JP3624667B2 - Method for producing modified polyethylene terephthalate resin - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は、改質ポリエチレンテレフタレート樹脂の製造方法に関し、更に詳しくは、透明性を低下させることなく、結晶化温度を低温化ならしめ、特に食品包装用ボトル容器等の成形に有用な改質ポリエチレンテレフタレート樹脂の製造方法に関する。
【０００２】
【従来の技術】
従来より、炭酸飲料、果汁飲料、アルコール飲料、茶やミネラルウォーター等の飲料、液体調味料、食用油、液体洗剤、化粧品等のボトル容器として、ポリエチレンテレフタレート樹脂が、優れた機械的性質及び化学的特性に加え、その優れた透明性、ガスバリア性、安全衛生性等の面から注目され、著しい伸びを示している。
【０００３】
これらのポリエチレンテレフタレート樹脂のボトル容器は、通常、射出成形したプリフォームをブロー金型内で延伸ブロー成形して成形されるが、果汁飲料等のように熱充填を必要とする内容物の容器の場合には、ボトルの耐熱性を上げるために、プリフォーム又はボトルの口栓部を熱処理して結晶化させることが行われており、又、小容量の容器の場合には、ボトル胴部の密度を上げるために、ブロー金型の温度を１２０〜１８０℃程度の高温に設定して胴部の結晶化を促進することが行われている。
しかしながら、ポリエチレンテレフタレート樹脂は、一般に結晶化速度が遅いため、ボトル成形時のこれら処理に時間を要するという問題があり、又、結晶化速度を早めると透明性の低下が避けられず、従来よりその改良が強く望まれている。
【０００４】
一方、本発明者は、先に、ポリエチレンテレフタレート樹脂のチップを流動条件下にポリエチレン樹脂製部材と接触させて、ポリエチレンテレフタレート樹脂のチップ表面に該ポリエチレン樹脂を付着せしめることにより、ポリエチレンテレフタレート樹脂の結晶化温度を低温化ならしめる方法を提案した（特開平９−７１６３９号公報参照。）。
しかし、この方法は、ポリエチレンテレフタレート樹脂の結晶化速度にある程度の改良を与えるものの、透明性とのバランスにおいて、市場の要求を十分に満足させ得ているとは言い難かった。
【０００５】
【発明が解決しようとする課題】
本発明は、前述の現状に鑑み、透明性を低下させることなく、結晶化温度を低温化ならしめて結晶化速度を改良した改質ポリエチレンテレフタレート樹脂の製造方法を提供することを目的とする。
【０００６】
【課題を解決するための手段】
本発明は、前記目的を達成すべくなされたものであって、即ち、本発明は、ポリエチレンテレフタレート樹脂の粒状体を、流動条件下に、ポリプロピレン系樹脂又はポリアミド系樹脂からなる部材に接触させて該ポリプロピレン系樹脂又はポリアミド系樹脂を粒状体表面に付着させる改質ポリエチレンテレフタレート樹脂の製造方法、を要旨とする。
【０００７】
【発明の実施の形態】
本発明において、ポリエチレンテレフタレート樹脂としては、テレフタル酸又はそのアルキル（炭素数１〜４程度）エステルを主成分とするジカルボン酸単位とエチレングリコールを主成分とするグリコール単位との重縮合体であつて、このオキシエチレンオキシテレフタロイル単位が全構成単位の８０当量％以上を占めることが好ましい。
又、全グリコール単位に対し、ジエチレングリコール単位の含有量が１〜４モル％の範囲であるのが好ましい。
【０００８】
尚、テレフタル酸及びそのアルキルエステル以外のジカルボン酸単位としては、例えば、フタル酸、イソフタル酸、４，４’−ジフェニルジカルボン酸、４，４’−ジフェノキシエタンジカルボン酸、４，４’−ジフェニルエーテルジカルボン酸、４，４’−ジフェニルスルホンジカルボン酸、２，６−ナフタレンジカルボン酸等の芳香族ジカルボン酸、ヘキサヒドロテレフタル酸、ヘキサヒドロイソフタル酸等の脂環式ジカルボン酸、マロン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸等の脂肪族ジカルボン酸、又、エチレングリコール以外のグリコール単位として、例えば、プロピレングリコール、トリメチレングリコール、テトラメチレングリコール、ペンタメチレングリコール、ヘキサメチレングリコール、デカメチレングリコール、ネオペンチルグリコール、ジエチレングリコール等の脂肪族グリコール、１，１−シクロヘキサンジメチロール、１，４−シクロヘキサンジメチロール等の脂環式グリコール、４，４’−ジヒドロキシビフェニル、２，２−ビス（４’−ヒドロキシフェニル）プロパン、２，２−ビス（４’−β−ヒドロキシエトキシフェニル）プロパン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−β−ヒドロキシエトキシフェニル）スルホン酸等の芳香族グリコール、更に、例えば、ｐ−ヒドロキシ安息香酸、ｐ−β−ヒドロキシエトキシ安息香酸等のヒドロキシカルボン酸やアルコキシカルボン酸、等の一種又は二種以上が、共重合成分として用いられる。
【０００９】
これらのテレフタル酸又はそのアルキルエステルを主成分とするジカルボン酸単位とエチレングリコールを主成分とするグリコール単位等を含む原料は、常法により、エステル化触媒又はマンガン等の金属化合物等のエステル交換触媒の存在下、２４０〜２８０℃程度の温度、１〜３ｋｇ／ｃｍ２ 程度の圧力でエステル化反応又はエステル交換反応を行ってビス（β−ヒドロキシエチル）テレフタレート及び／又はそのオリゴマーとされた後、ゲルマニウム等の金属化合物等の重縮合触媒及び燐酸等の燐化合物等の安定剤の存在下、２５０〜３００℃程度の温度、５００〜０．１ｍｍＨｇ程度の圧力で溶融重縮合を行ってポリマーとされ、溶融重合槽の底部に設けた抜き出し口からストランド状に抜き出される等した後、カッターで切断されてチップ状、ペレット状、あるいは球状等の粒状体とされる。更に、必要に応じて、溶融重縮合により得られた粒状体ポリマーは、通常、１２０〜２００℃程度の温度で１分間以上加熱して予備結晶化がなされた後、窒素等の不活性ガス流通下、１９０〜２３０℃程度の温度、１ｋｇ／ｃｍ２ 〜１０ｍｍＨｇ程度の圧力で１〜５０時間、固相重合がなされる。
【００１０】
本発明において、前記ポリエチレンテレフタレート樹脂の粒状体を、流動条件下に接触させる部材を構成す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等の他のα−オレフィンとの共重合体等が挙げられ、具体的には、例えば、プ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共重合体等が挙げられる。
【００１１】
又、同様の部材を構成するポリアミド系樹脂としては、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。
【００１２】
前記ポリプロピレン系樹脂及び前記ポリアミド系樹脂の中で、本発明においては、融点が１５５℃以上の樹脂が好ましい。
【００１３】
本発明においては、前記ポリエチレンテレフタレート樹脂の粒状体を、流動条件下に、前記ポリプロピレン系樹脂又は前記ポリアミド系樹脂からなる部材に接触させて該ポリプロピレン系樹脂又はポリアミド系樹脂を粒状体表面に付着させて改質ポリエチレンテレフタレート樹脂を製造する。
【００１４】
その際の部材及び接触方法としては、ポリプロピレン系樹脂又はポリアミド系樹脂からなる部材が存在する空間内で、ポリエチレンテレフタレート樹脂の粒状体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、ポリエチレンテレフタレート樹脂の溶融重合直後、予備結晶化直後、固相重合直後等の製造工程時、又、ポリエチレンテレフタレート樹脂粒状体の製品としての輸送段階等での輸送容器充填・排出時、又、ポリエチレンテレフタレート樹脂粒状体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、振動篩のパンチング板、マグネットキャッチャーのマグネット部等の一部をポリプロピレン系樹脂又はポリアミド系樹脂製とするか、又はこれらの樹脂をライニングするとか、あるいは前記移送経路内に棒状又は網状体等のポリプロピレン系樹脂又はポリアミド系樹脂製部材を設置する等して、ポリエチレンテレフタレート樹脂の粒状体を移送する方法が挙げられる。
ここで、ポリエチレンテレフタレート樹脂の粒状体の前記部材との接触時間は、通常、０．０１〜１秒程度の極短時間であるが、ポリエチレンテレフタレート樹脂の粒状体表面にポリプロピレン系樹脂又はポリアミド系樹脂を微量付着させることができる。
【００１５】
本発明において、前記改質ポリエチレンテレフタレート樹脂への前記ポリプロピレン系樹脂又はポリアミド系樹脂の付着量は、ポリエチレンテレフタレート樹脂との合計量に対して、０．１〜４５ｐｐｂであるのが好ましく、１〜４０ｐｐｂであるのが特に好ましい。付着量が前記範囲未満では、樹脂成形体としての結晶化の低温化効果が不十分となり、又、前記範囲超過では、樹脂成形体の透明性が損なわれる傾向となる。
又、改質ポリエチレンテレフタレート樹脂の固有粘度は、フェノール／テトラクロロエタン（重量比１／１）の混合溶媒中で３０℃で測定した値として、０．６〜１．０ｄｌ／ｇであるのが好ましい。
【００１６】
以上の方法によって製造された本発明の改質ポリエチレンテレフタレート樹脂は、例えば、押出成形によってフィルムやシート等に成形され、又、射出成形によってプリフォームに成形された後、ブロー成形によってボトル等に成形される。尚、その際の押出成形条件としては、通常採用されている範囲であって、例えば、シリンダー温度２４０〜３００℃、スクリュー回転数４０〜３００ｒｐｍ、吐出圧力４０〜１４０ｋｇ／ｃｍ２ 、冷却ドラム温度５〜４０℃等の範囲で成形することができる。又、射出成形条件としては、シリンダー温度２７０〜３００℃、金型温度５〜４０℃、スクリュー回転数４０〜３００ｒｐｍ、射出圧力４０〜１４０ｋｇ／ｃｍ２ 等の範囲で成形することができる。
【００１７】
本発明の製造方法による改質ポリエチレンテレフタレート樹脂は、成形時の結晶化温度を低温化ならしめ得るが、具体的には、成形体とされた改質樹脂の示差走査熱量計による昇温結晶化温度が１５０〜１７０℃であるのが好ましく、１５５〜１６５℃であるのが特に好ましい。
尚、ここで、昇温結晶化温度とは、示差走査熱量計にて、室温から２８５℃まで２０℃／分の速度で昇温させ、その途中で観察される結晶化ピークのトップ温度を言う。
【００１８】
以上の成形方法による成形体の中で、本発明による改質樹脂は、射出成形方法によって得られるプリフォームを、再加熱後に二軸延伸するコールドパリソン法等のブロー成形法よってボトルを成形するのに好適であり、例えば、炭酸飲料、果汁飲料、アルコール飲料、茶やミネラルウォーター等の飲料、醤油、ソース、みりん、ドレッシング等の液体調味料、食用油、液体洗剤、化粧品等の容器として好適に用いられる。
【００１９】
【実施例】
以下、実施例により本発明を更に詳細に説明するが、本発明はその要旨を越えない限り以下の実施例に限定されるものではない。
実施例１
テレフタル酸１３．０ｋｇとエチレングリコール５．８２ｋｇのスラリーを調製し、予め０．３０ｋｇのビス（２−ヒドロキシエチル）テレフタレートを投入して２５０℃の温度に保持したエステル化槽に、４時間かけて順次供給した。供給終了後、１時間かけてエステル化反応を進行させた後、半量を重縮合槽に移し、燐酸０．９１ｇと二酸化ゲルマニウム０．９２ｇを仕込み、２５０℃から２７８℃まで漸次昇温すると共に、常圧から漸次減圧し、０．５ｍｍＨｇに保持して重縮合反応を３時間行った後、生成したポリマーを重縮合槽の底部に設けた抜き出し口からストランド状に抜き出し、水冷後、カッターで切断して楕円柱状のポリマーチップを得た。
引き続いて、得られたポリマーチップを、径１００ｍｍのＳＵＳ製気力輸送配管の一部を長さ１ｍにわたってポリプロピレン（日本ポリケム社製、「ＦＡ３Ｄ」、融点１６３℃）製とした気力輸送配管内を気力輸送して攪拌結晶化機（Ｂｅｐｅｘ社式）に移送し、ポリマーチップ表面を１５０℃で結晶化させた後、静置固相重合塔に移し、２０リットル／ｋｇ・ｈｒの窒素流通下、約１４０℃で３時間乾燥後、２１０℃で２０時間固相重合して、チップ状の改質ポリエチレンテレフタレート樹脂を製造した。
得られた改質ポリエチレンテレフタレート樹脂は、ポリプロピレンを１０ｐｐｂ付着し、その固有粘度は、０．７９ｄｌ／ｇであった。
【００２０】
得られた改質ポリエチレンテレフタレート樹脂から、射出成形機（名機製作所製、「Ｍ−７０Ａ」）にて、シリンダー各部及びノズルヘッドの温度２８０℃、スクリュー回転数２００ｒｐｍ、射出時間６０秒、金型冷却水温度１０℃で、厚さ４ｍｍと５ｍｍを有する段付角板状成形板を射出成形した。
得られた成形板について、改質樹脂の結晶化温度、及び透明性を測定し、結果を表１に示した。
尚、各物性の測定方法は以下の通りである。
【００２１】
結晶化温度
示差走査熱量計（セイコー電子社製、「ＤＳＣ２２０Ｃ」）にて、成形板の厚さ５ｍｍの部分を用い、室温から２８５℃まで２０℃／分の速度で昇温させ、その途中で観察される結晶化ピークのトップ温度（昇温結晶化温度：ＴＣ１ ）を測定し、更に昇温を続けて２８５℃に達した時点で３分間保持した後、１０℃／分の速度で降温させ、その途中で観察される結晶化ピークのトップ温度（降温結晶化温度：ＴＣ２ ）を測定した。
透明性
ヘーズメータ（日本電色社製、「ＮＤＨ−３００Ａ」）にて、成形板の厚さ４ｍｍと５ｍｍの部分について、ヘーズを測定した。
【００２２】
更に、得られた改質ポリエチレンテレフタレート樹脂から、射出成形機（東芝社製、「ＩＳ−６０Ｂ」）にて、シリンダー各部及びノズルヘッドの温度２８０℃、スクリュー回転数２００ｒｐｍ、射出時間１０秒、金型冷却水温度１０℃で、プリフォームを射出成形し、その口栓部を結晶化機で加熱し結晶化させた後、予熱炉温度９０℃、ブロー圧力２０ｋｇ／ｃｍ２ 、成形サイクル１０秒に設定したブロー成形機で延伸ブロー成形し、胴部平均肉厚３００μｍ、内容積１リットルのボトルとし、引き続いて１５０℃に設定した金型内で圧空緊張下、１０秒間熱固定した。
得られたボトルの外観を目視にて観察し、以下の基準で評価した。
○；濁りがなく透明であり、又、変形もない。
△；濁りがなく透明であるが、変形がある。
×；結晶化時に白化。
【００２３】
比較例１
重縮合槽で得られたポリマーチップを、重縮合槽から攪拌結晶化機にＳＵＳ製気力輸送配管のままで移送した外は、実施例１と同様にして、射出成形して各物性を測定し、結果を表１に併記した。
【００２４】
実施例２
比較例１と同様にして得られたチップ状のポリエチレンテレフタレート樹脂を、１段に５本の棒状マグネット（直径２１ｍｍ）がセットできるマグネットキャッチャーを用い、１段分を実施例１にて用いたと同じポリプロピレン製のパイプに換えて処理した外は、実施例１と同様にして、射出成形して各物性を測定し、結果を表１に示した。
【００２５】
実施例３
比較例１と同様にして得られたチップ状のポリエチレンテレフタレート樹脂を、１段に５本の棒状マグネット（直径２１ｍｍ）がセットできるマグネットキャッチャーを用い、１段分をポリアミド樹脂（三菱エンジニアリングプラスチック社製、「ノバミッド１０３０」、融点２２４℃）製のパイプに換えて処理した外は、実施例１と同様にして、射出成形して各物性を測定し、結果を表１に示した。
【００２６】
【表１】
【発明の効果】
本発明によれば、透明性を低下させることなく、結晶化温度を低温化ならしめて結晶化速度を改良した改質ポリエチレンテレフタレート樹脂の製造方法を提供することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a modified polyethylene terephthalate resin, and more particularly, a modified polyethylene useful for forming a food container such as a bottle container for food packaging by lowering the crystallization temperature without lowering transparency. The present invention relates to a method for producing a terephthalate resin.
[0002]
[Prior art]
Conventionally, polyethylene terephthalate resin has excellent mechanical properties and chemical properties as bottle containers for carbonated beverages, fruit juice beverages, alcoholic beverages, beverages such as tea and mineral water, liquid seasonings, edible oils, liquid detergents, cosmetics, etc. In addition to its characteristics, it has attracted attention from the standpoints of its excellent transparency, gas barrier properties, safety and hygiene, and has shown remarkable growth.
[0003]
These bottles of polyethylene terephthalate resin are usually formed by stretch-blow-molding an injection-molded preform in a blow mold, but are containers of contents that require heat filling such as fruit juice beverages. In some cases, in order to increase the heat resistance of the bottle, the preform or the stopper of the bottle is crystallized by heat treatment, and in the case of a small capacity container, In order to increase the density, the temperature of the blow mold is set to a high temperature of about 120 to 180 ° C. to promote crystallization of the body portion.
However, since polyethylene terephthalate resin generally has a low crystallization rate, there is a problem that it takes time for these treatments during bottle molding, and when the crystallization rate is increased, a decrease in transparency cannot be avoided. Improvement is strongly desired.
[0004]
On the other hand, the present inventor previously made a polyethylene terephthalate resin crystal by bringing a polyethylene terephthalate resin chip into contact with a polyethylene resin member under flow conditions and attaching the polyethylene resin to the surface of the polyethylene terephthalate resin chip. A method for reducing the temperature is proposed (see JP-A-9-71639).
However, although this method gives a certain degree of improvement in the crystallization speed of the polyethylene terephthalate resin, it cannot be said that the demand of the market can be sufficiently satisfied in balance with transparency.
[0005]
[Problems to be solved by the invention]
An object of the present invention is to provide a method for producing a modified polyethylene terephthalate resin in which the crystallization temperature is lowered and the crystallization speed is improved without lowering transparency.
[0006]
[Means for Solving the Problems]
The present invention has been made to achieve the above-mentioned object. That is, the present invention is made by bringing a polyethylene terephthalate resin granule into contact with a member made of a polypropylene resin or a polyamide resin under flow conditions. The gist is a method for producing a modified polyethylene terephthalate resin in which the polypropylene resin or polyamide resin is adhered to the surface of a granular material.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, the polyethylene terephthalate resin is a polycondensate of a dicarboxylic acid unit mainly composed of terephthalic acid or an alkyl (about 1 to 4 carbon atoms) ester thereof and a glycol unit mainly composed of ethylene glycol. It is preferable that the oxyethyleneoxyterephthaloyl unit occupies 80 equivalent% or more of all the structural units.
Moreover, it is preferable that content of a diethylene glycol unit is a range of 1-4 mol% with respect to all the glycol units.
[0008]
Examples of dicarboxylic acid units other than terephthalic acid and alkyl esters thereof include, for example, phthalic acid, isophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, and 4,4′-diphenyl ether. Dicarboxylic acids, aromatic dicarboxylic acids such as 4,4′-diphenylsulfone dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, alicyclic dicarboxylic acids such as hexahydroterephthalic acid, hexahydroisophthalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, and glycol units other than ethylene glycol include, for example, propylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol , Aliphatic glycols such as neopentyl glycol and diethylene glycol, alicyclic glycols such as 1,1-cyclohexanedimethylol and 1,4-cyclohexanedimethylol, 4,4′-dihydroxybiphenyl, 2,2-bis ( Aromatics such as 4′-hydroxyphenyl) propane, 2,2-bis (4′-β-hydroxyethoxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, bis (4-β-hydroxyethoxyphenyl) sulfonic acid Glycol and, for example, one or two or more of hydroxycarboxylic acid and alkoxycarboxylic acid such as p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid are used as a copolymerization component.
[0009]
A raw material containing a dicarboxylic acid unit containing terephthalic acid or an alkyl ester thereof as a main component and a glycol unit containing ethylene glycol as a main component is an esterification catalyst or a transesterification catalyst such as a metal compound such as manganese by a conventional method. In the presence of bis (β-hydroxyethyl) terephthalate and / or an oligomer thereof, an esterification reaction or a transesterification reaction is performed at a temperature of about 240 to 280 ° C. and a pressure of about 1 to 3 kg / cm 2 . In the presence of a polycondensation catalyst such as a metal compound such as germanium and a stabilizer such as a phosphorous compound such as phosphoric acid, melt polycondensation is performed at a temperature of about 250 to 300 ° C. and a pressure of about 500 to 0.1 mmHg to obtain a polymer. After being drawn into a strand from the outlet provided at the bottom of the melt polymerization tank, it is cut with a cutter. Chip-like, it is pellets or granules such as spherical. Furthermore, if necessary, the granular polymer obtained by melt polycondensation is usually heated at a temperature of about 120 to 200 ° C. for 1 minute or longer and pre-crystallized, and then an inert gas such as nitrogen is circulated. Below, solid phase polymerization is performed at a temperature of about 190 to 230 ° C. and a pressure of about 1 kg / cm 2 to 10 mmHg for 1 to 50 hours.
[0010]
In the present invention, examples of the polypropylene resin constituting the member for contacting the polyethylene terephthalate resin granules under flow conditions include, for example, propylene homopolymer, propylene, and other α such as ethylene and butene-1. -A copolymer with an olefin, etc. are mentioned, specifically, for example, a propylene homopolymer, a propylene-ethylene copolymer, a propylene-ethylene-butene-1 copolymer, etc. are mentioned.
[0011]
In addition, examples of the polyamide resin constituting the same member include lactam polymers such as butyrolactam, δ-valerolactam, ε-caprolactam, enantolactam, and ω-laurolactam, 6-aminocaproic acid, and 11-aminoundecane. Acid, polymer of aminocarboxylic acid such as 12-aminododecanoic acid, hexamethylenediamine, nonamethylenediamine, decamethylenediamine, dodecamethylenediamine, undecamethylenediamine, 2,2,4- or 2,4,4- Aliphatic diamines such as trimethylhexamethylenediamine, alicyclic diamines such as 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminocyclohexylmethane), m- or p-xylylenediamine, etc. Diamine units such as aromatic diamines, glutaric acid, Polycondensates with aliphatic dicarboxylic acids such as acid, suberic acid and sebacic acid, cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, dicarboxylic acid units such as aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and the like Specifically, for example, nylon 4, nylon 6, nylon 7, nylon 8, nylon 9, nylon 11, nylon 12, nylon 66, nylon 69, 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.
[0012]
Among the polypropylene-based resin and the polyamide-based resin, a resin having a melting point of 155 ° C. or higher is preferable in the present invention.
[0013]
In the present invention, the polyethylene terephthalate resin granules are brought into contact with the polypropylene resin or the polyamide resin under flow conditions to adhere the polypropylene resin or polyamide resin to the surface of the granules. Modified polyethylene terephthalate resin.
[0014]
As a member and a contact method at that time, it is preferable to make the polyethylene terephthalate resin particles collide with the member in a space where a member made of a polypropylene resin or a polyamide resin exists. Immediately after melt polymerization of polyethylene terephthalate resin, immediately after pre-crystallization, immediately after solid-phase polymerization, etc., at the time of filling and discharging a transport container in the transport stage etc. as a product of polyethylene terephthalate resin granules, and polyethylene Parts such as pneumatic transport pipe, gravity transport pipe, silo, punching plate of vibrating screen, magnet part of magnet catcher, etc. made of polypropylene resin or polyamide resin when the molding machine is put in the molding stage of terephthalate resin granules Or lining these resins or before By, for example placing the polypropylene resin or polyamide resin rod-like member or reticular body or the like in the transport path, and a method of transferring the granules of polyethylene terephthalate resin.
Here, the contact time of the polyethylene terephthalate resin granule with the member is usually an extremely short time of about 0.01 to 1 second, but the polyethylene terephthalate resin granule surface has a polypropylene resin or a polyamide resin. Can be attached in a small amount.
[0015]
In this invention, it is preferable that the adhesion amount of the said polypropylene resin or polyamide-type resin to the said modified polyethylene terephthalate resin is 0.1-45 ppb with respect to the total amount with a polyethylene terephthalate resin, and 1-40 ppb. Is particularly preferred. If the adhesion amount is less than the above range, the effect of lowering the crystallization temperature as the resin molded body becomes insufficient, and if it exceeds the above range, the transparency of the resin molded body tends to be impaired.
The intrinsic viscosity of the modified polyethylene terephthalate resin is preferably 0.6 to 1.0 dl / g as a value measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1). .
[0016]
The modified polyethylene terephthalate resin of the present invention produced by the above method is formed into a film or sheet by extrusion molding, for example, or formed into a preform by injection molding and then molded into a bottle or the like by blow molding Is done. In addition, as extrusion molding conditions in that case, it is the range normally employ | adopted, for example, cylinder temperature 240-300 degreeC, screw rotation speed 40-300 rpm, discharge pressure 40-140 kg / cm < 2 >, cooling drum temperature 5 It can shape | mold in -40 degreeC etc. range. Further, as injection molding conditions, molding can be performed in a range of cylinder temperature of 270 to 300 ° C., mold temperature of 5 to 40 ° C., screw rotation speed of 40 to 300 rpm, injection pressure of 40 to 140 kg / cm 2, and the like.
[0017]
The modified polyethylene terephthalate resin produced by the production method of the present invention can reduce the crystallization temperature during molding, but specifically, the temperature-programmed crystallization of the modified resin formed into a molded product by a differential scanning calorimeter. The temperature is preferably from 150 to 170 ° C, particularly preferably from 155 to 165 ° C.
Here, the temperature rising crystallization temperature refers to the top temperature of the crystallization peak observed in the middle of the temperature rising from room temperature to 285 ° C. at a rate of 20 ° C./min with a differential scanning calorimeter. .
[0018]
Among the molded articles obtained by the above molding method, the modified resin according to the present invention molds a preform by a blow molding method such as a cold parison method in which a preform obtained by an injection molding method is biaxially stretched after reheating. Suitable for containers such as carbonated beverages, fruit juice beverages, alcoholic beverages, beverages such as tea and mineral water, liquid seasonings such as soy sauce, sauces, mirin, dressings, edible oils, liquid detergents, cosmetics, etc. Used.
[0019]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to a following example, unless the summary is exceeded.
Example 1
A slurry of 13.0 kg of terephthalic acid and 5.82 kg of ethylene glycol was prepared, and placed in an esterification tank in which 0.30 kg of bis (2-hydroxyethyl) terephthalate was previously added and maintained at a temperature of 250 ° C. over 4 hours. Sequentially supplied. After the completion of the supply, the esterification reaction was allowed to proceed over 1 hour, then half of the amount was transferred to a polycondensation tank, 0.91 g of phosphoric acid and 0.92 g of germanium dioxide were charged, and the temperature was gradually raised from 250 ° C. to 278 ° C., The pressure is gradually reduced from normal pressure, and the polycondensation reaction is performed for 3 hours while maintaining the pressure at 0.5 mmHg. Then, the produced polymer is extracted in a strand form from the outlet provided in the bottom of the polycondensation tank, cooled with water, and then cut with a cutter. Thus, an elliptical columnar polymer chip was obtained.
Subsequently, the obtained polymer chip was partly made of polypropylene (Nippon Polychem, “FA3D”, melting point: 163 ° C.) with a part of a 100 mm diameter SUS pneumatic transport pipe over a length of 1 m. After transporting to a stirrer crystallizer (Bepex company type), the polymer chip surface was crystallized at 150 ° C., then transferred to a stationary solid phase polymerization tower, and under a nitrogen flow of 20 liters / kg · hr, about After drying at 140 ° C. for 3 hours, solid state polymerization was carried out at 210 ° C. for 20 hours to produce a chip-like modified polyethylene terephthalate resin.
The resulting modified polyethylene terephthalate resin had 10 ppb of polypropylene attached and had an intrinsic viscosity of 0.79 dl / g.
[0020]
From the obtained modified polyethylene terephthalate resin, in an injection molding machine (“M-70A” manufactured by Meiki Seisakusho), the temperature of each part of the cylinder and the nozzle head is 280 ° C., the screw rotation speed is 200 rpm, the injection time is 60 seconds, the mold Stepped square plate shaped plates having a thickness of 4 mm and 5 mm were injection molded at a cooling water temperature of 10 ° C.
The resulting molded plate was measured for the crystallization temperature and transparency of the modified resin, and the results are shown in Table 1.
In addition, the measuring method of each physical property is as follows.
[0021]
Crystallization temperature Using a differential scanning calorimeter ("DSC220C", manufactured by Seiko Denshi Co., Ltd.), the temperature of the molded plate was increased from room temperature to 285 [deg.] C. at a rate of 20 [deg.] C./min. Then, the top temperature of the crystallization peak observed during the measurement (temperature rise crystallization temperature: TC 1 ) was measured, and the temperature was further raised and kept at 285 ° C. for 3 minutes, then 10 ° C./min. The temperature was lowered at a rate of 5 ° C., and the top temperature of the crystallization peak observed during the measurement (temperature-falling crystallization temperature: TC 2 ) was measured.
Transparency Haze was measured with respect to the 4 mm and 5 mm thick portions of the molded plate using a haze meter (NDH-300A, manufactured by Nippon Denshoku Co., Ltd.).
[0022]
Further, from the obtained modified polyethylene terephthalate resin, in an injection molding machine (“TOSHIBA Co., Ltd.,“ IS-60B ”), the temperature of each part of the cylinder and the nozzle head is 280 ° C., the screw rotation speed is 200 rpm, the injection time is 10 seconds, gold The preform is injection-molded at a mold cooling water temperature of 10 ° C., and the plug portion is heated and crystallized by a crystallizer, followed by a preheating furnace temperature of 90 ° C., a blow pressure of 20 kg / cm 2 , and a molding cycle of 10 seconds. Stretch blow molding was performed with the set blow molding machine to form a bottle having an average body thickness of 300 μm and an internal volume of 1 liter, and subsequently heat-fixed for 10 seconds in a mold set at 150 ° C. under pneumatic tension.
The appearance of the obtained bottle was visually observed and evaluated according to the following criteria.
○: No turbidity and transparency, and no deformation.
Δ: Transparent with no turbidity, but deformed.
X: Whitening during crystallization.
[0023]
Comparative Example 1
Except that the polymer chip obtained in the polycondensation tank was transferred from the polycondensation tank to the agitating crystallizer as it was in the SUS-made aerodynamic transportation pipe, it was injection molded in the same manner as in Example 1 to measure each physical property. The results are also shown in Table 1.
[0024]
Example 2
The chip-like polyethylene terephthalate resin obtained in the same manner as in Comparative Example 1 was used in the same manner as in Example 1, using a magnet catcher capable of setting five bar magnets (diameter 21 mm) in one stage. The physical properties were measured by injection molding in the same manner as in Example 1 except that the processing was performed in place of the polypropylene pipe, and the results are shown in Table 1.
[0025]
Example 3
A chip-shaped polyethylene terephthalate resin obtained in the same manner as in Comparative Example 1 was used with a magnet catcher capable of setting five rod-shaped magnets (21 mm in diameter) in one stage, and one stage of polyamide resin (manufactured by Mitsubishi Engineering Plastics). Except that the pipe was made of “Novamid 1030”, melting point 224 ° C., the physical properties were measured by injection molding in the same manner as in Example 1, and the results are shown in Table 1.
[0026]
[Table 1]
【The invention's effect】
According to the present invention, it is possible to provide a method for producing a modified polyethylene terephthalate resin in which the crystallization temperature is lowered and the crystallization speed is improved without decreasing the transparency.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP845998A JP3624667B2 (en) | 1998-01-20 | 1998-01-20 | Method for producing modified polyethylene terephthalate resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP845998A JP3624667B2 (en) | 1998-01-20 | 1998-01-20 | Method for producing modified polyethylene terephthalate resin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11209492A JPH11209492A (en) | 1999-08-03 |
| JP3624667B2 true JP3624667B2 (en) | 2005-03-02 |
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| Application Number | Title | Priority Date | Filing Date |
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| JP845998A Expired - Fee Related JP3624667B2 (en) | 1998-01-20 | 1998-01-20 | Method for producing modified polyethylene terephthalate resin |
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| JP (1) | JP3624667B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4624590B2 (en) * | 2001-04-05 | 2011-02-02 | 三井化学株式会社 | Method for producing metal compound-containing polyester resin composition, preform for hollow molded article, and method for producing hollow molded article |
| JP2002317052A (en) * | 2001-04-20 | 2002-10-31 | Mitsui Chemicals Inc | Method and apparatus for production of modified polyethylene terephthalate |
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