right angles means that the vertical or horizontal steel wires constituting each wire mesh are overlapped so as to be orthogonal to each other.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, embodiments of the present invention will be described using examples and the like. It should be noted that these examples and the like and the description illustrate the present invention, and do not limit the scope of the present invention. It goes without saying that other embodiments can also be included in the scope of the present invention as long as they conform to the gist of the present invention. In addition, although the description will be made mainly with the fibers in the present specification, it is needless to say that the same effect can be obtained even when used in other shapes, for example, a film shape. For example, “diffuse light reflection on the fiber surface” can be read as “diffuse light reflection on the film surface”.
[0014]
In the present invention, Ca having an average particle diameter in the range of 0.01 to 0.1 μm is used. _a H _b P _c O _d (Where a represents a real number of 1 to 10, b represents a real number of 0 to 10, c represents a real number of 1 to 6, and d represents a real number of 1 to 10), which are contained in the polyester composition. Need to be done.
[0015]
If the average particle size is less than 0.01 μm, the diameter of the pores formed when the fibers are formed is small, so that irregular reflection of light on the fiber surface does not occur and the color depth when dyed is lacking, which is not preferable. When the thickness exceeds 0.1 μm, the pore size becomes large, so that the color depth at the time of dyeing is lacking. In addition, a part of the color tends to agglomerate during the polymerization reaction or in the fiber-forming process, forming coarse particles, increasing the pressure of the polymer filter, or spinning. It is not preferable because the pack pressure is easily increased in the process and the yarn breakage is easily induced. The average particle diameter can be measured by a method according to JISZ8823-1.
[0016]
The calcium phosphate fine particles used in the present invention are Ca _a H _b P _c O _d Where a, b, c, and d indicate compositions, and need not necessarily be integers. When a is less than 1, fine pores are not formed, and when a is more than 10, coarse particles or gelation are apt to occur, which is not preferable. When b exceeds 10, the thermal stability of the polyester composition becomes inferior, which is not preferable. If c is less than 1, it has no ability to form micropores, and if it exceeds 10, the acidity of the system changes due to the effect of phosphoric acid, and Ca _a H _b P _c O _d Is not preferred because the intrinsic viscosity of the polyester does not easily increase. If d is less than 1, the particles will not be fine pore-forming particles, and if d is more than 10, the hue of the polyester will be inferior. As a result of study from the viewpoint of forming appropriate micropores, a / c is more preferably 1.3 to 1.7. The micropores referred to here are, for example, when formed into a fibrous shape, a large number is arranged in the fiber axis direction on the fiber surface, with a minor axis of about 0.1 to 2.0 μm and a major axis of about 0.1 to 5.0 μm. Are fine particles that mean fine pores.
[0017]
Examples of the calcium phosphate compound forming such calcium phosphate fine particles include Ca (H ₂ PO ₄ ) ₂ , CaHPO ₄ , Ca (PO ₄ ) ₂ , Apatite, hydroxyapatite, calcium acid pyrophosphate, calcium pyrophosphate and the like. These may be contained singly, or a plurality thereof may be mixed and contained. Among them, monobasic calcium phosphate, dibasic calcium phosphate, and tribasic calcium phosphate are preferably used in that they are inexpensive and easy to pulverize particles.
[0018]
In the present invention, the content of the calcium phosphate fine particles needs to be in the range of 0.03 to 5% by weight. If the amount is less than 0.03% by weight, the number of micropores in the fiber becomes small. If the amount exceeds 5% by weight, aggregated particles are easily generated, or Ca _a H _b P _c O _d Is not preferred because it is difficult to sufficiently increase the intrinsic viscosity of the polyester. However, in some cases, a polyester composition containing calcium phosphate fine particles having a concentration of more than 5% by weight is prepared and diluted to a range of 0.03 to 5% by weight, which is also included in the scope of the present invention.
[0019]
In the present invention, the polyester is a dicarboxylic acid and / or an ester-forming derivative thereof (hereinafter, also referred to as an ester-forming acid component) and a diol and / or an ester-forming derivative thereof (hereinafter, also referred to as an ester-forming diol component). And other components may be copolymerized according to the purpose within a range that does not lose the physical properties of a general-purpose resin.
[0020]
Examples of the ester-forming acid component include terephthalic acid, 2,6-naphthalenedicarboxylic acid, isophthalic acid, 1,4-cyclohexyldicarboxylic acid, adipic acid, sebacic acid, phthalic acid, phthalic anhydride, 5-sodium sulfoisophthalic acid, -Tetrabutylphosphonium sulfoisophthalic acid, p-hydroxybenzoic acid, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl isophthalate, 1,4-cyclohexanedicarboxylic acid, dimethyl adipate, dimethyl sebacate, dimethyl phthalate Dimethyl 5-sodium sulfoisophthalate, dimethyl 5-tetrabutylphosphonium sulfoisophthalate, and the like. In particular, it is preferable to use terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, and dimethyl 2,6-naphthalenedicarboxylate.
[0021]
As the ester-forming diol component, ethylene glycol, 1,4-butanediol, diethylene glycol, propylene glycol, 2,2-dimethyl-1,3-propanediol, dipropylene glycol, 1,6-hexanediol, Examples thereof include 4-hexanedimethanol, dimethylolpropionic acid, poly (ethylene oxide) glycol, and poly (tetramethylene oxide) glycol. In particular, it is preferable to use ethylene glycol and 1,4-butanediol.
[0022]
As a combination of the ester-forming acid component and the ester-forming diol component, it is preferable that 80 mol% or more of the repeating units of the polyester are ethylene terephthalate units. This is because excellent physical properties can be realized.
[0023]
Each of these ester-forming acid components and ester-forming diol components may be used alone or in combination of two or more.
[0024]
The polyester in the present invention includes trimellitic acid, trimesic acid, trimellitic anhydride, pyromellitic acid, polycarboxylic acids such as trimellitic acid monopotassium salt, glycerin, sodium dimethylol ethyl sulfonate, dimethylol propion Polyhydric hydroxy compounds such as potassium acid may be copolymerized as long as the object of the present invention is achieved.
[0025]
The resin composition of the present invention is prepared by subjecting the required calcium phosphate to a predetermined average particle size by dry treatment and wet treatment, and dispersing water and / or an organic compound having a boiling point in the range of 50 to 240 ° C. It can be easily produced by adding it as a slurry during the production of the polyester. In addition, the polyester or the polyester composition after the completion of the polymerization reaction may be supplied to an extruder or a kneader, and the slurry of the calcium phosphate fine particles or the calcium phosphate fine particles may be directly added and kneaded. The predetermined average particle size may be in the range of 0.01 to 0.1 μm.
[0026]
Examples of the organic compound as the dispersion medium include alcohols such as methanol, ethanol, and 1,4-butanediol, aromatic hydrocarbon compounds such as benzene, toluene, and xylene, tetrahydrofuran, 1,3-dioxolan, and 2-methyl-. Examples thereof include ethers such as 1,3-dioxolan, other esters, ketones, and amines. As the dispersion medium of the slurry, one kind may be used alone including water, or a mixed dispersion medium of two or more kinds may be used.
[0027]
Further, in order to obtain a slurry in which calcium phosphate fine particles are uniformly dispersed, various additives may be used as long as the object of the present invention is achieved. Examples of the additive include protecting agents such as sodium polystyrene sulfonate, carboxymethyl cellulose, and polyvinyl alcohol; sodium salts such as sodium hydroxide and sodium hexametaphosphate; onium compounds such as tetramethylammonium chloride and tetraethylammonium hydroxide; and dodecylbenzene sulfone. Anionic surfactants such as sodium silicate and sodium lauryl sulfate; and nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyethylene glycol monostearate.
[0028]
In addition, after crushing or crushing in a dry system, and further performing classification processing, performing crushing or crushing alone processing, or performing only classification processing, water and / or a boiling point in the range of 50 to 240 ° C. And a slurry with the organic compound described in (1).
[0029]
Alternatively, a dry process and a wet process may be appropriately combined. For example, after slurried particles pulverized in a dry process, classification is performed in a wet process, and after crushing and / or classification process in a dry process, the wet process is performed. Any method such as performing a grinding process may be employed.
[0030]
Examples of the dry pulverization or pulverization treatment include pulverization using a high-speed rotary impact pulverizer, an airflow pulverizer, or the like. An example of the classification processing includes classification by an air classifier. Examples of the wet pulverization or crushing treatment include pulverization with beads. Examples of the classification treatment include classification using a centrifugal sedimentation classifier.
[0031]
The concentration of the slurry is not particularly limited, but is preferably as high as possible because the solvent is finally removed, and may be in the range of 5 to 50% by weight based on the total weight of the slurry. preferable. When the amount is within the above range, the amount of slurry added when producing the polyester composition can be reduced, so that decomposition and degradation of the polyester can be suppressed, and the slurry can be easily handled. There are many.
[0032]
In the polyester composition of the present invention, a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium, titanium or the like, which is usually used in the production of polyester, a phosphorus compound as a coloring inhibitor, and other polyesters Inactive particles and organic compounds used for the modification of the above may be contained within the range of achieving the object of the present invention.
[0033]
The polyester composition according to the present invention has a small amount of agglomerated foreign matters, and furthermore, a filter having a diameter of 64 mm and a filter made of a plain woven wire mesh having a nominal opening standard size of 0.026 mm according to JIS G3556 is superposed at right angles at a temperature of 290 ° C. When filtered at a flow rate of 33.3 g / min, the pressure is less than 5 MPa / day, which is very low for the particle-containing polyester. Therefore, it is possible to realize an effect that there is little filter clogging and a rise in pack pressure at the time of the melting process, and there are few process defects such as thread breakage and film breakage. It should be noted that the pressure increase after the elapse of 120 hours means a pressure increase value from the elapse of 120 hours to the elapse of 144 hours.
[0034]
The polyester composition of the present invention can be used as it is after spinning or as a so-called masterbatch, after diluting the polymer to a relatively low concentration in the spinning step or another molding step.
[0035]
If the case where the polyester composition thus obtained is melt-spun into fibers is described, there is no need to employ a special method for spinning, and a normal melt-spinning method for polyester fibers can be arbitrarily adopted. The fiber spun here may be a solid fiber having no hollow portion or a hollow fiber having a hollow portion. Further, the outer shape and the shape of the hollow portion in the cross section of the spun fiber may be circular or irregular. Further, when spinning, a composition containing the above-mentioned calcium phosphate fine particles and a polyester or polyester composition not containing the calcium phosphate fine particles are used. You may make a side type composite fiber.
[0036]
When fine pores are provided on the surface of the fibrous polyester composition thus obtained, the dyed composition exhibits improved color depth and sharpness when dyed. Wear durability can be satisfied. As a means for providing such fine pores, any method such as a physical or chemical method may be used, but a method of bringing a fibrous polyester composition into contact with a basic compound to reduce the weight is preferable. The contact with the basic compound can be easily performed by subjecting the fiber to a treatment such as stretching heat treatment or false twisting as necessary, or further forming the fabric, for example, by treating with an aqueous solution of a basic compound. It can be carried out.
[0037]
Examples of the basic compound used here include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, sodium carbonate, potassium carbonate and the like. Of these, sodium hydroxide and potassium hydroxide are particularly preferred.
[0038]
The concentration of the aqueous solution of the basic compound varies depending on the type of the basic compound, treatment conditions, and the like, but is preferably in the range of 0.1 to 30% by weight. The processing temperature is preferably in the range of room temperature to 100 ° C. Processing time is usually in the range of 1 minute to 4 hours.
[0039]
The amount reduced by the treatment of the aqueous solution of the basic compound is preferably in the range of 2% by weight or more based on the weight of the fiber. By treating with an aqueous solution of a basic compound in this way, a large number of micropores arranged in the fiber axis direction can be formed on the fiber surface and in the vicinity thereof, so that the dye exhibits a better color depth when dyed. . There is no particular upper limit on the weight loss. However, if the weight loss is excessive, physical properties are reduced and fibrillation is likely to occur. In many cases, the upper limit is preferably 30% by weight.
[0040]
【Example】
Hereinafter, the present invention will be described more specifically with reference to examples. The measurement of each characteristic in the examples was performed by the following methods. In the examples, "parts" means parts by weight.
[0041]
(Average particle size)
It was measured by a method according to JIS Z8823-1 using HORIBA CAPA-500.
[0042]
The average particle size of the calcium phosphate fine particles according to the present invention is measured before being added to the polyester composition, and it has been separately confirmed that the same average particle size can be maintained in the polyester composition.
[0043]
(Intrinsic viscosity ([η]))
The sample was dissolved in a mixed solvent of 40 parts by weight of 1,1,2,2-tetrachloroethane and 60 parts by weight of phenol, and measured at 35 ° C.
[0044]
(Filtration pressurization of polyester composition)
In order to evaluate the pressure increase during filtration of the polyester composition, the filtration pressure increase rate was evaluated as follows.
[0045]
A polymer fixed-quantity feeding device is attached to the exit side of the molten polymer of the small single screw type extruder, and a filter made of a plain woven wire mesh having a nominal opening standard size of 0.026 mm according to JIS G3556 having an inner diameter of 64 mm is further attached to the exit side. Two pieces were mounted orthogonally. Next, the temperature of the molten polymer was controlled to be constant at 290 ° C., and the polymer was continuously filtered for 24 hours so that the polymer flow rate was 33.3 g / min. Then, the pressure rise value on the inlet side of the filter was defined as a filtration pressure rise speed 1. Next, the filtration operation was further continued, and the pressure increase value from the time point of 120 hours to the time point of 144 hours was defined as the filtration pressure increase rate 2. Filtration pressure rise rate 2 corresponds to “filtration pressure increase” according to the present invention.
[0046]
(Depth of color)
As a measure of the depth of color, the chromaticity (K / S) was used. This value was obtained by measuring the spectral reflectance of the sample fabric with an RC-330 type self-recording spectrophotometer manufactured by Shimadzu and using the following Kubelka-Munk equation. The larger this value is, the larger the deep color effect is.
[0047]
K / S = (1-R) ² / 2R
Note that R represents the reflectance, K represents the absorption coefficient, and S represents the scattering coefficient.
[0048]
(Friction discoloration resistance)
Using a Gakushin type flat abrasion machine for friction fastness test, using a georgette made of 100% polyethylene terephthalate as a friction cloth, flat wear a predetermined number of times under a load of 500 g of test cloth to change the degree of discoloration. It was determined by using a gray scale. The case where the abrasion was extremely low was defined as Class 1, and the case where it was extremely high was defined as Class 3. Only the first grade is the level that is practically used.
[0049]
[Reference Example 1]
(Preparation of calcium phosphate fine particle slurry)
The average particle size was adjusted to 0.08 μm by using a sand grinder manufactured by Igarashi Kikai Co., Ltd. using 20% by weight of ethylene glycol slurry of tertiary calcium phosphate manufactured by Taihei Chemical Co., Ltd. and zirconia beads having a diameter of 0.8 mm as a crushed material.
[0050]
[Example 1]
(Manufacture of polyester)
Using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, the slurry prepared in Reference Example 1 was converted into an oligomer produced by a transesterification reaction according to a conventional method using 0.038 parts by weight of manganese acetate tetrahydrate as a catalyst. Then, the amount of tricalcium phosphate was added so as to be 2.5% by weight based on the final product composition, and the reaction was continued for 15 minutes. Then, 0.045 parts by weight of antimony trioxide was added, and the mixture was further reacted for 5 minutes. Then, the temperature was raised to 290 ° C. under reduced pressure, and a polycondensation reaction was performed under a high vacuum of 0.03 kPa or less to obtain polyester pellets having an intrinsic viscosity of 0.64.
[0051]
The pellets were dried at 140 ° C. for 6 hours and melt-spun at 290 ° C. using a spinneret having 36 circular spinning holes having a hole diameter of 0.3 mm. Spinning was performed for 120 hours. Then, it was drawn 3.5 times to obtain a drawn yarn of 83 dtex / 36 fill. This raw yarn was subjected to strong twisting of 2500 T / m in S-twist and 2500 T / m in Z-twist, followed by steaming the strong twist at 80 ° C. for 30 minutes to perform twisting. The pressure increase during spinning was 1 MPa / day, and the yarn breakage rate during spinning and drawing was only 1%. These values were almost the same as those obtained when the polyester containing no calcium phosphate fine particles according to the present invention was spun and drawn.
[0052]
The yarn breakage rate is the number of spinning breaks that occurred during the operation of the spinning machine, excluding the yarn breakage caused by artificial or mechanical factors. (%).
[0053]
Spun yarn breakage rate (%) = [number of times of yarn breakage / (number of operating winders × number of doffs)] × 100 (where the number of doffs refers to the number of times the undrawn yarn package is wound up to a specified amount (10 kg)). )
Regarding the draw breakage rate, the number of draw breaks occurring during the operation of the drawing machine is recorded, excluding the breakage caused by artificial or mechanical factors, and the draw breakage rate (%) is calculated by the following formula. It was done.
[0054]
Stretch breaking rate (%) = [number of times of thread breakage / (number of working weights × number of doffs)] × 100 (where the number of doffs is the number of times the false twisted yarn package is wound up to a specified amount (2.5 kg). .)
The twisted strong twist yarn was alternately arranged with two S and Z at a warp density of 47 yarns / cm and a weft density of 32 yarns / cm to weave a satin georgette fabric.
[0055]
The obtained greige was relaxed at a boiling temperature for 20 minutes with a rotary washer, embossed, preset by a conventional method, and treated with a 3.5% by weight aqueous sodium hydroxide solution at a boiling temperature to reduce the weight loss by 20%. % Of the fabric was obtained. On the surface of the reduced fabric, a large number of micropores having a short diameter of 0.1 to 0.5 μm and a long diameter of 0.1 to 0.8 μm arranged in the fiber axis direction are formed on the fiber surface. It was confirmed with an electron microscope.
[0056]
After dyeing these fabrics after alkali treatment with Dianix Black HG-FS (manufactured by Mitsubishi Chemical) 15% owf at 130 ° C. for 60 minutes, the fabric was treated at 70 ° C. with an aqueous solution containing 1 g / L of sodium hydroxide and 1 g / L of hydrosulfite. After being reduced and washed for 20 minutes, a black dyed cloth was obtained. Table 1 shows the color depth of these black cloths and the abrasion discoloration resistance at 200 times of wear.
[0057]
In addition, separately from the above, the above-mentioned "pressure increase of filtration of the polyester composition" was performed, and the filtration pressure increasing speed 1 and the filtration pressure increasing speed 2 were measured. The results are also shown in Table 1.
[0058]
[Example 2]
The procedure was performed in the same manner as in Example 1 except that the content of the calcium phosphate fine particles was changed as shown in Table 1. Table 1 shows the results. The pressure increase during spinning and the yarn breakage rate during spinning and drawing were almost the same as in Example 1.
[0059]
[Example 3]
The operation was performed in the same manner as in Example 1 except that the average particle size of the calcium phosphate fine particles was changed as shown in Table 1. Table 1 shows the results. The pressure increase during spinning and the yarn breakage rate during spinning and drawing were almost the same as in Example 1.
[0060]
[Example 4]
Example 3 was carried out in the same manner as in Example 3, except that the type of particles was changed as shown in Table 1. Table 1 shows the results. The pressure increase during spinning and the yarn breakage rate during spinning and drawing were almost the same as in Example 1.
[0061]
[Comparative Example 1]
The same procedure as in Example 1 was carried out except for using fine particles, except that silica particles having an average particle size of 0.03 μm were used instead of the tribasic calcium phosphate fine particles. Table 1 shows the results. The surface of the reduced fabric had irregular irregularities of 0.2 to 0.7 μm, and fine irregularities of 0.05 to 0.2 μm were present in the irregularities.
[0062]
[Table 1]

[0063]
【The invention's effect】
According to the present invention, there is provided a polyester composition having fine pores when imparting the shape of a fiber or a film, and exhibiting improved color depth and sharpness when dyed. Wear durability can be satisfied. This composition has a small amount of foreign matter, and therefore, there is little filter clogging and increase in pack pressure during melt processing such as blending, spinning, and film formation, and there are few process defects such as thread breakage and film breakage.

Claims (8)

With polyester,
An average particle size in the range of _{0.01~0.1μm Ca a H b P c O} d ( where, a is 1 to 10 real, b is 0-10 real, c is a real number of 1 to 6 , D represents a real number of 1 to 10).
A polyester composition having a content of the calcium phosphate fine particles in a range of 0.03 to 5% by weight. The polyester composition according to claim 1, wherein the calcium phosphate fine particles include at least one member selected from the group consisting of monocalcium phosphate, calcium diphosphate, tricalcium phosphate, and a mixture thereof. The polyester composition according to claim 1, wherein at least 80 mol% of the repeating units of the polyester are ethylene terephthalate units. Two filters, each having an inner diameter of 64 mm and made of a plain woven wire mesh having a nominal mesh size of 0.026 mm based on JIS G3556, are superposed at right angles, and the polyester composition is filtered at a temperature of 290 ° C. and a filtration rate of 33.3 g / min. The polyester composition according to any one of claims 1 to 3, wherein, when filtered, the pressure increase in filtration measured after 120 hours is less than 5 MPa / day. The polyester composition according to any one of claims 1 to 4, which has a fibrous or film-like shape. The polyester composition according to any one of claims 1 to 4, wherein the polyester composition is provided with a fibrous or film-like shape, and then brought into contact with a basic compound to reduce the weight. The polyester composition according to claim 6, wherein the weight is reduced by 2% by weight or more. The polyester composition according to any one of claims 5 to 7, which has micropores on the surface.