JP3758089B2 - Polyester composition and molded article comprising the same - Google Patents

Description

【００５２】
【化２】

【００５３】
【化３】

【００５４】
【化４】

【００５５】
(ただし、Ｒ₁〜Ｒ₇は水素、アルキル基、アリール基、シクロアルキル基またはアリールアルキル基、Ｘ₁〜Ｘ₅は水素、アルキル基、アリール基、シクロアルキル基、アリールアルキル基またはアルカリ金属、あるいは各式中のＸ₁〜Ｘ₅とＲ₁〜Ｒ₇のうちそれぞれ１個は互いに連結して環構造を形成してもよい)
【００５６】
化学式（Ｃ−１）で表されるホスフィン酸化合物としては、ジメチルホスフィン酸、フェニルメチルホスフィン酸、次亜リン酸、次亜リン酸ナトリウム、次亜リン酸カリウム、次亜リン酸リチウム、次亜リン酸エチル、
【化５】

または
【化６】

の化合物およびこれらの加水分解物、ならびに上記ホスフィン酸化合物の縮合物などがある。
【００５７】
化学式（Ｃ−２）で表される亜ホスホン酸化合物としては、フェニル亜ホスホン酸、フェニル亜ホスホン酸ナトリウム、フェニル亜ホスホン酸カリウム、フェニル亜ホスホン酸リチウム、フェニル亜ホスホン酸エチルなどがある。
化学式（Ｃ−３）で表されるホスホン酸化合物としてはフェニルホスホン酸、エチルホスホン酸、フェニルホスホン酸ナトリウム、フェニルホスホン酸カリウム、フェニルホスホン酸リチウム、フェニルホスホン酸ジエチル、エチルホスホン酸ナトリウム、エチルホスホン酸カリウムなどがある。
化学式（Ｃ−４）で表される亜リン酸化合物としては、亜リン酸、亜リン酸水素ナトリウム、亜リン酸ナトリウム、亜リン酸トリエチル、亜リン酸トリフェニル、ピロ亜リン酸などがある。
また、下記化学式（Ｄ）で表されるアルカリ化合物を添加すると、本発明のポリエステル組成物の熱安定性が更に向上することを見出した。
Ｚ−ＯＲ₈ （Ｄ）
（ただし、Ｚはアルカリ金属、Ｒ₈は水素、アルキル基、アリール基、シクロアルキル基、−Ｃ（Ｏ）ＣＨ₃ または−Ｃ（Ｏ）ＯＺ'、（Ｚ'は水素、アルカリ金属））
【００５８】
化学式（Ｄ）で表されるアルカリ化合物としては、水酸化ナトリウム、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムプロポキシド、ナトリウムブトキシド、カリウムメトキシド、リチウムメトキシド、酢酸ナトリウム、炭酸ナトリウム、およびアルカリ土類金属を含むアルカリ土類化合物などが挙げられるが、いずれもこれらの化合物に限定されるものではない。
【００５９】
本発明に用いられるメタキシリレン基含有ポリアミド（Ｂ）中の前記アルカリ化合物の含有量は、リン原子含有量（Ｘ）の１．５〜６．０倍が好ましい。より好ましくは１．８〜５．５倍、更に好ましくは２．０〜５．０倍である。アルカリ化合物の含有量がリン原子含有量（Ｘ）の１．５倍より少ないと、ゲル化が促進されやすくなる。一方、アルカリ化合物の含有量がリン原子含有量（Ｘ）の６．０倍より多いと、重合速度が遅くなり、粘度も充分に上がらず、かつ特に減圧系ではゲル化が促進され不経済である。
【００６０】
本発明で使用する前記化学式（Ｃ−１）〜（Ｃ−４），及び化学式（Ｄ）で表される化合物はそれぞれ単独で用いてもよいが、特に併用して用いる方が、ポリエステル組成物の熱安定性が向上するので好ましい。なお、前述の化合物の他に、従来公知の酸化防止剤、紫外線吸収剤、耐候剤、艶消剤、滑剤、粘度安定剤などを中空成形体の香味保持性、ガスバリアー性、透明性を損なわない程度で併用してもよい。
【００６１】
本発明で用いられるメタキシリレン基含有ポリアミド（Ｂ）に前記、リン原子含有化合物およびアルカリ化合物を配合するには、ポリアミドの重合前の原料、重合中に添加するかあるいは該重合体に溶融混合してもよい。
【００６２】
本発明で用いられるメタキシリレン基含有ポリアミド（Ｂ）の三級窒素の含有量は好ましくは２．０モル％以下、より好ましくは１．５モル％以下、さらに好ましくは１．０モル％以下である。三級窒素の含有量が２．０モル％を超えるメタキシリレン基含有ポリアミド（Ｂ）を含むポリエステル組成物を用いて得た成形体は、ゲル化物による着色した異物状物を含み、また色も悪くなることがある。特に延伸成形して得た延伸フイルムや二軸延伸中空成形体では、ゲル状物の存在する個所は正常に延伸されずに肉厚となって、厚み斑の原因となり、商品価値のない成形体が多くなる場合がある。
【００６３】
また、３級窒素の含有量の下限は、製造上の理由から０．００１モル％、さらには０．０１モル％、特には０．０５モル％であることが好ましい。３級窒素の含有量が０．００１モル％以下のメタキシリレン基含有ポリアミドを製造しようとする際には、高度に精製した原料を用いる、劣化防止剤を大量に必要とする、重合温度を低く保つ必要がある等の生産性に問題が起こることがある。
【００６４】
なお，ここで言う三級窒素とは、イミノ化合物に基づく窒素と三級アミドに基づく窒素の両者であり、三級窒素の含有量は、二級アミド（ポリアミドの直鎖状主鎖を構成するアミド）に基づく窒素に対するモル比（モル％）で表わした含有量である。
【００６５】
本発明に用いられるメタキシリレン基含有ポリアミド（Ｂ）のチップの形状は、シリンダ−型、角型、球状または扁平な板状等の何れでもよい。その平均粒径は通常１．０〜５ｍｍ、好ましくは１．２〜４．５ｍｍ、さらに好ましくは１．５〜４．０ｍｍの範囲である。例えば、シリンダ−型の場合は、長さは１．０〜４ｍｍ、径は１．０〜４ｍｍ程度であるのが実用的である。球状粒子の場合は、最大粒子径が平均粒子径の１．１〜２．０倍、最小粒子径が平均粒子径の０．７倍以上であるのが実用的である。また、チップの重量は１０〜３０ｍｇ／個の範囲が実用的である。
【００６６】
本発明に用いられるメタキシリレン基含有ポリアミド（Ｂ）の密度は、１．２０〜１．２４ｍｇ／ｃｍ³が好ましく、より好ましくは１．２０ｍｇ／ｃｍ³以上であり、１．２３ｍｇ／ｃｍ³以下である。
【００６７】
本発明のポリエステル組成物を構成するポリエステル（Ａ）とメタキシリレン基含有ポリアミド（Ｂ）との混合割合は、前記ポリエステル（Ａ）１００重量部に対して前記メタキシリレン基含有ポリアミド（Ｂ）０．０１重量部〜１００重量部であることが好ましい。前記のポリエステル組成物からＡＡ含有量が非常に少ない成形体を得たい場合のメタキシリレン基含有ポリアミド（Ｂ）の添加量は、前記ポリエステル（Ａ）１００重量部に対して０．０１〜５重量部が好ましく、より好ましい下限は０．１重量部、さらに好ましい下限は０．５重量部であり、より好ましい上限は４重量部、さらに好ましい上限は３重量部である。
【００６８】
またガスバリヤ−性が非常に優れ、かつ実用性を損なわない透明性を持つ成形体を得たい場合は、前記ポリエステル（Ａ）１００重量部に対して１〜１００重量部が好ましく、より好ましい下限は３重量部さらに好ましい下限は５重量部であり、より好ましい上限は６０重量部、さらに好ましい上限は３０重量部である。メタキシリレン基含有ポリアミド（Ｂ）の混合量が、ポリエステル（Ａ）１００重量部に対して０．０１重量部未満の場合は、得られた成形体のＡＡ含有量が低減されず、成形体内容物の香味保持性が非常に悪くなることがある。また、メタキシリレン基含有ポリアミド（Ｂ）の混合量が、ポリエステル（Ａ）１００重量部に対して１００重量部を超える場合は、得られた成形体の透明性が非常に悪くことがあり、また成形体の機械的特性も低下することがある。
【００６９】
本発明に用いられるポリエステル組成物中のアジピン酸、メタキシリレンジアミン、及びアジピン酸とメタキシリレンジアミンからなる環状体から選ばれる１種以上のモノマー類、あるいは環状体の遊離した状態での含有量は合計量で０．２５重量％以下であることが好ましい。より好ましくは０．２３重量％以下であり、さらに好ましくは０．２０重量％以下である。本発明のポリエステル組成物から耐熱性の中空成形体等を成形する場合、モノマー類、あるいは環状体の含有量が０．２５重量％を超える場合には、加熱金型表面へのモノマー類、あるいは環状体の付着が急激に増加し、得られた中空成形体等の透明性が非常に悪化することがある。更には、得られた中空成形体等に充填された飲料の風味や臭いに影響を及ぼす場合がある。
【００７０】
前記のアジピン酸とメタキシリレンジアミンからなる環状体とは、下記式（式３）で表されるアジピン酸とメタキシリレンジアミンの縮合物である。
【００７１】
【化７】

（上記式３中、ｎは１〜８の整数を表す。）
【００７２】
また、本発明に用いられるポリエステル組成物中の環状エステル３量体の含有量は好ましくは０．５０重量％以下、より好ましくは０．４５重量％以下、さらに好ましくは０．４０重量％以下である。本発明のポリエステル組成物から耐熱性の中空成形体等を成形する場合、環状エステル３量体の含有量が０．５０重量％を超える場合には、加熱処理条件によっては加熱金型表面へのオリゴマ−付着が急激に増加し、得られた中空成形体等の透明性が非常に悪化することがある。
【００７３】
また、本発明に用いられるポリエステル組成物中のアセトアルデヒド含有量は好ましくは１５ｐｐｍ以下、より好ましくは１２ｐｐｍ以下、さらに好ましくは１０ｐｐｍ以下である。本発明のポリエステル組成物中のアセトアルデヒド含有量が１５ｐｐｍを超える場合には、得られた中空成形体等に充填された飲料の風味や臭いに影響を及ぼす場合がある。
【００７４】
また、本発明に用いられるポリエステル組成物中のホルムアルデヒド（以下、ＦＡと略することがある）含有量は好ましくは５ｐｐｍ以下、より好ましくは４ｐｐｍ以下、さらに好ましくは３ｐｐｍ以下である。本発明のポリエステル組成物中のホルムアルデヒド含有量が５ｐｐｍを超える場合には、得られた中空成形体等に充填された飲料の風味や臭いに影響を及ぼす場合がある。
【００７５】
また、本発明に用いられる主たる繰り返し単位がエチレンアリレートであるポリエステル（Ａ）を２９０℃の温度で６０分間溶融した時の環状エステル３量体の増加量が０．５０重量％以下であることが望ましい。環状エステル３量体の増加量は好ましくは０．２重量％以下、より好ましくは０．１重量％以下であることが望ましい。２９０℃の温度で６０分間溶融した時の環状エステル３量体の増加量が０．３０重量％を越えるポリエステルを用いると、ポリエステル組成物を成形する際の樹脂溶融時に環状エステル３量体量が増加し、加熱処理条件によっては加熱金型表面へのオリゴマ−付着が急激に増加し、得られた中空成形体等の透明性が非常に悪化することがある。
【００７６】
２９０℃の温度で６０分間溶融した時の環状エステル３量体の増加量が０．３０重量％以下である、本発明に用いられるポリエステル（Ａ）は、溶融重縮合後や固相重合後に得られたポリエステルに残存する重縮合触媒を失活処理することにより製造することができる。ポリエステル中の重縮合触媒を失活処理する方法としては、溶融重縮合後や固相重合後にポリエステルチップを水や水蒸気または水蒸気含有気体と接触処理する方法が挙げられる。
【００７７】
前記の目的を達成するためにポリエステルチップを水や水蒸気または水蒸気含有気体と接触処理する方法を次に述べる。
熱水処理方法としては、水中に浸ける方法やシャワ−でチップ上に水をかける方法等が挙げられる。処理時間としては５分〜２日間、好ましくは１０分〜１日間、さらに好ましくは３０分〜１０時間で、水の温度としては２０〜１８０℃、好ましくは４０〜１５０℃、さらに好ましくは５０〜１２０℃である。
また処理方法は連続方式、バッチ方式のいずれであっても差し支えないが、工業的に行うためには連続方式の方が好ましい。
【００７８】
ポリエステルのチップをバッチ方式で水処理する場合は、サイロタイプの処理槽が挙げられる。すなわちバッチ方式でポリエステルのチップをサイロへ受け入れ水処理を行う。ポリエステルのチップを連続方式で水処理する場合は、塔型の処理槽に継続的又は間欠的にポリエステルのチップを上部より受け入れ、水処理させることができる。
【００７９】
またポリエステルのチップと水蒸気または水蒸気含有ガスとを接触させて処理する場合は、５０〜１５０℃、好ましくは５０〜１１０℃の温度の水蒸気または水蒸気含有ガスあるいは水蒸気含有空気を好ましくは粒状ポリエチレンテレフタレ−ト１kg当り、水蒸気として０．５ｇ以上の量で供給させるか、または存在させて粒状ポリエチレンテレフタレ−トと水蒸気とを接触させる。
この、ポリエステルのチップと水蒸気との接触は、通常１０分間〜２日間、好ましくは２０分間〜１０時間行われる。
【００８０】
また処理方法は連続方式、バッチ方式のいずれであっても差し支えない。
ポリエステルのチップをバッチ方式で水蒸気と接触処理をする場合は、サイロタイプの処理装置が挙げられる。すなわちポリエステルのチップをサイロへ受け入れ、バッチ方式で、水蒸気または水蒸気含有ガスを供給し接触処理を行なう。
【００８１】
ポリエステルのチップを連続的に水蒸気と接触処理する場合は塔型の処理装置に連続で粒状ポリエチレンテレフタレ−トを上部より受け入れ、並流あるいは向流で水蒸気を連続供給し水蒸気と接触処理させることができる。
上記の如く、水又は水蒸気で処理した場合は、粒状ポリエチレンテレフタレ−トを必要に応じて振動篩機、シモンカ−タ−などの水切り装置で水切りし、コンベヤ−によって次の乾燥工程へ移送する。
【００８２】
水又は水蒸気と接触処理したポリエステルのチップの乾燥は、通常用いられるポリエステルの乾燥処理を用いることができる。連続的に乾燥する方法としては、上部よりポリエステルのチップを供給し、下部より乾燥ガスを通気するホッパ−型の通気乾燥機が通常使用される。
【００８３】
バッチ方式で乾燥する乾燥機としては大気圧下で乾燥ガスを通気しながら乾燥してもよい。
乾燥ガスとしては大気空気でも差し支えないが、ポリエステルの加水分解や熱酸化分解による分子量低下を防止する点からは乾燥窒素、除湿空気が好ましい。
【００８４】
また、本発明に用いられる、主たる繰り返し単位がエチレンアリレートであるポリエステル（Ａ）は、ポリオレフィン樹脂、ポリアミド樹脂、ポリアセタ−ル樹脂、ポリブチレンテレフタレ−ト樹脂からなる群から選ばれた少なくとも一種の樹脂０．１ｐｐｂ〜１０００ｐｐｍを配合してなることを特徴とするポリエステルであることができる。本発明に用いられるポリエステル（Ａ）中での前記のポリオレフィン樹脂等の配合割合は、０．１ｐｐｂ〜１０００ｐｐｍ、好ましくは０．３ｐｐｂ〜１００ｐｐｍ、より好ましくは０．５ｐｐｂ〜１ｐｐｍ、さらに好ましくは０．５ｐｐｂ〜４５ｐｂｂである。
【００８５】
配合量が０．１ｐｐｂ未満の場合は、結晶化速度が非常におそくなり、中空成形体の口栓部の結晶化が不十分となるため、サイクルタイムを短くすると口栓部の収縮量が規定値範囲内におさまらないためキャッピング不良となることがあったり、また、耐熱性中空成形体を成形する延伸熱固定金型の汚れが激しく、透明な中空成形体を得ようとすると頻繁に金型掃除をしなければならないことがある。また１０００ｐｐｍを超える場合は、結晶化速度が早くなり、中空成形体の口栓部の結晶化が過大となったり、このため口栓部の収縮収縮量が規定値範囲内におさまらないためキャッピング不良となり内容物の漏れが生じたり、また中空成形体用予備成形体が白化し、このため正常な延伸が不可能となることがある。また、シ−ト状物の場合、１０００ｐｐｍを越えると透明性が非常に悪くなり、また延伸性もわるくなって正常な延伸が不可能で、厚み斑の大きな、透明性の悪い延伸フイルムしか得られないことがある。
【００８６】
本発明に用いられるポリエステル（Ａ）に配合されるポリオレフィン樹脂としては、ポリエチレン系樹脂、ポリプロピレン系樹脂、またはα−オレフィン系樹脂が挙げられる。
【００８７】
本発明に用いられるポリエステル（Ａ）に配合されるポリエチレン系樹脂としては、例えば、エチレンの単独重合体、エチレンと、プロピレン、ブテン−１、３−メチルブテン−１、ペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、デセン−１等の炭素数２〜２０程度の他のα−オレフィンや、酢酸ビニル、塩化ビニル、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、スチレン等のビニル化合物との共重合体等が挙げられる。
具体的には、例えば、低・中・高密度ポリエチレン等（分岐状又は直鎖状）のエチレン単独重合体、エチレン−プロピレン共重合体、エチレン−ブテン−１共重合体、エチレン−４−メチルペンテン−１共重合体、エチレン−ヘキセン−１共重合体、エチレン−オクテン−１共重合体、エチレン−酢酸ビニル共重合体、エチレン−アクリル酸共重合体、エチレン−メタクリル酸共重合体、エチレン−アクリル酸エチル共重合体等のエチレン系樹脂が挙げられる。
【００８８】
また本発明に用いられるポリエステル（Ａ）に配合されるポリプロピレン系樹脂としては、例えば、プロピレンの単独重合体、プロピレンと、エチレン、ブテン−１、３−メチルブテン−１、ペンテン−１、４−メチルペンテン−１、ヘキセン−１、オクテン−１、デセン−１等の炭素数２〜２０程度の他のα−オレフィンや、酢酸ビニル、塩化ビニル、アクリル酸、メタクリル酸、アクリル酸エステル、メタクリル酸エステル、スチレン等のビニル化合物との共重合体等が挙げられる。具体的には、例えば、ブロピレン単独重合体、プロピレン−エチレン共重合体、プロピレン−エチレン−ブテン−１共重合体等のプロピレン系樹脂が挙げられる。
【００８９】
また本発明に用いられるポリエステル（Ａ）に配合されるα−オレフィン系樹脂としては、４−メチルペンテン−１等の炭素数２〜８程度のα−オレフィンの単独重合体、それらのα−オレフィンと、エチレン、プロピレン、ブテン−１、３−メチルブテン−１、ペンテン−１、ヘキセン−１、オクテン−１、デセン−１等の炭素数２〜２０程度の他のα−オレフィンとの共重合体等が挙げられる。具体的には、例えば、ブテン−１単独重合体、４−メチルペンテン−１単独重合体、ブテン−１−エチレン共重合体、ブテン−１−プロピレン共重合体等のブテン−１系樹脂や４−メチルペンテン−１とＣ２〜Ｃ１８のα−オレフィンとの共重合体、等が挙げられる。
【００９０】
また、本発明に用いられるポリエステル（Ａ）に配合されるポリアミド樹脂としては、例えば、ブチロラクタム、δ−バレロラクタム、ε−カプロラクタム、エナントラクタム、ω−ラウロラクタム等のラクタムの重合体、６−アミノカプロン酸、１１−アミノウンデカン酸、１２−アミノドデカン酸等のアミノカルボン酸の重合体、ヘキサメチレンジアミン、ノナメチレンジアミン、デカメチレンジアミン、ドデカメチレンジアミン、ウンデカメチレンジアミン、２，２，４−又は２，４，４−トリメチルヘキサメチレンジアミン等の脂肪族ジアミン、１，３−又は１，４−ビス（アミノメチル）シクロヘキサン、ビス（ｐ−アミノシクロヘキシルメタン）等の脂環式ジアミン、ｍ−又はｐ−キシリレンジアミン等の芳香族ジアミン等のジアミン単位と、グルタル酸、アジピン酸、スベリン酸、セバシン酸等の脂肪族ジカルボン酸、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸、テレフタル酸、イソフタル酸等の芳香族ジカルボン酸等のジカルボン酸単位との重縮合体、及びこれらの共重合体等が挙げられ、具体的には、例えば、ナイロン４、ナイロン６、ナイロン７、ナイロン８、ナイロン９、ナイロン１１、ナイロン１２、ナイロン６６、ナイロン６９、ナイロン６１０、ナイロン６１１、ナイロン６１２、ナイロン６Ｔ、ナイロン６Ｉ、ナイロンＭＸＤ６、ナイロン６／６６、ナイロン６／６１０、ナイロン６／１２、ナイロン６／６Ｔ、ナイロン６Ｉ／６Ｔ等が挙げられる。
【００９１】
また、本発明に用いられるポリエステル（Ａ）に配合されるポリアセタ−ル樹脂としては、例えばポリアセタ−ル単独重合体や共重合体が挙げられる。ポリアセタ−ル単独重合体としては、ＡＳＴＭ−Ｄ７９２の測定法により測定した密度が１．４０〜１．４２ｇ／ｃｍ³、ＡＳＴＭＤ−１２３８の測定法により、１９０℃、荷重２１６０ｇで測定したメルトインデックス（ＭＩ）が０．５〜５０ｇ／１０分の範囲のポリアセタ−ルが好ましい。
【００９２】
また、ポリアセタ−ル共重合体としては、ＡＳＴＭ−Ｄ７９２の測定法により測定した密度が１．３８〜１．４３ｇ／ｃｍ³、ＡＳＴＭＤ−１２３８の測定法により、１９０℃、荷重２１６０ｇで測定したメルトインデックス（ＭＩ）が０．４〜５０ｇ／１０分の範囲のポリアセタ−ル共重合体が好ましい。これらの共重合成分としては、エチレンオキサイドや環状エ−テルが挙げられる。
【００９３】
また、本発明に用いられるポリエステル（Ａ）に配合されるでポリブチレンテレフタレ−ト樹脂としては、例えばテレフタル酸と１，４−ブタンジオ−ルからなるポリブチレンテレフタレ−ト単独重合体やこれにナフタレンジカルボン酸、ジエチレングリコ−ル、１，４−シクロヘキサンジメタノ−ル等を共重合した共重合体が挙げられる。
【００９４】
また、本発明において用いられる前記のポリオレフィン樹脂等を配合したポリエステルは、前記ポリエステルに前記のポリオレフィン等の樹脂を、その含有量が前記範囲となるように、直接に添加し溶融混練する方法、または、マスタ−バッチとして添加し溶融混練する方法等の慣用の方法によるほか、前記のポリオレフィン等の樹脂を、前記ポリエステルの製造段階、例えば、溶融重縮合時、溶融重縮合直後、予備結晶化直後、固相重合時、固相重合直後等のいずれかの段階、または、製造段階を終えてから成形段階に到るまでの間に粉粒体として直接に添加するか、或いは、ポリエステルチップの流動条件下に前記のポリオレフィン等の樹脂製の部材に接触させる等の方法で混入させた後、溶融混練する方法等によることもできる。
【００９５】
ここで、ポリエステルチップ状体を流動条件下に前記のポリオレフィン等の樹脂製の部材に接触させる方法としては、前記のポリオレフィン等の樹脂製の部材が存在する空問内で、ポリエステルチップを該部材に衝突接触させることが好ましく、具体的には、例えば、ポリエステルの溶融重縮合直後、予備結晶化直後、固相重合直後等の製造工程時、また、ポリエステルチップの製品としての輸送段階等での輸送容器充填・排出時、また、ポリエステルチップの成形段階での成形機投入時、等における気力輸送配管、重力輸送配管、サイロ、マグネットキャッチャ−のマグネット部等の一部を前記のポリオレフィン等の樹脂製とするか、または、前記のポリオレフィン等の樹脂をライニングするとか、或いは前記移送経路内に棒状又は網状体等の前記のポリオレフィン等の樹脂製部材を設置する等して、ポリエステルチップを移送する方法が挙げられる。ポリエステルチップの前記部材との接触時間は、通常、０．０１秒〜数分程度の極短時間であるが、ポリエステルに前記のポリオレフィン等の樹脂を微量混入させることができる。
【００９６】
また、本発明に用いられる、主たる繰り返し単位がエチレンアリレートであるポリエステル（Ａ）のアセトアルデヒド含有量は１０ｐｐｍ以下、好ましくは８ｐｐｍ以下、より好ましくは６ｐｐｍ以下、さらに好ましくは４ｐｐｍ以下、ホルムアルデヒド含有量は６ｐｐｍ以下、好ましくは５ｐｐｍ以下、より好ましくは４ｐｐｍ以下であることが望ましい。アセトアルデヒド含有量が１０ｐｐｍを超え、およびホルムアルデヒド含有量が６ｐｐｍを超える場合は、このポリエステルから成形された成形体等の内容物の香味保持性の効果が悪くなる。
なお、アセトアルデヒド量、ホルムアルデヒド量の下限は０．１ｐｐｂであることが好ましい。
【００９７】
また本発明に用いられる、主たる繰り返し単位がエチレンアリレートであるポリエステル（Ａ）中に共重合されたジエチレングリコ−ル量は前記ポリエステル（Ａ）を構成するグリコ−ル成分の下限は好ましくは１．０モル％、より好ましくは１．３モル％、さらに好ましくは１．５モル％であり、上限は好ましくは５．０モル％、より好ましくは４．５モル％、さらに好ましくは４．０モル％である。ジエチレングリコ−ル量が５．０モル％を越える場合は、熱安定性が悪くなり、成型時に分子量低下が大きくなったり、またアセトアルデヒド含有量やホルムアルデヒド含有量の増加量が大となることがあり好ましくない。またジエチレングリコ−ル含有量が１．０モル％未満の場合は、得られた成形体の透明性が悪くなることがある。
【００９８】
本発明のポリエステル組成物は、従来公知の方法により前記のポリエステル（Ａ）と前記のメタキシリレン基含有ポリアミド（Ｂ）を混合して得ることができる。例えば、前記のポリアミドチップと前記のポリエステルチップとをタンブラー、Ｖ型ブレンダー、ヘンシェルミキサー等でドライブレンドしたもの、さらにドライブレンドした混合物を一軸押出機、二軸押出機、ニーダー等で１回以上溶融混合したもの、さらには必要に応じて溶融混合物を高真空下または不活性ガス雰囲気下で固相重合したものなどが挙げられる。また、あらかじめ前記のポリエステル（Ａ）と前記のメタキシリレン基含有ポリアミド（Ｂ）を溶融混合したものを、前記のポリエステル（Ａ）とドライブレンドしたもの、さらにドライブレンドした混合物を溶融混合したものが挙げられる。
【００９９】
本発明のポリエステル組成物に飽和脂肪酸モノアミド、不飽和脂肪酸モノアミド、飽和脂肪酸ビスアミド、不飽和脂肪酸ビスアミド等を同時に併用することも可能である。
【０１００】
飽和脂肪酸モノアミドの例としては、ラウリン酸アミド、パルミチン酸アミド、ステアリン酸アミド、ベヘン酸アミド等が挙げられる。不飽和脂肪酸モノアミドの例としては、オレイン酸アミド、エルカ酸アミドリシノ−ル酸アミド等が挙げられる。飽和脂肪酸ビスアミドの例としては、メチレンビスステアリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスラウリン酸アミド、エチレンビスステアリン酸アミド、エチレンビスベヘン酸アミド、ヘキサメチレンビスステアリン酸アミド、ヘキサメチレンビスベヘン酸アミド等が挙げられる。また、不飽和脂肪酸ビスアミドの例としては、エチレンビスオレイン酸アミド、ヘキサメチレンビスオレイン酸アミド等が挙げられる。好ましいアミド系化合物は、飽和脂肪酸ビスアミド、不飽和脂肪酸ビスアミド等である。このようなアミド化合物の配合量は、１０ｐｐｂ〜１×１０⁵ｐｐｍの範囲であることが好ましい。
【０１０１】
また炭素数８〜３３の脂肪族モノカルボン酸の金属塩化合物、例えばナフテン酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、モンタン酸、メリシン酸、オレイン酸、リノ−ル酸等の飽和及び不飽和脂肪酸のリチュウム塩、ナトリウム塩、カリウム塩、マグネシウム塩、カルシウム塩、及びコバルト塩等を同時に併用することも可能である。これらの化合物の配合量は、１０ｐｐｂ〜３００ｐｐｍの範囲であることが好ましい。
【０１０２】
本発明のポリエステル組成物には、必要に応じて他の添加剤、例えば、公知の紫外線吸収剤、酸化防止剤、酸素吸収剤、酸素捕獲剤、外部より添加する滑剤や反応中に内部析出させた滑剤、離型剤、核剤、安定剤、帯電防止剤、顔料などの各種の添加剤を配合してもよい。また、紫外線遮断性樹脂、耐熱性樹脂、使用済みポリエチレンテレフタレ−トボトルからの回収品等を適当な割合で混合することも可能である。
【０１０３】
また、無色透明の樹脂が望ましい用途においては、溶融加工の間に発生するかすかな黄色い色を青色着色剤の添加によって消すことができる。着色剤は重合の間、又は配合の間にブレンド物に直接添加することができる。配合の間に添加される場合には、着色剤はそのまま添加することもできるし、マスターバッチなどのような濃縮物として添加することもできる。着色剤の量は、その吸光係数およびその用途に望ましい色に調整することができる。好ましい着色剤としては、１−シアノ−６−（４−（２−ヒドロキシエチル）アニリノ）−３−メチル−３Ｈ−ジベンゾ（Ｆ，Ｉ，Ｊ）−イソキノリン−２，７−ジオンが挙げられる。着色剤の添加量は２〜１５ｐｐｍの範囲であることが好ましい。
【０１０４】
また、本発明のポリエステル組成物をフイルム用途に使用する場合には、滑り性、巻き性、耐ブロッキング性などのハンドリング性を改善するために、ポリエステル組成物中に炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、硫酸カルシウム、硫酸バリウム、リン酸リチウム、リン酸カルシウム、リン酸マグネシウム等の無機粒子、蓚酸カルシウムやカルシウム、バリウム、亜鉛、マンガン、マグネシウム等のテレフタル酸塩等の有機塩粒子やジビニルベンゼン、スチレン、アクリル酸、メタクリル酸、アクリル酸またはメタクリル酸のビニル系モノマーの単独または共重合体等の架橋高分子粒子などの不活性粒子を含有させることが出来る。
【０１０５】
本発明のポリエステル組成物は、一般的に用いられる溶融成形法を用いてフィルム、シート、容器、その他の包装材料を成形することができる。本発明のポリエステル組成物からなる延伸フィルムは射出成形もしくは押出成形して得られたシート状物を、通常ＰＥＴの延伸に用いられる一軸延伸、逐次二軸延伸、同時二軸延伸のうちの任意の延伸方法を用いて成形される。また圧空成形、真空成形によリカップ状やトレイ状に成形することもできる。
【０１０６】
延伸フィルムを製造するに当たっては、延伸温度は通常は８０〜１３０℃である。延伸は一軸でも二軸でもよいが、好ましくはフィルム実用物性の点から二軸延伸である。延伸倍率は一軸の場合であれば通常１．１〜１０倍、好ましくは１．５〜８倍の範囲で行い、二軸延伸であれば縦方向および横方向ともそれぞれ通常１．１〜８倍、好ましくは１．５〜５倍の範囲で行えばよい。また、縦方向倍率／横方向倍率は通常０．５〜２、好ましくは０．７〜１．３である。得られた延伸フィルムは、さらに熱固定して、耐熱性、機械的強度を改善することもできる。熱固定は通常緊張下、１２０℃〜２４０、好ましくは１５０〜２３０℃で、通常数秒〜数時間、好ましくは数十秒〜数分間行われる。
【０１０７】
中空成形体を製造するにあたっては、本発明のＰＥＴから成形したブリフォームを延伸ブロー成形してなるもので、従来ＰＥＴのブロー成形で用いられている装置を用いることができる。具体的には例えば、射出成形または押出成形で一旦プリフォームを成形し、そのままあるいは口栓部、底部を加工後、それを再加熱し、ホットパリソン法あるいはコールドパリソン法などの二軸延伸ブロー成形法が適用される。この場合の成形温度、具体的には成形機のシリンダー各部およびノズルの温度は通常２６０〜２９０℃の範囲である。延伸温度ば通常７０〜１２０℃、好ましくは９０〜１１０℃で、延伸倍率は通常縦方向に１．５〜３．５倍、円周方向に２〜５倍の範囲で行えばよい。得られた中空成形体は、そのまま使用できるが、特に果汁飲料、ウーロン茶などのように熱充填を必要とする飲料の場合には一般的に、さらにブロー金型内で熱固定処理を行い、耐熱性を付与して使用される。熱固定は通常、圧空などによる緊張下、１００〜２００℃、好ましくは１２０〜１８０℃で、数秒〜数時間、好ましくは数秒〜数分間行われる。
【０１０８】
また、口栓部に耐熱性を付与するために、射出成形または押出成形により得られたプリフォ−ムの口栓部を遠赤外線や近赤外線ヒ−タ設置オ−ブン内で結晶化させたり、あるいはボトル成形後に口栓部を前記のヒ−タで結晶化させる。
【０１０９】
また、本発明のポリエステル組成物は、積層成形体や積層フイルム等の一構成層としても用いることが出来る。特に、ＰＥＴとの積層体の形で容器等の製造に使用される。積層成形体の例としては、本発明のポリエステル組成物からなる外層とＰＥＴ内層との二層から構成される二層構造あるいは本発明のポリエステル組成物からなる内層とＰＥＴ外層との二層から構成される二層構造の成形体、本発明のポリエステル組成物を含む中間層とＰＥＴの外層および最内層から構成される三層構造あるいは本発明のポリエステル組成物を含む外層および最内層とＰＥＴの中間層から構成される三層構造の成形体、本発明のポリエステル組成物を含む中間層とＰＥＴの最内層、中心層および最内層から構成される五層構造の成形体等が挙げられる。ＰＥＴ層には、他のガスバリア−性樹脂、紫外線遮断性樹脂、耐熱性樹脂、使用済みポリエチレンテレフタレ−トボトルからの回収品等を適当な割合で混合使用することができる。
【０１１０】
また、その他の積層成形体の例としては、ポリオレフィン等のポリエステル以外の樹脂との積層成形体、紙や金属板等の異種の基材との積層成形体が挙げられる。
前記の積層成形体の厚み及び各層の厚みには特に制限は無い。また前記の積層成形体は、シ−ト状物、フイルム状物、板状物、中空体、容器等、種々の形状で使用可能である。
【０１１１】
前記の積層体の製造は、樹脂層の種類に対応した数の押出機と多層多種ダイスを使用して共押出しにより行うこともできるし、また樹脂層の種類に対応した数の射出機と共射出ランナ−および射出型を使用して共射出により行うこともできる。
本発明のポリエステル組成物は、中空成形体、トレ−、二軸延伸フイルム等の包装材、金属缶被覆用フイルム等として好ましく用いることが出来る。
また、本発明の組成物は、電子レンジおよび／またはオ−ブンレンジ等で食品を調理したり、あるいは冷凍食品を加熱するためのトレイ状容器の用途にも用いることができる。この場合は、ポリエステル組成物からのシ−ト状物をトレイ形状に成形後、熱結晶化させて耐熱性を向上させる。
なお、本発明における、主な特性値の測定法を以下に説明する。
【０１１２】
【実施例】
以下本発明を実施例により具体的に説明するが、本発明はこれらの実施例に限定させるものではない。なお、本明細書中における主な特性値の測定法を以下に説明する。
【０１１３】
（評価方法）
（１）ポリエステルの極限粘度（ＩＶ）
１，１，２，２−テトラクロルエタン／フェノ−ル（２：３重量比）混合溶媒中３０℃での溶液粘度から求めた。
【０１１４】
（２）ポリエステル中に共重合されたジエチレングリコ−ル含有量（以下［ＤＥＧ含有量」という）
メタノ−ルにより分解し、ガスクロマトグラフィ−によりＤＥＧ量を定量し、全グリコ−ル成分に対する割合（モル％）で表した。
【０１１５】
（３）環状エステル３量体の含有量（以下「ＣＴ含有量」という）
試料３００ｍｇをヘキサフルオロイソプロパノ−ル／クロロフォルム混合液（容量比＝２／３）３ｍｌに溶解し、さらにクロロフォルム３０ｍｌを加えて希釈する。これにメタノ−ル１５ｍｌを加えてポリマ−を沈殿させた後、濾過する。濾液を蒸発乾固し、ジメチルフォルムアミド１０ｍｌで定容とし、高速液体クロマトグラフ法により環状エステル３量体を定量した。
【０１１６】
（４）アセトアルデヒド含有量（以下「ＡＡ含有量」という）
試料／蒸留水＝１グラム／２ｃｃを窒素置換したガラスアンプルに入れた上部を溶封し、１６０℃で２時間抽出処理を行い、冷却後抽出液中のアセトアルデヒドを高感度ガスクロマトグラフィ−で測定し、濃度をｐｐｍで表示した。
【０１１７】
（５）ポリエステルの溶融時の環状エステル３量体増加量（△ＣＴ量）
乾燥したポリエステルチップ３ｇをガラス製試験管に入れ、窒素雰囲気下で２９０℃のオイルバスに６０分浸漬させ溶融させる。溶融時の環状エステル３量体増加量は、次式により求める。
溶融時の環状エステル３量体増加量（重量％）＝
溶融後の環状エステル３量体含有量（重量％）−溶融前の環状エステル３量体含有量（重量％）
【０１１８】
（６）メタキシリレン基含有ポリアミドの相対粘度（ＲＶ）
試料０．２５ｇを９６％硫酸２５ｍｌに溶解し、この溶液１０ｍｌをオストワルド粘度管にて２０℃で測定、下式より求めた。
ＲＶ＝ｔ／ｔ₀
ｔ₀：溶媒の落下秒数
ｔ ：試料溶液の落下秒数
【０１１９】
（７）メタキシリレン基含有ポリアミド中のナトリウム原子含有量（以下「Ｎａ含有量」という）
試料を白金るつぼにて灰化分解し、６ｍｏｌ／Ｌ塩酸を加えて蒸発乾固する。１．２ｍｏｌ／Ｌ塩酸で溶解し、原子吸光で定量して求めた。
【０１２０】
（８）メタキシリレン基含有ポリアミドの末端アミノ基濃度（ＡＥＧ，μｍｏｌ／ｇ）
試料０．５ｇをフェノール／エタノール混合溶媒（容積比４／１）５０ｍｌに室温で溶解させた後、水／エタノール混合溶媒（容積比３／２）２０ｍｌを加え、撹拌する。その後、塩酸を用いて中和滴定を行い、末端アミノ基濃度を求めた。
【０１２１】
（９）メタキシリレン基含有ポリアミドの末端カルボキシル基濃度（ＣＥＧ，μｍｏｌ／ｇ）
試料０．５ｇにベンジルアルコール２０ｍｌを加え、１７０〜１８０℃のオイルバス中で加熱溶解後、水酸化ナトリウム水溶液で中和滴定を行い、末端カルボキシル基濃度を求めた。
【０１２２】
（１０）段付き成形板の成形
乾燥したポリエステル組成物を名機製作所製Ｍ−１５０Ｃ（ＤＭ）射出成形機により、シリンダー温度２９０℃において、１０℃に冷却した段付き平板金型を用い成形する。得られた段付き成形板は、２，３，４，５，６，７，８，９，１０，１１ｍｍの厚みの約３ｃｍ×約５ｃｍ角のプレートを階段状に備えたもので、段付き成形板１個の重量は約１４６ｇである。５ｍｍ厚みのプレートはヘイズ（霞度％）測定に使用する。
【０１２３】
（１１）ヘイズ（霞度％）およびヘイズ斑
上記（１０）の成形体（肉厚５ｍｍ）を切り取り、日本電色（株）製ヘイズメーターで測定する。
【０１２４】
（１２）金型汚れの評価
窒素ガスを用いた乾燥機で乾燥したポリエステルの所定量および窒素ガスを用いた乾燥機で乾燥したメタキシリレン基含有ポリアミドチップの所定量を用いて、各機製作所製Ｍ−１５０Ｃ（ＤＭ）射出成型機により樹脂温度２９０℃でプリフォ−ムを成形した。このプリフォ−ムの口栓部を自家製の口栓部結晶化装置で加熱結晶化させた後、コ−ポプラスト社製ＬＢ−０１Ｅ延伸ブロ−成型機を用いて二軸延伸ブロ−成形し、引き続き約１４５℃に設定した金型内で約７秒間熱固定し、１０００ｃｃの中空成形体を得た。同様の条件で２０００本の中空成形体を連続的に延伸ブロ−成形し、その前後における金型表面の状態を目視で観察し、下記のように評価した。
○ ： 連続成形試験の前後において変化なし
△ ： 連続成形試験後にかなり付着物あり
× ： 連続成形試験後に付着物が非常に多い
【０１２５】
（１３）中空成形体の透明性
（１２）の２０００本成形後に得られた中空成形体の外観を目視で観察し、下記のように評価した。
◎ ： 透明である
○ ： 実用的な範囲で透明であり、未溶融物は見られない
× ： 透明性に劣る、又は未溶融物が見られる
【０１２６】
（１４）官能試験
上記の中空成形体に沸騰した蒸留水を入れ密栓後３０分保持し、室温へ冷却し室温で１ヶ月間放置し、開栓後風味、臭いなどの試験を行った。比較用のブランクとして、蒸留水を使用。官能試験は１０人のパネラーにより次の基準により実施し、平均値で比較した。
（評価基準）
０：異味、臭いを感じない
１：ブランクとの差をわずかに感じる
２：ブランクとの差を感じる
３：ブランクとのかなりの差を感じる
４：ブランクとの非常に大きな差を感じる
【０１２７】
（１５）酸素透過量（ｃｃ／容器１本・２４hr・atm）
Modern Controls社製酸素透過量測定器ＯＸ−ＴＲＡＮ１００により、１０００ｃｃのボトル１本当りの透過量として２０℃、０％ＲＨで測定した。
【０１２８】
（実施例および比較例に使用したポリエチレンテレフタレ−ト（ＰＥＴ））
試験に用いたＰＥＴ（Ｇｅ残存量＝約４０〜５０ｐｐｍ、リン残存量＝約３０〜３５ｐｐｍ）の特性を表１に示す。これらは、すべて連続溶融重縮合−固相重合装置で重合したものである。
ＰＥＴ（ａ）は、固相重合後イオン交換水中で約９０℃で３時間、熱水処理したものである。
なお、ＰＥＴ（ａ）〜ＰＥＴ（ｂ）のＤＥＧ含有量はすべて約２．７モル％である。
【０１２９】
【表１】

【０１３０】
（実施例および比較例に使用したメタキシリレン基含有ポリアミド（ＭＸＤ６））
【０１３１】
ＭＸＤ６(c)の製造方法
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７.６６ｋｇ、アジピン酸２９.６５ｋｇ、を内温８５℃にて調合し、スラリー状の透明な溶液とした。缶内のＰＨ値を７．９５に調製した後、ゲル化抑制剤としてＮａＯＨ ３４.０９ｇ、ＮａＨ₂ＰＯ₂・Ｈ₂Ｏ ２５.８１ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度２６０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３２】
ＭＸＤ６(d)の製造方法
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７.６６ｋｇ、アジピン酸２９.６５ｋｇ、を内温８５℃にて調合し、スラリー状の透明な溶液とした。缶内のＰＨ値を７．２０に調製した後、ゲル化抑制剤としてＮａＯＨ ６．８２ｇ、ＮａＨ₂ＰＯ₂・Ｈ₂Ｏ ５．１６ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度２６０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３３】
ＭＸＤ６(e)の製造方法
缶内のＰＨ値を７．０６に調製した以外は、ＭＸＤ６(c)の製造方法と同様にして樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３４】
ＭＸＤ６(f)の製造方法
缶内のＰＨ値を６．９２に調製した以外は、ＭＸＤ６(c)の製造方法と同様にして樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３５】
ＭＸＤ６(g)の製造方法
攪拌機、分縮器、温度計、滴下ロートおよび窒素ガス導入管を備えた内容積２５０リットルの調製缶に、精秤したメタキシリレンジアミン２７.６６ｋｇ、アジピン酸２９.６５ｋｇ、を内温８５℃にて調合し、スラリー状の透明な溶液とした。缶内のＰＨ値を７．２０に調製した後、ゲル化抑制剤としてＮａＯＨ １０２．２７ｇ、ＮａＨ₂ＰＯ₂・Ｈ₂Ｏ ７７．４３ｇを投入して１５分攪拌した。その溶液を内容積２７０リットルの反応缶に移送し、缶内温度２６０℃、缶内圧１．０ＭＰａの条件下で攪拌して反応させた。留出する水を系外に除き、缶内温度が２３５℃になった時点で、缶内圧を６０分間かけて常圧に戻した。常圧で攪拌を行い、目標粘度に達した時点で攪拌を停止し、２０分間放置した。その後、反応缶下部の取り出し口より溶融樹脂を取り出し、冷却固化させてストランドカッターにて樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３６】
ＭＸＤ６(h)の製造方法
ゲル化抑制剤を添加せずに、ＭＸＤ６(d)の製造方法と同様にして樹脂チップを得た。得られた樹脂の特性を表２に示す。
【０１３７】
【表２】

【０１３８】
（実施例１）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｃ）０．５重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は８ｐｐｍ、官能試験評価は０．７、外観は実用的な範囲で透明であり、また金型汚れは認められなかった。
【０１３９】
（実施例２）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｃ）３．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は７ｐｐｍ、官能試験評価は０．６、外観は実用的な範囲で透明であり、また金型汚れは認められなかった。
【０１４０】
（実施例３）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｃ）２０．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は６ｐｐｍ、官能試験評価は０．６、酸素透過量は０．２０ｃｃ／容器１本・２４hr・atm、外観は実用的な範囲で透明であり、また金型汚れは認められなかった。
【０１４１】
（実施例４）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｄ）３．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は７ｐｐｍ、官能試験評価は０．７、外観は実用的な範囲で透明であり、また金型汚れは認められなかった。
【０１４２】
（比較例１）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｅ）０．５重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は１０ｐｐｍと低く、官能試験評価は０．８、金型汚れも認められなかったが、透明性が悪く、実用性に乏しかった。
【０１４３】
（比較例２）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｅ）３．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は８ｐｐｍと低く、官能試験評価は０．７、金型汚れも認められなかったが、透明性が悪く、実用性に乏しかった。
【０１４４】
（比較例３）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｆ）０．５重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体の金型汚れは認められなかったが、ＡＡ含有量は１７ｐｐｍ、官能試験評価は２．１とブランクの蒸留水と差があった。また、透明性が悪く、実用性に乏しかった。
【０１４５】
（比較例４）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｇ）０．５重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体の金型汚れは認められなかったが、ＡＡ含有量は２０ｐｐｍ、官能試験評価は２．３とブランクの蒸留水と差があった。また、透明性が悪く、実用性に乏しかった。
【０１４６】
（比較例５）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｇ）２０．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体の酸素透過量は０．２１ｃｃ／容器１本・２４hr・atm、金型汚れは認められなかったが、ＡＡ含有量は２８ｐｐｍ、官能試験評価は２．７とブランクの蒸留水と差があった。また、透明性が悪く、実用性に乏しかった。
【０１４７】
（比較例６）
ＰＥＴ（ａ）１００重量部に対してＭＸＤ６（ｈ）３．０重量部を用いて、評価方法（１２）の方法により中空成形体を成形し、その成形体のＣＴ含有量、ＡＡ含有量を測定した。また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
中空成形体のＡＡ含有量は９ｐｐｍ、官能試験評価は０．８、金型汚れも認められなかったが、数本の中空成形体に未溶融物が見られ、実用性に乏しかった。
【０１４８】
（比較例７）
ＰＥＴ（ａ）のみを用いて、評価方法（１２）の方法により中空成形体を成形し、また金型汚れ評価も行った。
得られた中空成形体の特性及び金型汚れ評価結果を表３に示す。
【０１４９】
【表３】

【０１５０】
【発明の効果】
本発明のポリエステル組成物によれば、透明性、香味保持性および／またはガスバリヤー性に優れ、さらには成形時での金型汚れを発生させにくい中空成形体やシ−ト状物および延伸フィルムが得られる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a polyester composition suitably used as a raw material for a molded article such as a bottle for beverages, a film, a sheet, and the like, and a molded article excellent in flavor retention (flavorability) comprising the same. It is about. Moreover, the polyester composition with little mold stain | pollution | contamination at the time of shape | molding a hollow molded object is given.
[0002]
[Prior art]
Polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) are excellent in both mechanical properties and chemical properties, and thus have high industrial value, such as fibers, films, sheets, and bottles. Widely used as such.
[0003]
As a material for containers such as seasonings, oils, beverages, cosmetics, and detergents, various resins are employed depending on the type of filling contents and the purpose of use.
[0004]
Of these, polyester is excellent in mechanical strength, heat resistance, transparency, and gas barrier properties, and is particularly suitable as a material for molded articles such as beverage filling containers such as juices, soft drinks, and carbonated drinks. .
[0005]
For example, such a polyester is supplied to a molding machine such as an injection molding machine to form a preform for a hollow molded body, and the preform is inserted into a mold having a predetermined shape and stretched and blown to form a bottle. In general, the body portion of the bottle is heat-treated (heat set) to be formed into a hollow molded container, and further, if necessary, the stopper portion of the bottle is heat-treated (crystallization of the stopper portion).
[0006]
However, PET contains acetaldehyde (hereinafter sometimes abbreviated as AA) as a by-product during melt polycondensation. Moreover, PET produced acetaldehyde by thermal decomposition when thermoforming a molded body such as a hollow molded body, and the acetaldehyde content in the material of the obtained molded body was increased, and the hollow molded body was filled. Affects the flavor and odor of beverages.
[0007]
Therefore, various measures have heretofore been taken to reduce the acetaldehyde content in the polyester molded body. Generally, a method of reducing AA content by solid-phase polymerization of melt-polycondensed polyester, a method of reducing AA generation during molding using a copolyester having a lower melting point, and thermoforming A method for reducing the molding temperature as much as possible and a method for reducing the shear stress during thermoforming as much as possible are used.
[0008]
In recent years, polyester containers such as polyethylene terephthalate have come to be used as containers for low flavor beverages such as mineral water and oolong tea. In the case of such beverages, these beverages are generally heat-filled or sterilized by heating after filling, but these container contents can be obtained only by reducing the AA content in the polyester molded material by the above method. It has been found that the flavor and odor of the fish are not improved.
[0009]
Further, for example, a method using a polyester composition in which 0.05 parts by weight or more and less than 1 part by weight of a metaxylylene group-containing polyamide resin is added to 100 parts by weight of a polyester resin (see Patent Document 1), or a thermoplastic polyester A polyester container made of a polyester composition containing a specific polyamide whose terminal amino group concentration is regulated within a certain range has been proposed (see Patent Document 2), but a low flavor such as mineral water is proposed. It has been found that in some cases it is insufficient as a material for beverage containers.
[0010]
For example, in Patent Document 1 (Japanese Patent Publication No. 6-6662), a method using a polyester composition in which 0.05 parts by weight or more and less than 1 part by weight of a metaxylylene group-containing polyamide resin is added to 100 parts by weight of a polyester resin. Although it is used, the relative viscosity and end group concentration of the metaxylylene group-containing polyamide are not particularly mentioned, and may be insufficient as a material for containers for low flavor beverages such as mineral water. I understand that.
[0011]
Further, in Patent Document 2 (Japanese Patent Publication No. 4-71425), a polyester container comprising a polyester composition containing a specific polyamide whose terminal amino group concentration is regulated within a certain range in a thermoplastic polyester, the polyamide It is said that the relative viscosity of the glass may be in a range having a general film forming ability, but a transparent beverage container such as a mineral water is made using a polyamide having a relative viscosity actually applied within the range. In some cases, the resulting polyester composition is poor in transparency and practical.
[0012]
Further, in Patent Document 3 (Japanese Patent No. 3229321), a polyester composition having improved flavor retention composed of polyester and polyamide having an average molecular weight defined in a certain range is proposed (see Patent Document 3). However, there is no particular mention of additives added to prevent burnout lines due to thermal degradation of polyamide and unmelted substances due to gelation, and there are many cases in which practical use is poor. In particular, the sodium atom in the polyamide not only promotes thermal degradation of the polyester to be blended, but also acts as a crystallization nucleating agent, so that the transparency of the molded product obtained from the polyester composition may be poor. However, the present inventors have found that a polyester composition excellent in transparency and flavor retention can be obtained by regulating the sodium atom content in the polyamide within a specific range.
[0013]
On the other hand, a polyester molded body mainly composed of PET is excellent in gas barrier properties as described above, but is unsatisfactory as a hollow molded body for contents containing a compound very sensitive to oxygen such as vitamin C. It is.
[0014]
In order to solve such a problem, for example, we have a polyester hollow molded body containing 1 to 100 parts by weight of a metaxylylene group-containing polyamide resin with respect to 100 parts by weight of a polyester resin (Japanese Patent Publication No. 4-54702). Proposal). However, when producing a heat-resistant hollow molded article using such a polyester composition, monomers and oligomer components contained in the polyester composition migrate to and accumulate on the mold surface, and the appearance of the hollow molded article is improved. There was a problem of losing. In addition, troublesome mold cleaning has to be frequently performed, and there is a problem that productivity is lowered.
[0015]
[Patent Document 1]
Japanese Examined Patent Publication No. 6-6661
[Patent Document 2]
Japanese Examined Patent Publication No. 4-71425
[Patent Document 3]
Japanese Patent No. 3229321
[0016]
[Problems to be solved by the invention]
An object of the present invention is to provide a polyester composition excellent in transparency, flavor retention and / or gas barrier property. Another object of the present invention is to provide a polyester composition that hardly causes mold contamination during molding.
[0017]
[Means for Solving the Problems]
  In order to achieve the above purpose, the polyester composition of the present invention is a polyester comprising 100 parts by weight of a polyester (A) whose main repeating unit is ethylene arylate and 0.01 to 100 parts by weight of a metaxylylene group-containing polyamide (B). It is a composition, Comprising: The sodium atom content in this metaxylylene group containing polyamide (B) exists in the range of 0.01-1000 ppm.And the haze of the 5 mm-thick molded product obtained by molding the polyester composition at 290 ° C. is 20% or less.It is a polyester composition characterized by this.
[0018]
In this case, the relative viscosity (RV) of the metaxylylene group-containing polyamide (B) can be in the range of 1.3 to 2.1.
In this case, the metaxylylene group-containing polyamide (B) can satisfy both of the following formulas (1) and (2).
AEG + CEG ≧ 150 (1)
AEG / CEG ≧ 1.0 (2)
(In the formulas (1) and (2), AEG represents the terminal amino group concentration (μmol / g) of the metaxylylene group-containing polyamide, and CEG represents the terminal carboxyl group concentration (μmol / g) of the metaxylylene group-containing polyamide.)
[0019]
In this case, the content of the cyclic ester trimer in the polyester composition may be 0.50% by weight or less.
In this case, the acetaldehyde content in the polyester composition can be 15 ppm or less.
In this case, the increase amount of the cyclic ester trimer when the polyester (A) whose main repeating unit is ethylene arylate is melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less. it can.
In this case, the molded article of the present invention is a molded article obtained by molding the above-described polyester composition.
In this case, the haze of a 5 mm-thick molded product obtained by molding the above polyester composition at 290 ° C. can be 20% or less.
[0020]
(In this case, the claim2The molded body described in 1 can be a hollow molded body. In this case, the claim2The molded article described in 1 can be a sheet-like product. In this case, the claim2Can be a stretched film formed by stretching a sheet-like material in at least one direction.
[0021]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the polyester composition of the present invention and a molded article comprising the same will be described in detail.
The polyester (A) used in the present invention is a polyester whose main repeating unit is ethylene arylate, preferably a linear polyester containing 85 mol% or more of ethylene arylate units, more preferably 90 mol% or more, particularly A linear polyester containing 95% or more is preferable. Among these, polyethylene terephthalate and polyethylene 2,6-naphthalate are preferable. Hereinafter, the case where the polyester (A) is a polyester whose main repeating unit is ethylene terephthalate will be mainly described.
[0022]
Examples of the dicarboxylic acid used as a copolymerization component when the polyester is a copolymer include isophthalic acid, 2,6-naphthalenedicarboxylic acid, diphenyl-4,4′-dicarboxylic acid, and diphenoxyethanedicarboxylic acid. Aromatic dicarboxylic acids such as acids and functional derivatives thereof, oxyacids such as p-oxybenzoic acid and oxycaproic acid and functional derivatives thereof, aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, glutaric acid, and the like Examples thereof include functional derivatives thereof, aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and functional derivatives thereof.
[0023]
Examples of the glycol used as a copolymer component when the polyester is a copolymer include aliphatic glycols such as diethylene glycol, trimethylene glycol, tetramethylene glycol, and neopentyl glycol. And aromatic glycols such as alicyclic glycols such as bisphenol and cyclohexanedimethanol, bisphenol A, and alkylene oxide adducts of bisphenol A.
[0024]
Furthermore, examples of the polyfunctional compound as a copolymer component used when the polyester is a copolymer include trimellitic acid and pyromellitic acid as acid components, and glycerin as a glycol component. And pentaerythritol. The amount of copolymerization component used should be such that the polyester remains substantially linear. Monofunctional compounds such as benzoic acid and naphthoic acid may be copolymerized.
[0025]
The polyester is prepared by reacting terephthalic acid with ethylene glycol and, if necessary, the above copolymerization component to distill off water and esterify it, and then, as a polycondensation catalyst, Sb compound, Ge compound, Ti compound or Al Direct esterification method in which polycondensation is performed under reduced pressure using one or more compounds selected from the compounds, or dimethyl terephthalate and ethylene glycol and, if necessary, the above copolymerization component in the presence of a transesterification catalyst After the methyl alcohol is distilled off and transesterified, the polycondensation catalyst is mainly subjected to reduced pressure using one or more compounds selected from Sb compounds, Ge compounds, Ti compounds or Al compounds. Is produced by a transesterification method in which polycondensation is carried out.
Furthermore, in order to increase the intrinsic viscosity of the polyester and reduce the acetaldehyde content, solid phase polymerization may be performed.
[0026]
The esterification reaction, transesterification reaction, melt polycondensation reaction and solid phase polymerization reaction may be performed in a batch reactor or a continuous reactor. In any of these methods, the melt polycondensation reaction may be performed in one stage or may be performed in multiple stages. The solid phase polymerization reaction can be carried out by a batch type apparatus or a continuous type apparatus, similarly to the melt polycondensation reaction. Melt polycondensation and solid phase polymerization may be carried out continuously or separately.
[0027]
Examples of the Sb compound used in the production of the polyester (A) used in the present invention include antimony trioxide, antimony acetate, antimony tartrate, antimony tartrate, antimony oxychloride, antimony glycolate, antimony pentoxide, and triphenyl. Antimony etc. are mentioned. The Sb compound is added so that the residual amount of Sb in the produced polymer is in the range of 50 to 250 ppm.
[0028]
Examples of the Ge compound used in the production of the polyester (A) used in the present invention include amorphous germanium dioxide, crystalline germanium dioxide, germanium chloride, germanium tetraethoxide, germanium tetra-n-butoxide, germanium phosphite, and the like. Is mentioned. When a Ge compound is used, the amount used is 5 to 150 ppm, preferably 10 to 100 ppm, more preferably 15 to 70 ppm as the residual amount of Ge in the polyester.
[0029]
Examples of the Ti compound used in the production of the polyester (A) used in the present invention include tetraethyl titanate, tetraisopropyl titanate, tetra-n-propyl titanate, tetra-n-butyl titanate and the like. Tetraalkyl titanates and their partial hydrolysates, titanyl oxalate, titanyl ammonium oxalate, sodium titanyl oxalate, potassium titanyl oxalate, titanyl calcium oxalate, titanyl succinate, titanium trimellitic acid, titanium sulfate, Examples include titanium chloride. The Ti compound is added so that the residual amount of Ti in the produced polymer is in the range of 0.1 to 10 ppm.
[0030]
Examples of the Al compound used in the production of the polyester (A) used in the present invention include carboxylates such as aluminum formate, aluminum acetate, aluminum propionate, and aluminum oxalate, oxides, aluminum hydroxide, aluminum chloride, Inorganic acid salts such as aluminum hydroxide chloride and aluminum carbonate, aluminum alkoxides such as aluminum methoxide and aluminum ethoxide, aluminum chelate compounds with aluminum acetylacetonate and aluminum acetylacetate, trimethylaluminum And organoaluminum compounds such as triethylaluminum and partial hydrolysates thereof. Of these, aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum acetylacetonate are particularly preferred. The Al compound is added so that the Al remaining amount in the produced polymer is in the range of 5 to 200 ppm.
[0031]
In the case of an Al compound, an alkali metal compound or an alkaline earth metal compound may be used in combination. Examples of the alkali metal compound or alkaline earth metal compound include carboxylates such as acetates of these elements, alkoxides, and the like, and are added to the reaction system as powders, aqueous solutions, ethylene glycol solutions, and the like. The alkali metal compound or alkaline earth metal compound is added so that the residual amount of these elements in the produced polymer is in the range of 1 to 50 ppm.
[0032]
The catalyst compound can be added at any stage of the polyester formation reaction step.
Moreover, various phosphorus compounds can be used as a stabilizer. Examples of the phosphorus compound used in the present invention include phosphoric acid, phosphorous acid, phosphonic acid, and derivatives thereof. Specific examples include phosphoric acid, phosphoric acid trimethyl ester, phosphoric acid triethyl ester, phosphoric acid tributyl ester, phosphoric acid triphenyl ester, phosphoric acid monomethyl ester, phosphoric acid dimethyl ester, phosphoric acid monobutyl ester, phosphoric acid dibutyl ester, Phosphoric acid, phosphorous acid trimethyl ester, phosphorous acid triethyl ester, phosphorous acid tributyl ester, methylphosphonic acid, methylphosphonic acid dimethyl ester, ethylphosphonic acid dimethyl ester, phenylphosphonic acid dimethyl ester, phenylphosphonic acid diethyl ester, phenyl -Luphosphonic acid diphenyl ester, etc., and these may be used alone or in combination of two or more. The phosphorus compound is added at an arbitrary stage of the polyester forming reaction step so that the amount of phosphorus remaining in the produced polymer is in the range of 5 to 100 ppm.
[0033]
The intrinsic viscosity of the polyester (A) used in the present invention is preferably 0.55 to 1.30 deciliter / gram, the lower limit is more preferably 0.58 deciliter / gram, still more preferably 0.60 deciliter / gram, and the upper limit. Is more preferably in the range of 1.10 deciliter / gram, and still more preferably 0.90 deciliter / gram. When the intrinsic viscosity is less than 0.55 deciliter / gram, the mechanical properties of the obtained molded article and the like may be poor. If it exceeds 1.30 deciliters / gram, the resin temperature may increase when melted by a molding machine or the like, resulting in severe thermal decomposition, increasing the amount of free low molecular weight compounds that affect the fragrance retention, Problems such as yellowing of the molded product may occur.
[0034]
The shape of the polyester (A) chip used in the present invention may be any of a cylinder type, a square type, a spherical shape, a flat plate shape, and the like. The average particle size is usually 1.3 to 5 mm, preferably 1.5 to 4.5 mm, and more preferably 1.6 to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.3 to 4 mm and the diameter is about 1.3 to 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. The weight of the chip is practically in the range of 10 to 30 mg / piece.
[0035]
The density of the polyester (A) used in the present invention is 1.33-1.43 mg / cm.^Three, Preferably 1.37 to 1.42 mg / cm^ThreeRange.
[0036]
In general, polyesters contain a significant amount of copolymer components and fines having the same copolymer component content as the polyester chips that are produced during the manufacturing process. Such fines have the property of promoting crystallization of polyester, and when they are present in large quantities, the molded product molded from such polyesters becomes very poor in transparency or in the case of bottles. However, there is a problem that the amount of shrinkage at the time of crystallization of the bottle cap portion does not fall within the range of the specified value, so that the cap cannot be sealed with the cap.
[0037]
Therefore, the fine content in the polyester (A) used in the present invention is 500 ppm or less, preferably 300 ppm or less. When the content exceeds 500 ppm, the crystallization speed is increased, for example, the crystallization of the plug portion of the hollow molded container becomes excessive, and therefore the shrinkage amount of the plug portion does not fall within the range of the specified value. In some cases, the capping portion of the plug portion becomes defective, the contents are leaked, and the preform for hollow molding is whitened, which makes normal stretching impossible.
[0038]
Further, the metaxylylene group-containing polyamide (B) used in the present invention is produced from metaxylylenediamine, or a mixed xylylenediamine containing metaxylylenediamine and 30% or less of the total amount of paraxylylenediamine and a dicarboxylic acid. The polyamide resin contains at least 70 mol% or more, more preferably 75 mol% or more, particularly preferably 80 mol% or more in the molecular chain.
[0039]
Examples of the dicarboxylic acid as a copolymerization component include adipic acid, sebacic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, spellic acid, azelaic acid, undecanoic acid, undecadioic acid, dodecanedioic acid, and dimer acid. Aliphatic dicarboxylic acids such as aliphatic dicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, xylylene dicarboxylic acid and naphthalene dicarboxylic acid can be used.
[0040]
Moreover, as a diamine component as a copolymerization component, ethylenediamine, 1-methylethylenediamine, 1,3-propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, Aliphatic diamines such as decamethylene diamine, undecamethylene diamine and dodecamethylene diamine, cycloaliphatic diamine, alicyclic diamines such as bis- (4,4′-aminohexyl) methane, para-bis- (2-amino) Aromatic diamines such as ethyl) benzene and alicyclic diamines such as 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane can be used.
These dicarboxylic acids and diamines can be used by combining one kind or two or more kinds in an arbitrary ratio.
[0041]
In addition to the diamine and dicarboxylic acid, lactams such as ε-caprolactam and laurolactam, aminocarboxylic acids such as aminocaproic acid and aminoundecanoic acid, aromatic aminocarboxylic acids such as para-aminomethylbenzoic acid, etc. It can be used as a copolymerization component. In particular, the use of ε-caprolactam is desirable.
[0042]
Examples of these polymers include homopolymers such as polymetaxylylene adipamide, polymetaxylylene sebacamide, polymetaxylylene speramide, and metaxylylenediamine / adipic acid / isophthalic acid copolymers, metaxylylene. / Paraxylylene adipamide copolymer, metaxylylenediamine / adipic acid / terephthalic acid copolymer, metaxylylenediamine / hexamethylenediamine / adipic acid copolymer, metaxylylenediamine / hexamethylenediamine / terephthalate Examples thereof include an acid copolymer, a metaxylylenediamine / hexamethylenediamine / isophthalic acid copolymer, a metaxylylene / paraxylylene piperamide copolymer, and a metaxylylene / paraxylylene azelamide copolymer.
[0043]
The sodium atom content in the metaxylylene group-containing polyamide (B) used in the present invention is preferably in the range of 0.01 to 1000 ppm. The lower limit is more preferably 0.1 ppm, still more preferably 1.0 ppm. The upper limit is more preferably 900 ppm, and still more preferably 800 ppm.
When the sodium atom content in the metaxylylene group-containing polyamide (B) is less than 0.01 ppm, as will be described later, gelation tends to proceed, and when a heat-resistant hollow molded article is produced using a polyester composition, Unmelted material is easily generated. Further, when the sodium atom content in the metaxylylene group-containing polyamide (B) is more than 1000 ppm, not only the transparency of the molded product obtained from the polyester composition becomes poor, but also the molecular weight of the polyester composition is lowered and obtained. The mechanical strength of the molded body may be reduced.
[0044]
The sodium atom content in the metaxylylene group-containing polyamide (B) used in the present invention is atomic absorption spectrometry, emission spectrometry, inductively coupled plasma (hereinafter abbreviated as ICP) emission spectrometry, ICP mass spectrometry, fluorescence X It is obtained by line analysis and can be used properly depending on the sodium atom concentration.
[0045]
The relative viscosity (RV) of the metaxylylene group-containing polyamide (B) used in the present invention is preferably in the range of 1.3 to 2.1. The lower limit is more preferably 1.5, and the upper limit is more preferably 2.0. If the relative viscosity is less than 1.5, the molecular weight is too small, and the molded article made of the polyester composition of the present invention may be inferior in mechanical properties. Further, when taking out the metaxylylene group-containing polyamide (B) from the polymerization can, cooling and applying to a strand cutter, not only the resin chip size becomes non-uniform, but also a large amount of fines is produced, resulting in poor efficiency. It is not preferable. On the other hand, if the relative viscosity is greater than 2.1, the hollow molded body obtained from the polyester composition of the present invention has poor transparency and may lack practicality.
[0046]
Further, the end group concentration of the metaxylylene group-containing polyamide (B) used in the present invention is represented by the following formula (1).
AEG + CEG ≧ 150 (1)
(In formula (1), AEG represents the terminal amino group concentration (μmol / g) of the metaxylylene group-containing polyamide, and CEG represents the terminal carboxyl group concentration (μmol / g) of the metaxylylene group-containing polyamide.)
It is preferable that it is the range of these. More preferably, AEG + CEG ≧ 160, and further preferably AEG + CEG ≧ 180. When the total terminal group concentration (AEG + CEG) comprising the terminal carboxyl group concentration and the terminal amino group concentration in the metaxylylene group-containing polyamide is less than 150 (μmol / g), the flavor retention of the hollow molded article obtained from the polyester composition of the present invention is maintained. As a beverage container for low flavor, the practicality may be poor.
[0047]
Further, the end group concentration of the metaxylylene group-containing polyamide (B) used in the present invention is expressed by the following formula (2).
AEG / CEG ≧ 1.0 (2)
(In formula (2), AEG represents the terminal amino group concentration (μmol / g) of the metaxylylene group-containing polyamide, and CEG represents the terminal carboxyl group concentration (μmol / g) of the metaxylylene group-containing polyamide.)
It is preferable that it is the range of these. More preferably, AEG / CEG ≧ 1.5, and even more preferably AEG / CEG ≧ 2.0. If the ratio of the terminal amino group concentration to the terminal carboxyl group concentration in the metaxylylene group-containing polyamide (AEG / CEG) is less than 1.0, the flavor retention of the hollow molded body obtained from the polyester composition of the present invention becomes poor, As a beverage container for low flavor, there are cases where the practicality is poor.
[0048]
The above-mentioned metaxylylene group-containing polyamide is a method in which an aqueous solution of an aminocarboxylate salt formed from a diamine and a dicarboxylic acid is heated to react under pressure and normal pressure, or a method in which the diamine and dicarboxylic acid are heated to react directly under normal pressure. Can be manufactured. In particular, the metaxylylene group-containing polyamide used in the present invention can adjust the end group concentration by adding an excessive amount of diamine to dicarboxylic acid. Further, a higher viscosity metaxylylene group-containing polyamide can be obtained by solid-phase polymerization of the polyamide chips obtained by the melt polycondensation reaction.
The polycondensation reaction of the metaxylylene group-containing polyamide may be performed in a batch reactor or a continuous reactor.
[0049]
Usually, in the production of the metaxylylene group-containing polyamide (B), in order to prevent gelation due to thermal deterioration, a phosphorus stabilizer is often added for polymerization.
When the phosphorus atom content in the metaxylylene group-containing polyamide (B) used in the present invention is X, the range is preferably 0.01 ≦ X ≦ 400 ppm. The lower limit is more preferably 0.1 ppm, even more preferably 1 ppm, particularly preferably 3 ppm, and most preferably 5 ppm. The upper limit is preferably 380 ppm, more preferably 350 ppm. When X is less than 0.01 ppm, burnout lines and unmelted products are likely to occur when a heat-resistant hollow molded article is produced using a polyester composition. Moreover, the thermal deterioration at the time of a molding process is also large, and the effect as a stabilizer cannot be found. On the other hand, when X is more than 400 ppm, although the thermal stability is excellent, the transparency of the obtained hollow molded article may be deteriorated. In particular, when an Sb-based compound is added to a polymerization catalyst or PET used as an additive, darkening that may be derived from metal Sb may occur, and the transparency may be remarkably deteriorated.
[0050]
The compound containing a phosphorus atom in the metaxylylene group-containing polyamide (B) is preferably at least one selected from compounds represented by the following chemical formulas (C-1) to (C-4).
[0051]
[Chemical 1]

[0052]
[Chemical formula 2]

[0053]
[Chemical Formula 3]

[0054]
[Formula 4]

[0055]
(However, R₁~ R₇Is hydrogen, alkyl group, aryl group, cycloalkyl group or arylalkyl group, X₁~ X_FiveIs hydrogen, an alkyl group, an aryl group, a cycloalkyl group, an arylalkyl group or an alkali metal, or X in each formula₁~ X_FiveAnd R₁~ R₇Each of which may be linked together to form a ring structure)
[0056]
Examples of the phosphinic acid compound represented by the chemical formula (C-1) include dimethylphosphinic acid, phenylmethylphosphinic acid, hypophosphorous acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, hypochlorous acid. Ethyl phosphate,
[Chemical formula 5]

Or
[Chemical 6]

And hydrolysates thereof, and condensates of the above phosphinic acid compounds.
[0057]
Examples of the phosphonous acid compound represented by the chemical formula (C-2) include phenylphosphonous acid, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, and ethyl phenylphosphonite.
Examples of the phosphonic acid compound represented by the chemical formula (C-3) include phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, ethylphosphone. Examples include potassium acid.
Examples of the phosphorous acid compound represented by the chemical formula (C-4) include phosphorous acid, sodium hydrogen phosphite, sodium phosphite, triethyl phosphite, triphenyl phosphite, pyrophosphorous acid and the like. .
Moreover, when the alkali compound represented by following Chemical formula (D) was added, it discovered that the thermal stability of the polyester composition of this invention improved further.
Z-OR₈(D)
(However, Z is an alkali metal, R₈Is hydrogen, alkyl group, aryl group, cycloalkyl group, -C (O) CH_Three            Or -C (O) OZ '(where Z' is hydrogen or alkali metal))
[0058]
Examples of the alkali compound represented by the chemical formula (D) include sodium hydroxide, sodium methoxide, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxide, lithium methoxide, sodium acetate, sodium carbonate, and alkaline earth Examples include alkaline earth compounds containing metals, but they are not limited to these compounds.
[0059]
The content of the alkali compound in the metaxylylene group-containing polyamide (B) used in the present invention is preferably 1.5 to 6.0 times the phosphorus atom content (X). More preferably, it is 1.8-5.5 times, More preferably, it is 2.0-5.0 times. When the content of the alkali compound is less than 1.5 times the phosphorus atom content (X), gelation tends to be promoted. On the other hand, when the content of the alkali compound is more than 6.0 times the phosphorus atom content (X), the polymerization rate is slow, the viscosity is not sufficiently increased, and gelation is promoted particularly in a reduced pressure system, which is uneconomical. is there.
[0060]
The compounds represented by the chemical formulas (C-1) to (C-4) and chemical formula (D) used in the present invention may be used singly, but the polyester composition is particularly used in combination. This is preferable because the thermal stability is improved. In addition to the above-mentioned compounds, conventionally known antioxidants, ultraviolet absorbers, weathering agents, matting agents, lubricants, viscosity stabilizers, and the like lose the flavor retention, gas barrier properties, and transparency of the hollow molded body. You may use together in the extent which is not.
[0061]
In order to mix the phosphorus atom-containing compound and the alkali compound with the metaxylylene group-containing polyamide (B) used in the present invention, the raw material before the polymerization of the polyamide is added during the polymerization or melt-mixed into the polymer. Also good.
[0062]
The tertiary nitrogen content of the metaxylylene group-containing polyamide (B) used in the present invention is preferably 2.0 mol% or less, more preferably 1.5 mol% or less, and even more preferably 1.0 mol% or less. . A molded product obtained using a polyester composition containing a metaxylylene group-containing polyamide (B) having a tertiary nitrogen content exceeding 2.0 mol% contains a colored foreign substance due to a gelled product, and also has a poor color. May be. In particular, in stretched films and biaxially stretched hollow molded products obtained by stretch molding, the portions where gel-like materials exist are not normally stretched and become thick, causing thickness spots, and having no commercial value. May increase.
[0063]
Further, the lower limit of the tertiary nitrogen content is preferably 0.001 mol%, more preferably 0.01 mol%, and particularly preferably 0.05 mol% for the reason of production. When attempting to produce a metaxylylene group-containing polyamide having a tertiary nitrogen content of 0.001 mol% or less, a highly purified raw material is used, a large amount of deterioration inhibitor is required, and the polymerization temperature is kept low. There may be problems in productivity such as necessity.
[0064]
The tertiary nitrogen mentioned here refers to both nitrogen based on imino compounds and nitrogen based on tertiary amide, and the content of tertiary nitrogen is secondary amide (which constitutes the linear main chain of polyamide). The content is expressed as a molar ratio (mol%) to nitrogen based on (amide).
[0065]
The shape of the tip of the metaxylylene group-containing polyamide (B) used in the present invention may be any of a cylinder shape, a square shape, a spherical shape, a flat plate shape, and the like. The average particle size is usually in the range of 1.0 to 5 mm, preferably 1.2 to 4.5 mm, more preferably 1.5 to 4.0 mm. For example, in the case of a cylinder type, it is practical that the length is about 1.0 to 4 mm and the diameter is about 1.0 to 4 mm. In the case of spherical particles, it is practical that the maximum particle size is 1.1 to 2.0 times the average particle size and the minimum particle size is 0.7 times or more the average particle size. The weight of the chip is practically in the range of 10 to 30 mg / piece.
[0066]
The density of the metaxylylene group-containing polyamide (B) used in the present invention is 1.20 to 1.24 mg / cm.^ThreeIs preferable, more preferably 1.20 mg / cm^ThreeAbove, 1.23 mg / cm^ThreeIt is as follows.
[0067]
The mixing ratio of the polyester (A) and the metaxylylene group-containing polyamide (B) constituting the polyester composition of the present invention is 0.01 weight of the metaxylylene group-containing polyamide (B) with respect to 100 parts by weight of the polyester (A). The amount is preferably from 100 parts by weight to 100 parts by weight. The addition amount of the metaxylylene group-containing polyamide (B) when it is desired to obtain a molded article having a very low AA content from the polyester composition is 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyester (A). A more preferred lower limit is 0.1 parts by weight, a still more preferred lower limit is 0.5 parts by weight, a more preferred upper limit is 4 parts by weight, and a still more preferred upper limit is 3 parts by weight.
[0068]
When it is desired to obtain a molded article having excellent gas barrier properties and transparency that does not impair practicality, 1 to 100 parts by weight is preferable with respect to 100 parts by weight of the polyester (A), and a more preferable lower limit is 3 parts by weight A more preferred lower limit is 5 parts by weight, a more preferred upper limit is 60 parts by weight and a still more preferred upper limit is 30 parts by weight. When the mixing amount of the metaxylylene group-containing polyamide (B) is less than 0.01 parts by weight with respect to 100 parts by weight of the polyester (A), the AA content of the obtained molded body is not reduced, and the molded body content The flavor retention may be very poor. In addition, when the amount of the metaxylylene group-containing polyamide (B) exceeds 100 parts by weight with respect to 100 parts by weight of the polyester (A), the resulting molded article may have very poor transparency, and may be molded. The mechanical properties of the body may also be reduced.
[0069]
One or more monomers selected from adipic acid, metaxylylenediamine, and a cyclic product composed of adipic acid and metaxylylenediamine in the polyester composition used in the present invention, or inclusion of the cyclic product in a free state The total amount is preferably 0.25% by weight or less. More preferably, it is 0.23 weight% or less, More preferably, it is 0.20 weight% or less. When molding a heat-resistant hollow molded article or the like from the polyester composition of the present invention, if the monomer or cyclic content exceeds 0.25% by weight, the monomers on the surface of the heating mold, or The adhesion of the annular body increases rapidly, and the transparency of the obtained hollow molded body or the like may be extremely deteriorated. Furthermore, the flavor and odor of the beverage filled in the obtained hollow molded body may be affected.
[0070]
The cyclic product composed of adipic acid and metaxylylenediamine is a condensate of adipic acid and metaxylylenediamine represented by the following formula (formula 3).
[0071]
[Chemical 7]

(In the above formula 3, n represents an integer of 1 to 8.)
[0072]
The content of the cyclic ester trimer in the polyester composition used in the present invention is preferably 0.50% by weight or less, more preferably 0.45% by weight or less, and still more preferably 0.40% by weight or less. is there. When a heat-resistant hollow molded article or the like is molded from the polyester composition of the present invention, if the cyclic ester trimer content exceeds 0.50% by weight, depending on the heat treatment conditions, Oligomer adhesion increases rapidly, and the transparency of the obtained hollow molded article or the like may be extremely deteriorated.
[0073]
The acetaldehyde content in the polyester composition used in the present invention is preferably 15 ppm or less, more preferably 12 ppm or less, and further preferably 10 ppm or less. When the acetaldehyde content in the polyester composition of the present invention exceeds 15 ppm, the flavor and odor of the beverage filled in the obtained hollow molded article may be affected.
[0074]
The content of formaldehyde (hereinafter sometimes abbreviated as FA) in the polyester composition used in the present invention is preferably 5 ppm or less, more preferably 4 ppm or less, and even more preferably 3 ppm or less. When the formaldehyde content in the polyester composition of the present invention exceeds 5 ppm, the flavor and odor of the beverage filled in the obtained hollow molded article may be affected.
[0075]
In addition, the increase amount of the cyclic ester trimer when the polyester (A) whose main repeating unit used in the present invention is ethylene arylate is melted at a temperature of 290 ° C. for 60 minutes is 0.50% by weight or less. desirable. The increase amount of the cyclic ester trimer is preferably 0.2% by weight or less, more preferably 0.1% by weight or less. When a polyester having an increase in cyclic ester trimer of more than 0.30% by weight when melted at a temperature of 290 ° C. for 60 minutes is used, the amount of cyclic ester trimer at the time of melting the resin when molding the polyester composition Depending on the heat treatment conditions, oligomer adhesion to the surface of the heating mold increases rapidly, and the transparency of the resulting hollow molded article may be extremely deteriorated.
[0076]
The polyester (A) used in the present invention in which the increase amount of the cyclic ester trimer when melted at a temperature of 290 ° C. for 60 minutes is 0.30% by weight or less is obtained after melt polycondensation or after solid phase polymerization. The polycondensation catalyst remaining in the obtained polyester can be produced by deactivation treatment. Examples of the method for deactivating the polycondensation catalyst in the polyester include a method in which the polyester chip is contacted with water, water vapor or water vapor-containing gas after melt polycondensation or after solid phase polymerization.
[0077]
In order to achieve the above-mentioned object, a method of contacting the polyester chip with water, water vapor or water vapor-containing gas will be described below.
Examples of the hot water treatment method include a method of immersing in water and a method of applying water on a chip with a shower. The treatment time is 5 minutes to 2 days, preferably 10 minutes to 1 day, more preferably 30 minutes to 10 hours, and the water temperature is 20 to 180 ° C., preferably 40 to 150 ° C., more preferably 50 to 120 ° C.
The treatment method may be either a continuous method or a batch method, but the continuous method is preferred for industrial use.
[0078]
A silo-type treatment tank is used when water-treating polyester chips in a batch system. In other words, the polyester chip is received in a silo and treated with water in a batch system. In the case where the polyester chips are water-treated in a continuous manner, the polyester chips can be continuously or intermittently received in the tower-type treatment tank from the upper part and water-treated.
[0079]
When the polyester chip and water vapor or water vapor-containing gas are contacted, the water vapor or water vapor containing gas or water vapor containing air at a temperature of 50 to 150 ° C., preferably 50 to 110 ° C., is preferably granular polyethylene terephthalate. -0.5 kg or more of water vapor is supplied per 1 kg of tort, or the granular polyethylene terephthalate and water vapor are brought into contact with each other.
The contact between the polyester chip and water vapor is usually performed for 10 minutes to 2 days, preferably 20 minutes to 10 hours.
[0080]
The processing method may be either a continuous method or a batch method.
When a polyester chip is contact-treated with water vapor in a batch system, a silo type processing apparatus can be used. That is, a polyester chip is received in a silo, and contact processing is performed by supplying steam or a steam-containing gas in a batch manner.
[0081]
In the case where polyester chips are continuously contacted with water vapor, a granular polyethylene terephthalate is continuously received from the top in a tower-type processing apparatus, and water vapor is continuously supplied in parallel flow or countercurrent to be contacted with water vapor. Can do.
As described above, when treated with water or steam, the granular polyethylene terephthalate is drained with a draining device such as a vibrating sieve or a Simon Carter as necessary, and transferred to the next drying step by a conveyor. .
[0082]
The polyester chip that has been contact-treated with water or water vapor can be dried by a commonly used polyester drying process. As a continuous drying method, a hopper-type ventilation dryer is generally used in which a polyester chip is supplied from the upper part and a drying gas is supplied from the lower part.
[0083]
As a dryer for drying in a batch mode, drying may be performed while aeration gas is passed under atmospheric pressure.
As the dry gas, atmospheric air may be used, but dry nitrogen and dehumidified air are preferable from the viewpoint of preventing molecular weight reduction due to hydrolysis or thermal oxidative decomposition of polyester.
[0084]
In addition, the polyester (A) whose main repeating unit is ethylene arylate used in the present invention is at least one selected from the group consisting of polyolefin resins, polyamide resins, polyacetal resins, and polybutylene terephthalate resins. It can be polyester characterized by blending 0.1 ppb to 1000 ppm of resin. The blending ratio of the polyolefin resin or the like in the polyester (A) used in the present invention is 0.1 ppb to 1000 ppm, preferably 0.3 ppb to 100 ppm, more preferably 0.5 ppb to 1 ppm, and still more preferably 0.00. 5 ppb to 45 pbb.
[0085]
When the blending amount is less than 0.1 ppb, the crystallization speed becomes very slow and the crystallization of the plug part of the hollow molded body becomes insufficient. Therefore, if the cycle time is shortened, the shrinkage amount of the plug part is specified. Capping failure may occur because it does not fall within the value range, and the stretched heat-fixed mold for forming a heat-resistant hollow molded body is heavily soiled, so it is frequently necessary to obtain a transparent hollow molded body. You may need to clean it. If it exceeds 1000 ppm, the crystallization rate will be faster, the crystallization of the plug part of the hollow molded body will be excessive, and the shrinkage and shrinkage amount of the plug part will not fall within the specified range, so capping failure As a result, leakage of the contents may occur, or the preform for the hollow molded body may be whitened, and thus normal stretching may be impossible. Also, in the case of a sheet-like material, if it exceeds 1000 ppm, the transparency becomes very poor, the stretchability is also impaired and normal stretching is impossible, and only a stretched film with large thickness unevenness and poor transparency is obtained. It may not be possible.
[0086]
Examples of the polyolefin resin blended in the polyester (A) used in the present invention include a polyethylene resin, a polypropylene resin, and an α-olefin resin.
[0087]
Examples of the polyethylene resin blended in the polyester (A) used in the present invention include ethylene homopolymer, ethylene, propylene, butene-1,3-methylbutene-1, pentene-1, and 4-methylpentene. -1, hexene-1, octene-1, decene-1, etc., other α-olefins having about 2 to 20 carbon atoms, vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester, Examples thereof include a copolymer with a vinyl compound such as styrene.
Specifically, for example, ethylene homopolymer, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-4-methyl, such as low, medium and high density polyethylene (branched or linear) Penten-1 copolymer, ethylene-hexene-1 copolymer, ethylene-octene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene -Ethylene resin, such as an ethyl acrylate copolymer, is mentioned.
[0088]
Moreover, as a polypropylene resin mix | blended with the polyester (A) used for this invention, the homopolymer of propylene, propylene, ethylene, butene-1, 3-methylbutene-1, pentene-1, 4-methyl, for example Other α-olefins having about 2 to 20 carbon atoms such as pentene-1, hexene-1, octene-1, decene-1, etc., vinyl acetate, vinyl chloride, acrylic acid, methacrylic acid, acrylic ester, methacrylic ester And copolymers with vinyl compounds such as styrene. Specifically, propylene-type resins, such as a propylene homopolymer, a propylene-ethylene copolymer, a propylene-ethylene-butene-1 copolymer, are mentioned, for example.
[0089]
Moreover, as alpha-olefin type resin mix | blended with the polyester (A) used for this invention, the homopolymer of about C2-C8 alpha olefins, such as 4-methylpentene-1, those alpha olefins And other α-olefins having about 2 to 20 carbon atoms such as ethylene, propylene, butene-1,3-methylbutene-1, pentene-1, hexene-1, octene-1 and decene-1. Etc. Specifically, for example, butene-1 homopolymers, 4-methylpentene-1 homopolymers, butene-1-ethylene copolymers, butene-1-propylene copolymers, etc. -A copolymer of methylpentene-1 and a C2-C18 α-olefin, and the like.
[0090]
Examples of the polyamide resin blended in the polyester (A) used in the present invention include lactam polymers such as butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam, ω-laurolactam, and 6-aminocapron. Acids, polymers of aminocarboxylic acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecanediamine, undecamethylenediamine, 2,2,4- or Aliphatic diamines such as 2,4,4-trimethylhexamethylenediamine, alicyclic diamines such as 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or Dia such as aromatic diamines such as p-xylylenediamine Units and aliphatic dicarboxylic acids such as glutaric acid, adipic acid, suberic acid and sebacic acid, cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, and dicarboxylic acid units such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid And, for example, nylon 4, nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 66, nylon 69, and the like. Nylon 610, nylon 611, nylon 612, nylon 6T, nylon 6I, nylon MXD6, nylon 6/66, nylon 6/610, nylon 6/12, nylon 6 / 6T, nylon 6I / 6T and the like.
[0091]
Moreover, as a polyacetal resin mix | blended with the polyester (A) used for this invention, a polyacetal homopolymer and a copolymer are mentioned, for example. As the polyacetal homopolymer, the density measured by the measuring method of ASTM-D792 is 1.40 to 1.42 g / cm.^ThreeA polyacetal having a melt index (MI) measured at 190 ° C. under a load of 2160 g by a measurement method of ASTM D-1238 in the range of 0.5 to 50 g / 10 min is preferable.
[0092]
Moreover, as a polyacetal copolymer, the density measured by the measuring method of ASTM-D792 is 1.38 to 1.43 g / cm.^ThreeA polyacetal copolymer having a melt index (MI) measured at 190 ° C. and a load of 2160 g by a measuring method of ASTM D-1238 in the range of 0.4 to 50 g / 10 min is preferable. Examples of these copolymer components include ethylene oxide and cyclic ether.
[0093]
Examples of the polybutylene terephthalate resin blended in the polyester (A) used in the present invention include a polybutylene terephthalate homopolymer composed of terephthalic acid and 1,4-butanediol, and the like. And a copolymer obtained by copolymerizing naphthalene dicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol and the like.
[0094]
The polyester blended with the polyolefin resin or the like used in the present invention is a method in which the resin such as the polyolefin is directly added to the polyester and melt-kneaded so that the content is in the range, or In addition to conventional methods such as a method of adding and melting and kneading as a master batch, the resin such as polyolefin is used in the production stage of the polyester, for example, during melt polycondensation, immediately after melt polycondensation, immediately after precrystallization, Add it directly as a granular material during the solid phase polymerization, immediately after the solid phase polymerization, or between the end of the production stage and the molding stage, or the flow conditions of the polyester chip It is also possible to use a method such as melt-kneading after mixing by a method such as bringing it into contact with a resin-made member such as polyolefin.
[0095]
Here, as a method of bringing the polyester chip-like body into contact with the resin member such as the polyolefin under flow conditions, the polyester chip is attached to the member within the space where the resin member such as the polyolefin exists. Specifically, for example, in the manufacturing process such as immediately after melt polycondensation of polyester, immediately after precrystallization, immediately after solid phase polymerization, or in the transportation stage as a product of polyester chips, etc. Some of the magnet parts of pneumatic transport pipes, gravity transport pipes, silos, magnet catchers, etc. at the time of filling and discharging the transport container, and when the molding machine is put in the polyester chip molding stage, etc. Made of, or lined with a resin such as polyolefin, or a rod-like or net-like body in the transfer path By, for example placing the resin member such as the polyolefins, and a method of transferring the polyester chips. The contact time of the polyester chip with the member is usually an extremely short time of about 0.01 seconds to several minutes, but a small amount of the resin such as polyolefin can be mixed into the polyester.
[0096]
The acetaldehyde content of the polyester (A) whose main repeating unit is ethylene arylate used in the present invention is 10 ppm or less, preferably 8 ppm or less, more preferably 6 ppm or less, further preferably 4 ppm or less, and the formaldehyde content is 6 ppm. Hereinafter, it is preferably 5 ppm or less, more preferably 4 ppm or less. When the content of acetaldehyde exceeds 10 ppm and the content of formaldehyde exceeds 6 ppm, the effect of maintaining the flavor of contents such as a molded article formed from this polyester is deteriorated.
The lower limit of the amount of acetaldehyde and the amount of formaldehyde is preferably 0.1 ppb.
[0097]
The amount of diethylene glycol copolymerized in the polyester (A) whose main repeating unit is ethylene arylate used in the present invention is preferably 1.0 as the lower limit of the glycol component constituting the polyester (A). Mol%, more preferably 1.3 mol%, still more preferably 1.5 mol%, and the upper limit is preferably 5.0 mol%, more preferably 4.5 mol%, still more preferably 4.0 mol%. It is. When the amount of diethylene glycol exceeds 5.0 mol%, the thermal stability is deteriorated, the molecular weight decrease during molding is increased, and the increase in acetaldehyde content and formaldehyde content is preferably increased. Absent. On the other hand, when the diethylene glycol content is less than 1.0 mol%, the transparency of the obtained molded product may be deteriorated.
[0098]
The polyester composition of the present invention can be obtained by mixing the polyester (A) and the metaxylylene group-containing polyamide (B) by a conventionally known method. For example, the polyamide chip and the polyester chip are dry blended with a tumbler, V-type blender, Henschel mixer, etc., and the dry blended mixture is melted at least once with a single screw extruder, twin screw extruder, kneader, etc. Examples thereof include those obtained by mixing, and those obtained by subjecting a molten mixture to solid phase polymerization under a high vacuum or an inert gas atmosphere as necessary. Moreover, what melt-mixed the said polyester (A) and the said metaxylylene group containing polyamide (B) previously with the said polyester (A), and what melt-mixed the mixture which carried out dry blend further is mentioned. It is done.
[0099]
Saturated fatty acid monoamides, unsaturated fatty acid monoamides, saturated fatty acid bisamides, unsaturated fatty acid bisamides, and the like can be used in combination with the polyester composition of the present invention.
[0100]
Examples of saturated fatty acid monoamides include lauric acid amide, palmitic acid amide, stearic acid amide, and behenic acid amide. Examples of unsaturated fatty acid monoamides include oleic acid amide, erucic acid amide ricinoleic acid amide, and the like. Examples of saturated fatty acid bisamides include methylene bis stearic acid amide, ethylene biscapric acid amide, ethylene bis lauric acid amide, ethylene bis stearic acid amide, ethylene bis behenic acid amide, hexamethylene bis stearic acid amide, hexamethylene bis behenic acid Examples include amides. Examples of unsaturated fatty acid bisamides include ethylene bisoleic acid amide and hexamethylene bisoleic acid amide. Preferred amide compounds are saturated fatty acid bisamides, unsaturated fatty acid bisamides, and the like. The amount of such an amide compound is 10 ppb to 1 × 10 6^FiveA range of ppm is preferred.
[0101]
Also, a metal salt compound of an aliphatic monocarboxylic acid having 8 to 33 carbon atoms, such as naphthenic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, melicic acid, oleic acid It is also possible to simultaneously use lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, cobalt salts and the like of saturated and unsaturated fatty acids such as linoleic acid. The compounding amount of these compounds is preferably in the range of 10 ppb to 300 ppm.
[0102]
In the polyester composition of the present invention, other additives such as known ultraviolet absorbers, antioxidants, oxygen absorbers, oxygen scavengers, lubricants added from the outside, and internal precipitation during the reaction are carried out as necessary. Various additives such as lubricants, mold release agents, nucleating agents, stabilizers, antistatic agents, and pigments may be blended. It is also possible to mix ultraviolet ray-blocking resin, heat-resistant resin, recovered products from used polyethylene terephthalate bottles, and the like at an appropriate ratio.
[0103]
In applications where a colorless and transparent resin is desired, the faint yellow color generated during melt processing can be eliminated by the addition of a blue colorant. Colorants can be added directly to the blend during polymerization or during compounding. When added during blending, the colorant can be added as it is, or as a concentrate such as a masterbatch. The amount of colorant can be adjusted to its extinction coefficient and the color desired for its application. A preferred colorant includes 1-cyano-6- (4- (2-hydroxyethyl) anilino) -3-methyl-3H-dibenzo (F, I, J) -isoquinoline-2,7-dione. The addition amount of the colorant is preferably in the range of 2 to 15 ppm.
[0104]
In addition, when the polyester composition of the present invention is used for a film application, calcium carbonate, magnesium carbonate, barium carbonate is contained in the polyester composition in order to improve handling properties such as slipperiness, rollability, and blocking resistance. , Inorganic particles such as calcium sulfate, barium sulfate, lithium phosphate, calcium phosphate, magnesium phosphate, organic salt particles such as terephthalate such as calcium oxalate, calcium, barium, zinc, manganese, magnesium, divinylbenzene, styrene, acrylic Inactive particles such as crosslinked polymer particles such as acid, methacrylic acid, acrylic acid or a vinyl monomer of methacrylic acid, or a copolymer thereof can be contained.
[0105]
The polyester composition of the present invention can be used to form films, sheets, containers, and other packaging materials using a commonly used melt molding method. The stretched film composed of the polyester composition of the present invention is a sheet-like material obtained by injection molding or extrusion molding, and can be any one of uniaxial stretching, sequential biaxial stretching, and simultaneous biaxial stretching that are usually used for PET stretching. It is molded using a stretching method. It can also be formed into a cup shape or a tray shape by pressure forming or vacuum forming.
[0106]
In producing a stretched film, the stretching temperature is usually 80 to 130 ° C. Stretching may be uniaxial or biaxial, but biaxial stretching is preferred from the viewpoint of film physical properties. In the case of uniaxial stretching, the stretching ratio is usually 1.1 to 10 times, preferably 1.5 to 8 times. In the case of biaxial stretching, the longitudinal and transverse directions are usually 1.1 to 8 times, respectively. Preferably, it may be performed in a range of 1.5 to 5 times. The vertical / horizontal magnification is usually 0.5 to 2, preferably 0.7 to 1.3. The obtained stretched film can be further heat-set to improve heat resistance and mechanical strength. The heat setting is usually performed under tension at 120 to 240 ° C., preferably 150 to 230 ° C., usually for several seconds to several hours, preferably several tens of seconds to several minutes.
[0107]
In producing the hollow molded body, the blow molded from the PET of the present invention is stretch blow molded, and the apparatus conventionally used in blow molding of PET can be used. Specifically, for example, once a preform is formed by injection molding or extrusion molding, the plug part and the bottom part are processed as it is, and then reheated, and then biaxial stretch blow molding such as hot parison method or cold parison method The law applies. The molding temperature in this case, specifically, the temperature of each part of the cylinder of the molding machine and the nozzle is usually in the range of 260 to 290 ° C. The stretching temperature is usually 70 to 120 ° C., preferably 90 to 110 ° C., and the stretching ratio is usually 1.5 to 3.5 times in the longitudinal direction and 2 to 5 times in the circumferential direction. The obtained hollow molded body can be used as it is, but in particular in the case of beverages that require hot filling, such as fruit juice beverages and oolong teas, in general, heat-setting treatment is performed in a blow mold, Used to impart sex. The heat setting is usually performed at 100 to 200 ° C., preferably 120 to 180 ° C. for several seconds to several hours, preferably several seconds to several minutes, under tension by compressed air or the like.
[0108]
In order to impart heat resistance to the plug part, the plug part of the preform obtained by injection molding or extrusion molding is crystallized in a far infrared or near infrared heater installation oven, Alternatively, the mouthpiece is crystallized with the above heater after molding the bottle.
[0109]
Moreover, the polyester composition of this invention can be used also as one component layers, such as a laminated molded object and a laminated film. In particular, it is used for manufacturing containers and the like in the form of a laminate with PET. Examples of laminated molded products include a two-layer structure comprising two layers of an outer layer comprising the polyester composition of the present invention and a PET inner layer, or comprising two layers of an inner layer comprising the polyester composition of the present invention and a PET outer layer. A molded article having a two-layer structure, a three-layer structure composed of an intermediate layer containing the polyester composition of the present invention and an outer layer and an innermost layer of PET, or an intermediate between the outer layer and innermost layer containing the polyester composition of the present invention and PET Examples include a three-layered molded body composed of layers, a five-layered molded body composed of an intermediate layer containing the polyester composition of the present invention, an innermost layer of PET, a central layer, and an innermost layer. In the PET layer, other gas barrier resins, ultraviolet blocking resins, heat resistant resins, recovered products from used polyethylene terephthalate bottles, and the like can be mixed and used at an appropriate ratio.
[0110]
Other examples of the laminated molded body include a laminated molded body with a resin other than polyester such as polyolefin, and a laminated molded body with different types of base materials such as paper and metal plates.
There is no restriction | limiting in particular in the thickness of the said laminated molded object, and the thickness of each layer. The laminated molded body can be used in various shapes such as a sheet-like material, a film-like material, a plate-like material, a hollow body, and a container.
[0111]
The laminate can be produced by co-extrusion using a number of extruders corresponding to the type of the resin layer and a multi-layered multi-die, or with a number of injection machines corresponding to the type of the resin layer. It can also be done by co-injection using an injection runner and injection mold.
The polyester composition of the present invention can be preferably used as a packaging material such as a hollow molded article, a tray and a biaxially stretched film, a film for covering a metal can, and the like.
Moreover, the composition of this invention can be used also for the use of the tray-shaped container for cooking food with a microwave oven and / or an oven range etc., or heating frozen food. In this case, a sheet-like material from the polyester composition is molded into a tray shape and then thermally crystallized to improve heat resistance.
The main characteristic value measuring methods in the present invention will be described below.
[0112]
【Example】
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. The main characteristic value measuring methods in this specification will be described below.
[0113]
(Evaluation methods)
(1) Intrinsic viscosity of polyester (IV)
It calculated | required from the solution viscosity at 30 degreeC in a 1,1,2,2-tetrachloroethane / phenol (2: 3 weight ratio) mixed solvent.
[0114]
(2) Diethylene glycol content copolymerized in polyester (hereinafter referred to as [DEG content])
Decomposition with methanol, the amount of DEG was quantified by gas chromatography, and expressed as a ratio (mol%) to the total glycol components.
[0115]
(3) Content of cyclic ester trimer (hereinafter referred to as “CT content”)
300 mg of a sample is dissolved in 3 ml of a hexafluoroisopropanol / chloroform mixed solution (volume ratio = 2/3), and further diluted with 30 ml of chloroform. To this is added 15 ml of methanol to precipitate the polymer, followed by filtration. The filtrate was evaporated to dryness, adjusted to a constant volume with 10 ml of dimethylformamide, and the cyclic ester trimer was quantified by high performance liquid chromatography.
[0116]
(4) Acetaldehyde content (hereinafter referred to as “AA content”)
Sample / distilled water = 1 g / 2 cc of glass ampoule substituted with nitrogen was sealed and subjected to extraction treatment at 160 ° C for 2 hours. After cooling, acetaldehyde in the extract was measured by high-sensitivity gas chromatography. The concentration was expressed in ppm.
[0117]
(5) Increase amount of cyclic ester trimer during melting of polyester (Δ CT amount)
3 g of the dried polyester chip is put into a glass test tube, and immersed in an oil bath at 290 ° C. for 60 minutes in a nitrogen atmosphere and melted. The increase amount of the cyclic ester trimer at the time of melting is obtained by the following formula.
Increase amount of cyclic ester trimer during melting (% by weight) =
Cyclic ester trimer content after melting (wt%)-cyclic ester trimer content before melting (wt%)
[0118]
(6) Relative viscosity (RV) of metaxylylene group-containing polyamide
0.25 g of a sample was dissolved in 25 ml of 96% sulfuric acid, and 10 ml of this solution was measured at 20 ° C. with an Ostwald viscosity tube and obtained from the following formula.
RV = t / t₀
t₀: Solvent fall seconds
t : Sample solution dropping seconds
[0119]
(7) Sodium atom content in the metaxylylene group-containing polyamide (hereinafter referred to as “Na content”)
The sample is incinerated and decomposed with a platinum crucible, 6 mol / L hydrochloric acid is added and evaporated to dryness. It was determined by dissolving with 1.2 mol / L hydrochloric acid and quantifying by atomic absorption.
[0120]
(8) Terminal amino group concentration of the metaxylylene group-containing polyamide (AEG, μmol / g)
After 0.5 g of sample is dissolved in 50 ml of a phenol / ethanol mixed solvent (volume ratio 4/1) at room temperature, 20 ml of a water / ethanol mixed solvent (volume ratio 3/2) is added and stirred. Thereafter, neutralization titration was performed using hydrochloric acid to determine the terminal amino group concentration.
[0121]
(9) Terminal carboxyl group concentration of polyamide containing metaxylylene group (CEG, μmol / g)
To 0.5 g of the sample, 20 ml of benzyl alcohol was added and dissolved by heating in an oil bath at 170 to 180 ° C., followed by neutralization titration with an aqueous sodium hydroxide solution to determine the terminal carboxyl group concentration.
[0122]
(10) Molding of stepped molded plate
The dried polyester composition is molded by a M-150C (DM) injection molding machine manufactured by Meiki Seisakusho using a stepped flat plate mold cooled to 10 ° C. at a cylinder temperature of 290 ° C. The obtained stepped molded plate was provided with a plate of about 3 cm × about 5 cm square having a thickness of 2,3,4,5,6,7,8,9,10,11 mm in steps. The weight of one molded plate is about 146 g. A 5 mm thick plate is used for haze measurement.
[0123]
(11) Haze (degree of haze%) and haze spots
The molded product (thickness 5 mm) of the above (10) is cut out and measured with a Nippon Denshoku Co., Ltd. haze meter.
[0124]
(12) Evaluation of mold contamination
M-150C (DM) injection molding machine manufactured by each machine manufacturer using a predetermined amount of polyester dried with a dryer using nitrogen gas and a predetermined amount of metaxylylene group-containing polyamide chips dried with a dryer using nitrogen gas Thus, a preform was molded at a resin temperature of 290 ° C. The preform plug portion was heated and crystallized with a home-made plug portion crystallization apparatus, then biaxially stretched blow-molded using a Copoplast LB-01E stretch blow molding machine. It was heat-set in a mold set at about 145 ° C. for about 7 seconds to obtain a 1000 cc hollow molded body. Under the same conditions, 2000 hollow molded articles were continuously stretch blow molded, and the state of the mold surface before and after that was visually observed and evaluated as follows.
○: No change before and after the continuous molding test
△: There is considerable adhesion after the continuous molding test
×: Very much deposits after continuous molding test
[0125]
(13) Transparency of hollow molded body
The appearance of the hollow molded body obtained after the (12) 2000 molding was visually observed and evaluated as follows.
◎: Transparent
○: Transparent within a practical range, no unmelted material seen
×: Inferior in transparency or unmelted material is observed
[0126]
(14) Sensory test
Distilled water that had boiled was put in the hollow molded body and held for 30 minutes after sealing, cooled to room temperature, allowed to stand at room temperature for 1 month, and tested for flavor and odor after opening. Use distilled water as a blank for comparison. The sensory test was carried out by 10 panelists according to the following criteria, and the average values were compared.
(Evaluation criteria)
0: Does not feel strange or smelly
1: Feel slight difference from blank
2: Feel the difference from the blank
3: I feel a considerable difference from the blank
4: I feel a very big difference from the blank
[0127]
(15) Oxygen permeation rate (cc / one container / 24hr / atm)
The permeation amount per 1000 cc bottle was measured at 20 ° C. and 0% RH with an oxygen permeation meter OX-TRAN100 manufactured by Modern Controls.
[0128]
(Polyethylene terephthalate (PET) used in Examples and Comparative Examples)
Table 1 shows the characteristics of PET (Ge residual amount = about 40 to 50 ppm, phosphorus residual amount = about 30 to 35 ppm) used in the test. These are all polymerized by a continuous melt polycondensation-solid phase polymerization apparatus.
PET (a) has been subjected to hydrothermal treatment at about 90 ° C. for 3 hours in ion-exchanged water after solid phase polymerization.
Incidentally, the DEG contents of PET (a) to PET (b) are all about 2.7 mol%.
[0129]
[Table 1]

[0130]
(Metaxylylene group-containing polyamide (MXD6) used in Examples and Comparative Examples)
[0131]
Manufacturing method of MXD6 (c)
In a preparation can having an internal volume of 250 liters equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, precisely weighed 27.66 kg of metaxylylenediamine and 29.65 kg of adipic acid, an internal temperature of 85 ° C. To prepare a slurry-like transparent solution. After adjusting the PH value in the can to 7.95, as a gelation inhibitor, 34.09 g NaOH, NaH₂PO₂・ H₂25.81 g of O was added and stirred for 15 minutes. The solution was transferred to a reaction can with an internal volume of 270 liters, and reacted by stirring under conditions of an internal temperature of 260 ° C. and an internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The properties of the obtained resin are shown in Table 2.
[0132]
Manufacturing method of MXD6 (d)
In a preparation can having an internal volume of 250 liters equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, precisely weighed 27.66 kg of metaxylylenediamine and 29.65 kg of adipic acid, an internal temperature of 85 ° C. To prepare a slurry-like transparent solution. After adjusting the PH value in the can to 7.20, as a gelation inhibitor, 6.82 g of NaOH, NaH₂PO₂・ H₂5.16 g of O was added and stirred for 15 minutes. The solution was transferred to a reaction can with an internal volume of 270 liters, and reacted by stirring under conditions of an internal temperature of 260 ° C. and an internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The properties of the obtained resin are shown in Table 2.
[0133]
Manufacturing method of MXD6 (e)
A resin chip was obtained in the same manner as MXD6 (c) except that the PH value in the can was adjusted to 7.06. The properties of the obtained resin are shown in Table 2.
[0134]
Method for manufacturing MXD6 (f)
A resin chip was obtained in the same manner as MXD6 (c) except that the PH value in the can was adjusted to 6.92. The properties of the obtained resin are shown in Table 2.
[0135]
Method for producing MXD6 (g)
In a preparation can having an internal volume of 250 liters equipped with a stirrer, a condenser, a thermometer, a dropping funnel and a nitrogen gas introduction tube, precisely weighed 27.66 kg of metaxylylenediamine and 29.65 kg of adipic acid, an internal temperature of 85 ° C. To prepare a slurry-like transparent solution. After adjusting the PH value in the can to 7.20, 102.27 g of NaOH as a gelation inhibitor, NaH₂PO₂・ H₂77.43 g of O was added and stirred for 15 minutes. The solution was transferred to a reaction can with an internal volume of 270 liters, and reacted by stirring under conditions of an internal temperature of 260 ° C. and an internal pressure of 1.0 MPa. The distilled water was removed from the system, and when the internal temperature of the can reached 235 ° C., the internal pressure of the can was returned to normal pressure over 60 minutes. Stirring was performed at normal pressure, and when the target viscosity was reached, stirring was stopped and left for 20 minutes. Thereafter, the molten resin was taken out from the take-out port at the bottom of the reaction can, cooled and solidified, and a resin chip was obtained with a strand cutter. The properties of the obtained resin are shown in Table 2.
[0136]
Manufacturing method of MXD6 (h)
A resin chip was obtained in the same manner as MXD6 (d) without adding a gelation inhibitor. The properties of the obtained resin are shown in Table 2.
[0137]
[Table 2]

[0138]
(Example 1)
Using 0.5 parts by weight of MXD6 (c) with respect to 100 parts by weight of PET (a), a hollow molded body was molded by the method of evaluation method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was 8 ppm, the sensory test evaluation was 0.7, the appearance was transparent within a practical range, and no mold contamination was observed.
[0139]
(Example 2)
Using 3.0 parts by weight of MXD6 (c) with respect to 100 parts by weight of PET (a), a hollow molded body was molded by the method of evaluation method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was 7 ppm, the sensory test evaluation was 0.6, the appearance was transparent within a practical range, and no mold contamination was observed.
[0140]
(Example 3)
Using 20.0 parts by weight of MXD6 (c) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The hollow molded body has an AA content of 6 ppm, a sensory test evaluation of 0.6, an oxygen transmission rate of 0.20 cc / one container / 24 hr / atm, the appearance is transparent within a practical range, I was not able to admit.
[0141]
(Example 4)
Using 3.0 parts by weight of MXD6 (d) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was 7 ppm, the sensory test evaluation was 0.7, the appearance was transparent within a practical range, and mold contamination was not observed.
[0142]
(Comparative Example 1)
Using 0.5 parts by weight of MXD6 (e) with respect to 100 parts by weight of PET (a), a hollow molded body was molded by the method of evaluation method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was as low as 10 ppm, the sensory test evaluation was 0.8, and no mold contamination was observed, but the transparency was poor and the practicality was poor.
[0143]
(Comparative Example 2)
Using 3.0 parts by weight of MXD6 (e) with respect to 100 parts by weight of PET (a), a hollow molded body was molded by the method of evaluation method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was as low as 8 ppm, the sensory test evaluation was 0.7, and mold contamination was not observed, but the transparency was poor and the practicality was poor.
[0144]
(Comparative Example 3)
Using 0.5 parts by weight of MXD6 (f) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
Mold contamination of the hollow molded body was not observed, but the AA content was 17 ppm, and the sensory test evaluation was 2.1, which was different from blank distilled water. Further, the transparency was poor and the practicality was poor.
[0145]
(Comparative Example 4)
Using 0.5 parts by weight of MXD6 (g) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
Mold contamination of the hollow molded body was not observed, but the AA content was 20 ppm, and the sensory test evaluation was 2.3, which was different from blank distilled water. Further, the transparency was poor and the practicality was poor.
[0146]
(Comparative Example 5)
Using 20.0 parts by weight of MXD6 (g) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The oxygen permeation amount of the hollow molded body was 0.21 cc / one container / 24 hr · atm, and no mold contamination was observed, but the AA content was 28 ppm, and the sensory test evaluation was 2.7, which was different from blank distilled water. was there. Further, the transparency was poor and the practicality was poor.
[0147]
(Comparative Example 6)
Using 3.0 parts by weight of MXD6 (h) per 100 parts by weight of PET (a), a hollow molded body was molded by the method of Evaluation Method (12), and the CT content and AA content of the molded body were determined. It was measured. In addition, mold contamination was evaluated.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
The AA content of the hollow molded body was 9 ppm, the sensory test evaluation was 0.8, and mold contamination was not observed, but unmelted material was observed in several hollow molded bodies, and the practicality was poor.
[0148]
(Comparative Example 7)
Using only PET (a), a hollow molded body was formed by the method of evaluation method (12), and mold stain evaluation was also performed.
Table 3 shows the characteristics of the obtained hollow molded article and the evaluation results of mold contamination.
[0149]
[Table 3]

[0150]
【The invention's effect】
According to the polyester composition of the present invention, a hollow molded article, a sheet-like article and a stretched film which are excellent in transparency, flavor retention and / or gas barrier property and hardly cause mold contamination during molding. Is obtained.

Claims (5)

A polyester composition comprising 100 parts by weight of a polyester (A) whose main repeating unit is ethylene arylate and 0.01 to 100 parts by weight of a metaxylylene group-containing polyamide (B), wherein the metaxylylene group-containing polyamide (B) range der sodium atom content of 0.01~1000ppm of is, and polyester composition haze of the molded body of 5mm thickness that the polyester composition was molded at 290 ° C. is equal to or less than 20% object. A molded article obtained by molding the polyester composition according to claim 1 . The molded body according to claim 2 , wherein the molded body is a hollow molded body. The molded product according to claim 2 is a sheet-like product. A molded body according to claim 2 , wherein the molded body is a stretched film obtained by stretching the sheet-like material according to claim 4 in at least one direction.