JP4172872B2 - Propylene resin spool - Google Patents

Description

【００４６】
（式中、Ｒ¹ は水素原子又は炭素数１〜４のアルキル基を示し、Ｒ² 及びＲ³ はそれぞれ水素原子、炭素数１〜１２のアルキル基、シクロアルキル基、アリール基又はアラルキル基を示す。Ｍはアルカリ金属、アルカリ土類金属、アルミニウム及び亜鉛のうちのいずれかを示し、Ｍがアルカリ金属のときｍは０を、ｎは１を示し、Ｍがアルカリ土類金属又は亜鉛のときｎは１又は２を示し、ｎが１のときｍは１を、ｎが２のときｍは０を示し、Ｍがアルミニウムのときｍは１を、ｎは２を示す。）
有機リン酸金属塩の具体例としては、アデカスタブＮＡ−１１やアデカスタブＮＡ−２１（旭電化株式会社（製））が挙げられる。
【００４７】
▲３▼ソルビトール類としては、ベンジリデンソルビトール類が挙げられる。ベンジリデンソルビトール類とは、芳香族アルデヒド類と５価以上の多価アルコールとの縮合物である。ここで芳香族アルデヒド類としては、ベンズアルデヒド、炭素数１〜３のアルキル基が１〜５個置換したベンズアルデヒド置換体、ハロゲン原子が１〜５個置換したベンズアルデヒド置換体、炭素数１〜３のアルコキシ基が１〜５個置換したベンズアルデヒド置換体並びにそれらの任意の割合の混合物が挙げられる。又、多価アルコールとしては、ソルビット、キシリット等の糖アルコール並びにそれらの任意の割合の混合物が挙げられる。これらを縮合して得られる縮合物、すなわちベンジリデンソルビトール類としては、ベンズアルデヒドにおける芳香族の各置換基の種類や数が異なったり、或いは置換基の位置がオルト位、メタ位、パラ位と異なる位置異性体であったりする非対象型ベンズアルデヒド類あるいは芳香族の各置換基が同一である対象型ベンズアルデヒド類並びにそれらの混合物であってもい。たとえば、ベンジリデン基が１つのモノベンジリデンソルビトール類、２つのジベンジリデンソルビトール類、３つのトリベンジリデンソルビトール類或いはそれ以上ベンジリデンソルビトール類であってもよい。たとえば、ベンズアルデヒド類としてベンズアルデヒドとクミルアルデヒドの混合物を原料に用いることにより得られる非対称型ベンジリデンソルビトール類であってもよい。
【００４８】
一方の原料である多価アルコールとしては、ソルビット、キシリット等の糖アルコール並びにそれらの任意の割合の混合物に限定されず、ソルビット誘導体、キシリット誘導体並びにこれらの誘導体の任意の混合物も包含される。
本発明においては、ソルビトール類としては、ジベンジリデンソルビトール類が好ましく、なかでも特許２６３１６５２号公報に開示された下記一般式（２）
【００４９】
【化２】

【００５０】
（式中Ｘ¹ 、Ｘ² は夫々水素原子、炭素数１〜３のアルキル基、炭素数１〜３のアルコキシ基、ハロゲン原子を示し、同一であってもよい。ｍ、ｎは０〜５の整数、ｐは０又は１を示す。）
で表されるジベンジリデンソルビトール類がより好ましい。前記一般式（２）における炭素数１〜３のアルキル基としては、メチル基、エチル基、ｎ−プロピル基及びイソプロピル基が挙げられる。炭素数１〜３のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基が挙げられる。ハロゲン原子としては、塩素、フッ素、ヨウ素及び臭素が挙げられる。
【００５１】
さらに、本発明においては、前記一般式（２）で表されるジベンジリデンソルビトール類を、特定の溶媒により洗浄処理して得た精製物に特定の安定剤を添加したもものであることが、造核剤として用いた場合熱安定性が向上し好ましい。前記ジベンジリデンソルビトール類を精製するための洗浄溶媒としては、具体的には、炭素数１〜３の脂肪族低級アルコールの外、ｎ−ヘキサン等の炭素数６〜１２の飽和炭化水素、シクロヘキサン等の脂環式炭化水素及びトルエン等の芳香族炭化水素からなる群から選ばれる１種若しくは２種以上と、メタノール、エタノール、イソプロパノール等の脂肪族低級アルコール及びアセトン、メチルエチルケトン、メチルイソブチルケトン等に例示されるケトン類からなる群から選ばれる１種若しくは２種以上とからなる混合溶剤が例示される。
【００５２】
精製されたジベンジリデンソルビトール類に添加される安定剤としては、アルカリ性化合物及び／又はラジカル禁止剤が挙げられる。アルカリ性化合物としては、具体的に水酸化ナトリウム、水酸化カリウム等の無機アルカリやクエン酸、乳酸、乳酸ダイマーステアレート、コハク酸、安息香酸、ステアリン酸、ヒドロキシステアリン酸、オレイン酸、ベヘエン酸等に例示される脂肪酸、エチレンジアミンテトラ酢酸等の有機酸のナトリウム、カリウム等のアルカリ金属塩、カルシウム、マグネシウム等のアルカリ土類金属塩が挙げられる。
【００５３】
同じくラジカル禁止剤としては、ビスフェノールＡ、ブチルヒドロキシアニソール（別名、ＢＨＡ）、２，６−ジ−tert―ブチルヒドロキシトルエン（別名、ＢＨＴ）、２，６−ジ−tert−ブチル−ｐ−クレゾール、２，６−ジ−tert−ブチル−フェノール、４，４′−メチレンビス（２，６−ジ−tert−ブチルフェノール）、２，６−ジ−tert−ブチル−α−ジメチルアミノ−ｐ−クレゾール、２，６−ジ−tert−ブチル−ｐ−エチルフェノール、２，４，６−トリ−tert−ブチルフェノール、トリス（３，５−ジ−tert−ブチルー4 −ヒドロキシベンジル）イソシアヌレート、トリス［β−（３．５−tert−ブチル−４−ヒドロキシフェニル）プロピオニル−オキシエチル］イソシアヌレート、１，３，５−トリメチル−２，４，６−トリス（３．５−ジ−tert−ブチル−４−ヒドロキシベンジル）ベンゼン、１，６−ヘキサンジオール−ビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］、６−（４−ヒドロキシ−３，５−ジ−tert−ブチルアニリノ）−２，４−ビスオクチル−チオ−１，３，５−トリアジン、テトラキス［メチレン−３−（３，５−ジ−tert―ブチル−４−ヒドロキシフェニル）プロピオネート］メタン（別名Ｉｒｇａｎｏｘ １０１０１）、ｎ−オクタデシル−３−（３，５−ジーtert―ブチルー4 ーヒドロキシフェエル）プロピオネート、N ，N ′−ヘキサメチレンビス（３，５−ジ−tert―ブチル−４−ヒドロキシ−ヒドロシンナマミド、３．５−ジーtert―ブチル−４−ヒドロキシーベンジルフォスフォネートジエチルエステル、２，２−チオ−ジエチレンビス［３−（３，５−ジ−tert−ブチル−４−ヒドロキシフェニル）プロピオネート］等に例示されるポリメリックヒンダードフェノール類等のフェノール系化合物やトリス（ノニルフェニル）フォスファイト等のリン系化合物例示される。
【００５４】
上記のアルカリ性化合物又はラジカル禁止剤は、夫々単独若しくは２種以上を混合して使用され、精製されたジベンジリデンソルビトール類に添加される量としては、該精製処理物１００重量部に対しアルカリ性化合物及び／又はラジカル禁止剤を全量で５０〜１０，０００ｐｐｍ添加すればよい。
さらに、本発明においては、特開平８−２３９３８６号公報に開示されているように、上記一般式（２）で表されるジベンジリデンソルビトール類がＸ線回折法による測定により、結晶構造を有することが好ましく、なかでも六方晶結晶及び／又は立方晶結晶等の六方晶以外の結晶であることが特に好ましい。六方晶結晶と立方晶結晶では、六方晶結晶の方が溶融ポリオレフィン樹脂への分散速度及び溶解速度も優れており、結晶核剤としての性能が優れているので、六方晶結晶が好ましいが、両者の混合物であってもよい。混合物の割合としては、六方晶結晶１重量部に対して、立方晶結晶等の六方晶以外の結晶を１９重量部以下、好ましくは、０．０５〜１９重量部、特に好ましくは、０．０５〜５．７重量部である。本発明において、上記のように六方晶結晶単独を使用し、又は六方晶結晶と立方晶結晶等の六方晶以外の結晶との混合物の形態で使用するのに、好ましいジベンジリデンソルビトール類としては、例えば、次の化合物が挙げられる。
１，３：２，４−ビス（Ｏ−３，４−ジメチルベンジリデン）−Ｄ−ソルビトール、１，３：２，４−ビス（Ｏ−ｐ−メチルベンジリデン）−Ｄ−ソルビトール、１，３：２，４−ビス（Ｏ−ｐ−エチルベンジリデン）−Ｄ−ソルビトール、１，３−（Ｏ−ジメチルベンジリデン）−２，４−（Ｏ−ベンジリデン）−Ｄ−ソルビトール、１，３−（Ｏ−ベンジリデン）−２，４−（Ｏ−ジメチルベンジリデン）−Ｄ−ソルビトール、１，３：２，４−ビス（Ｏ−ベンジリデン）−Ｄ−ソルビトール、１，３：２，４−ビス（Ｏ−ｐ−クロロベンジリデン）−Ｄ−ソルビトール、１，３−（Ｏ−ｐ−クロロベンジリデン）−２，４−（Ｏ−Ｐ−メチルベンジリデン）−Ｄ−ソルビトール、及び１，３−（Ｏ−ｐ−メチルベンジリデン）−２，４−（Ｏ−ｐ−クロロベンジリデン）−Ｄ−ソルビトール。
【００５５】
また、具体的にソルビトール類としては、新日本理化（製）のゲルオールＭＤやゲルオールＭＤ−Ｒ（商品名）等も挙げられる。
本発明においては、前記（Ａ）成分には、前記（Ｂ）成分以外に、スプールの剛性を向上するために、無機又は有機充填剤を添加してもよい。無機又は有機充填剤としては、雲母、炭酸カルシウム、塩基性硫酸マグネシウム、チタン酸カルシウムウイスカー、ホウ酸アルミニウムウイスカー、ガラス繊維、炭素繊維、ボロン繊維等が挙げられる。添加量は、０．１〜５０重量部、好ましくは、０．１〜３０重量部である。
【００５６】
さらに、造核剤と無機又は有機充填剤の分散性を向上するために、各種カップリング剤を添加してもよい。カップリング剤としては、チタネート系カップリング剤、シラン系カップリング剤、飽和又は不飽和脂肪酸化合物、脂肪酸金属塩、脂肪酸エステル類、脂肪酸アミド類が挙げられる。
また、必要に応じて各種の添加剤を添加してもよい。添加剤としては、帯電防止剤や防曇剤などの表面機能用添加剤、アンチブロッキンング剤、酸化防止剤、耐候剤、熱安定剤、中和剤、滑剤、造核剤、着色剤、無機又は有機充填剤等があげられる。これらの添加剤は、１種用いてもよく、２種以上を組み合わせて用いてもよい。たとえば、 酸化防止剤としては、リン系酸化防止剤、フェノール系酸化防止剤及びイオウ系酸化防止剤等が挙げられる。
【００５７】
リン系酸化防止剤の具体例として、
トリスノニルフェニルホスファイト、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールホスファイト、ビス（２，６−ジ−ｔ−ブチル−４−メチルフェニル）ペンタエリスリトールホスファイト、２，２−メチレンビス（４，６−ジ−ｔ−ブチルフェニル）オクチルホスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）−４，４−ビフェニレン−ジ−ホスホナイト、アデカスタブ１１７８（旭電化（製））、スミライザーＴＮＰ（住友化学（製））、ＪＰ−１３５（城北化学（製））、アデカスタブ２１１２（旭電化（製））、ＪＰＰ−２０００（城北化学（製））、Ｗｅｓｔｏｎ６１８（ＧＥ（製））、アデカスタブＰＥＰ−２４Ｇ（旭電化（製））、アデカスタブＰＥＰ−３６（旭電化（製））、アデカスタブＨＰ−１０（旭電化（製））、ＳａｎｄｓｔａｂＰ−ＥＰＱ（サンド（製））、フォスファイト１６８（チバ・ガイギー（製））等が挙げられる。
【００５８】
フェノール系酸化防止剤の具体例として、
２，６−ジ−ｔ−ブチル−４−メチルフェノール、ｎ−オクタデシル−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート、テトラキス〔メチレン−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート〕メタン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、４，４’−ブチリデンビス−（３−メチル−６−ｔ−ブチルフェノール）、トリエチレングリコール−ビス〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオネート〕、３，９−ビス｛２−〔３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ〕−１，１−ジメチルエチル｝−２，４，８，１０−テトラオキサスピロ〔５，５〕ウンデカン、スミライザーＢＨＴ（住友化学（製））、ヨシノックスＢＨＴ（吉富製薬（製））、アンテージＢＨＴ（川口化学（製））、イルガノックス１０７６（チバ・ガイギー（製））、イルガノックス１０１０（チバ・ガイギー（製））、アデカスタブＡＯ−６０（旭電化（製））、スミライザーＢＰ−１０１（住友化学（製））、トミノックスＴＴ（吉富製薬（製））、ＴＴＨＰ（東レ（製））、イルガノックス３１１４（チバ・ガイギー（製））、アデカスタブＡＯ−２０（旭電化（製））、アデカスタブＡＯ−４０（旭電化（製））、スミライザーＢＢＭ−Ｓ（住友化学（製））、ヨシノックスＢＢ（吉富製薬（製））、アンテージＷ−３００（川口化学（製））、イルガノックス２４５（チバ・ガイギー（製））、アデカスタブＡＯ−７０（旭電化（製））、トミノックス９１７（吉富製薬（製））、アデカスタブＡＯ−８０（旭電化（製））、スミライザーＧＡ−８０（住友化学（製））等が挙げられる。
【００５９】
イオウ系酸化防止剤の具体例として、
ジラウリル−３，３’−チオジプロピオネート、ジミリスチル−３，３’−チオジプロピオネート、ジステアリル−３，３’−チオジプロピオネート、ペンタエリスリトールテトラキス（３−ラウリルチオプロピオネート）、スミライザーＴＰＬ（住友化学（製））、ヨシノックスＤＬＴＰ（吉富製薬（製））、アンチオックスＬ（日本油脂（製））、スミライザーＴＰＭ（住友化学（製））、ヨシノックスＤＭＴＰ（吉富製薬（製））、アンチオックスＭ（日本油脂（製））、スミライザーＴＰＳ（住友化学（製））、ヨシノックスＤＳＴＰ（吉富製薬（製））、アンチオックスＳ（日本油脂（製））、アデカスタブＡＯ−４１２Ｓ（旭電化（製））、ＳＥＥＮＯＸ ４１２Ｓ（シプロ化成（製））、スミライザーＴＤＰ（住友化学（製））等が挙げられる。
【００６０】
本発明において酸化防止剤を用いる場合は、（Ａ）成分に対し酸化防止剤を０．００１〜１重量部程度添加すればよい。これにより、黄変等を防ぐことができて好ましい。
【００６１】
【実施例】
以下、実施例により本発明をさらに詳細に説明するが、本発明は以下の実施例により何ら制限されるものではない。
なお、前記本文及び実施例で用いる試験方法は、以下の通りである。
（１）メルトフローレート（ＭＦＲ）の測定
ＪＩＳ Ｋ７２１０に準拠し、２３０℃、２．１６ｋｇ荷重で測定する。
（２）極限粘度〔η〕の測定
ＡＳＴＭＤ１６０１に準拠し、デカリンに溶解し１３５℃で測定した値とする。
（３）常温キシレン可溶成分量の測定
常温（２５℃）キシレン可溶成分及び不溶成分は、次のようにして取得した。
▲１▼試料を５±０．０５ｇ精秤して１０００ミリリットルナス型フラスコに入れ、さらにＢＨＴ（酸化防止剤）１±０．０５ｇを添加したのち、回転子及びパラキシレン７００±１０ミリリットルを投入する。
▲２▼次いでナス型フラスコに冷却器を取り付け、回転子を作動させながら、１４０±５℃のオイルバスでフラスコを１２０±３０分間加熱して、試料をパラキシレンに溶解させる。▲３▼次に、１０００ミリリットルビーカーにフラスコの内容物を注いだのち、ビーカー内の溶液をスターラーで攪拌しながら、室温（２５℃）になるまで放冷（８時間以上）後、析出物を金網でろ取する。
▲４▼ろ液は、さらにろ紙にてろ過したのち、このろ液を３０００ミリリットルビーカーに収容されたメタノール２０００±１００ミリリットル中に注ぎ、この液を室温（２５℃）にてスターラーで攪拌しながら、２時間以上放置する。
▲５▼次いで析出物を金網でろ取したのち、５時間以上風乾後、真空乾燥機にて１００±５℃で２４０〜２７０分間乾燥して、２５℃キシレン可溶成分を回収する。
▲６▼一方、上記▲３▼において金網でろ取した析出物を、再度上記▲１▼及び▲２▼の方法に準じてパラキシレンに溶解したのち、３０００ミリリットルビーカーに収容されたメタノール２０００±１００ミリリットル中に素早く熱いまま移し、２時間以上スターラーで攪拌後、一晩室温（２５℃）にて放置する。
▲７▼次いで析出物を金網でろ取したのち、５時間以上風乾後、真空乾燥機にて１００±５℃で２４０〜２７０分間乾燥して、２５℃キシレン不溶成分を回収する。
【００６２】
２５℃キシレンに対する可溶成分の含有量（ｗ）は、試料重量をＡｇ、前記▲５▼で回収した可溶成分の重量をＣｇとすれば、
ｗ（重量％）＝１００×Ｃ／Ａ
で表され、また不溶成分の含有量は（１００−ｗ）重量％で表される。
（４）常温キシレン可溶成分の¹³Ｃ−ＮＭＲによるエチレン含有量の測定
¹³Ｃ−ＮＭＲの測定はすべて下記の方法による。
【００６３】
すなわち、ＮＭＲ試料管に試料２２０ｍｇを採取し、これに１，２，４−トリクロロベンゼン／重ベンゼン混合溶媒（容量比９０／１０）３ミリリットルを加えたのち、キャップをして１３０℃で均一に溶解後、¹³Ｃ−ＮＭＲの測定を次に示す測定条件で行う。
装置： 日本電子（株）製ＪＮＭ−ＥＸ４００
パルス幅： ９μｓ（４５°）
パルス繰り返し時間：４秒
スペクトル幅： ２００００Ｈｚ
測定温度： １３０℃
積算回数： １０００〜１００００回
また、２５℃キシレンに対する可溶成分のエチレン単位含有量及び不溶成分のエチレン単位含有量は、下記の方法により求めた値である。
【００６４】
すなわち、試料の¹³Ｃ−ＮＭＲを測定し、そのスペクトルにおける３５〜２１ｐｐｍ〔テトラメチルシラン（ＴＭＳ）化学シフト基準〕領域の７本のピーク強度から、まずエチレン（Ｅ），プロピレン（Ｐ）のｔｒｉａｄ連鎖分率（モル％）を次式により計算する。
ｆ_EPE ＝〔Ｋ（Ｔδδ）／Ｔ〕×１００
ｆ_PPE ＝〔Ｋ（Ｔβδ）／Ｔ〕×１００
ｆ_EEE ＝〔Ｋ（Ｓγδ）／４Ｔ＋Ｋ（Ｓδδ）／２Ｔ〕×１００
ｆ_PPP ＝〔Ｋ（Ｔββ）／Ｔ〕×１００
ｆ_PEE ＝〔Ｋ（Ｓβδ）／Ｔ〕×１００
ｆ_PEP ＝〔Ｋ（Ｓββ）／Ｔ〕×１００
ただし、Ｔ＝Ｋ（Ｔδδ）＋Ｋ（Ｔβδ）＋Ｋ（Ｓγδ）／４＋Ｋ（Ｓδδ）／２＋Ｋ（Ｔββ）＋Ｋ（Ｓβδ）＋Ｋ（Ｓββ）
ここで例えばｆ_EPE はＥＰＥｔｒｉａｄ連鎖分率（モル％）を、Ｋ（Ｔδδ）はＴδδ炭素に帰属されるピークの積分強度を示す。
【００６５】
次に、エチレン単位含有量（ｘ（重量％））を上記ｔｒｉａｄ連鎖分率を用いて次式により計算する。
エチレン単位含有量（重量％）＝２８｛３ｆ_EEE ＋２（ｆ_PEE ＋ｆ_EPE ）＋ｆ_PPE ＋ｆ_PEP ｝×１００／〔２８｛３ｆ_EEE ＋２（ｆ_PEE ＋ｆ_EPE ）＋ｆ_PPE ＋ｆ_PEP ｝＋４２｛３ｆ_PPP ＋２（ｆ_PPE ＋ｆ_PEP ）＋ｆ_EPE ＋_PEE ｝〕
（５）常温キシレン不溶成分の¹³Ｃ−ＮＭＲによる立体規則性指標の測定
上記立体規則性指標は下記の方法により求めた値である。
【００６６】
すなわち、２５℃キシレンに対する不溶成分の¹³Ｃ−ＮＭＲスペクトルにおいて、メチル炭素のシグナルは、立体規則性の影響により低磁場から高磁場にわたり、ｍｍｍｍ，ｍｍｍｒ，ｒｍｍｒ，ｍｍｒｒ，ｍｍｒｍ＋ｒｒｍｒ，ｒｍｒｍ，ｒｒｒｒ，ｍｒｒｒ，ｍｒｒｍの９本のピークに分裂して観測される。この９本のうち、ピーク強度の強いｍｍｍｍ，ｍｍｍｒ，ｍｍｒｒ，ｍｍｒｍ＋ｒｒｍｒ，ｒｒｒｒ，ｍｒｒｍの６本のピークに着目し、該不溶成分の立体規則性指標を次式により算出する。
【００６７】
立体規則性指標（％）＝Ｌ_mmmm×１００／（Ｌ_mmmm＋Ｌ_mmmr＋Ｌ_mmrr＋Ｌ_mmrm+rrmr ＋Ｌ_rrrr＋Ｌ_mrrm）
ここで、Ｌ_mmmm，Ｌ_mmmr，Ｌ_mmrr，Ｌ_mmrm+rrmr ，Ｌ_rrrr及びＬ_mrrmは、それぞれ¹³Ｃ−ＮＭＲスペクトルにおけるｍｍｍｍ，ｍｍｍｒ，ｍｍｒｒ，ｍｍｒｍ＋ｒｒｍｒ，ｒｒｒｒ及びｍｒｒｍのピークのベースラインからの高さである。ただし、ｍｍｍｍのピークは、化学シフトとピーク高さの異なる複数の離散点から構成されており、またｍｍｍｒのピークはｍｍｍｍの主ピークのテーリング上に乗っているので、これらのピークのベースラインからの高さは、常法に従って補正を行う。
（６）常温キシレン可溶成分のパルスＮＭＲで測定したＴ₁ 緩和時間の測定
Ｔ₁ は、縦方向の磁化の回復の時定数であり、最も一般的な測定方法は、反転回復法（１８０°−τ−９０°パルス法）である。先ず、ｔ＝０でθ＝１８０°のパルスによって磁化を−ｚ’方向に与え、その後熱平衡値Ｍ₀ への回復が始まる。τ時間経過後に９０°パルスを与えると磁化はｙ’軸方向に回転し、磁化の大きさに比例したＦＩＤシグナルが観測される。τを連続的に変えれば、信号強度Ｍ（τ）の回復曲線が得られる。ブロッホの方程式に基づいて、Ｍ（０）＝−Ｍ₀ の初期条件によって、縦方向の磁化の回復は、
Ｍ＝Ｍ₀ ｛１−２ｅｘｐ（−τ／Ｔ₁ ）｝
で表される。更に、実用的には、ｌｎ｛Ｍ（∞）−Ｍ（τ）｝＝ｌｎ｛２Ｍ（∞）｝−τ／Ｔ₁ となり、ｌｎ｛Ｍ（∞）−Ｍ（τ）｝〜τのプロットから得られる直線の傾きでＴ₁ を決定することができる。
【００６８】
なお、積算の繰り返し実験も含め、一連の測定を行う場合、磁化が熱平衡状態に戻るまで待つ必要があり、少なくとも５Ｔ₁ 以上の待ち時間（５Ｔ₁ で９９．３％回復する）を要するので、Ｍ（∞）は、τ＞５Ｔ₁ を満たすτに対するＭ（τ）値を採用した。
ブルカー社製パルスＮＭＲ装置ＣＸＰ−９０を使用して以下の条件で測定した。
測定核：水素原子核
測定周波数：９０ＭＨＺ
測定温度：３０℃
測定法：反転回復法（１８０°−τ−９０°パルス法）
１８０°：１８０°パルス
９０°：９０°パルス
τ：可変時間、９０°パルス幅：２．３〜２．４μ秒
（７）耐衝撃性の測定
ＪＩＳ Ｋ７１１０に準拠して、射出成形品を用いて、２３℃、−２０℃でのノッチつきアイゾット衝撃強度を測定する。
（８）曲げ弾性率の測定
ＪＩＳ Ｋ７２０３に準拠し、射出成形品を用いて曲げ弾性率を測定する。
（９）落下テストの測定
落下テストは、ＪＩＳ Ｚ３３１２に規定されるＹＧＷ１１のワイヤ径１．２ｍｍである溶接用ソリッドワイヤを２０ｋｇ（１層７４列，５１層）ずつ自動的に、それぞれ２５コイル（ワイヤ：５００ｋｇ）巻き取ったスプールを、ワイヤを始端止穴を基準に８回落下させ、破壊の有無を調べた。落下させる高さは、２３℃では６０ｃｍ，−２０℃では３０ｃｍとした。なお、サンプル数は、ｎ＝３で実施した。
【００６９】
その結果、８回落下させても破壊しない場合を◎、５回以上８回未満落下させて破壊する場合を○、３回以上５回未満落下させて破壊する場合を△、３回未満落下させて破壊する場合を×とした。
（１０）フランジ破壊強度
フランジ破壊強度は、３０ｃｍ幅のフックをフランジ部に取付け、巻胴部フランジ部が破壊するときの荷重を求め、それをフランジ破壊強度とした。
（１１）巻き乱れテスト
スプールにＪＩＳ Ｚ３３１２に規定されるＹＧＷ１１のワイヤ径１．２ｍｍである溶接用ソリッドワイヤを２０ｋｇ（１層７４列，５１層）ずつ自動的に、それぞれ２５コイル（ワイヤ：５００ｋｇ）巻き取った。巻き初めの不良個数および上層部での乱巻数をそれぞれ調べ、いずれも良好であった試験例につき、パレットに積みトラックで５００ｋｍ輸送し、スプールの破損状況、整列巻ワイヤの乱れ状況を調べた。
〔実施例１〕
〔重合触媒の調製〕
（１）触媒Ａの調製
（固体触媒成分の調製）
窒素で置換した内容積８０リットルの攪拌機付ステンレス製反応器にジエトキシマグネシウム４．０ｋｇを投入する。更に脱水処理したデカンを２０リットルを加えた。４０℃に加熱し、四塩化珪素０．６リットルを加え、２０分間攪拌し、ジエチルフタレートを０．４リットルを加えた。溶液を８０℃まで昇温し、引き続き四塩化チタンを１９．２リットル加えた。内温を１２５℃として２時間接触させた。その後、攪拌を停止して固体を沈降させ、上澄みを抜き出した。２．６リットルの脱水デカンを加え、攪拌しながら１３５℃まで昇温し、１分間保持した後、攪拌を停止して固体を沈降させ、上澄みを抜き出した。この洗浄操作を７回繰り返した。更に四塩化チタンを３０．５リットル加え、内温を１３５℃とし、２時間接触させた。その後、１３５℃の脱水デカンによる洗浄を６回繰り返し、固体触媒成分を得た。
（予備重合）
上記８０リットル反応槽に固体触媒成分〔Ａ〕を３．８ｋｇ、脱水処理したヘプタンを３２リットル加えた。４０℃に加熱し、トリエチルアルミニウム０．１６リットルとジシクロペンチルジメトキシシランを０．５リットル加えた。これにプロピレンガス０．１２〜０．１８ＭＰａになるように連続的に供給しながら２時間反応させた。その後、固体成分を脱水ヘプタンを用いて充分洗浄を行い触媒Ａを得た。
（２）プロピレンの気相重合
１０リットル気相連続重合装置を用いてポリマーを製造した。すなわち、反応槽１を８５℃に保ち、プロピレンを圧力３．０ＭＰａ，トリエチルアルミニウムを４ミリモル／ｋｇＰＰ，ジシクロペンチルジメトキシシランを０．４ミリモル／ｋｇＰＰ，上記触媒Ａを０．０２ミリモル／ｋｇＰＰ，水素ガスを６５０リットル／時間の割合で連続的に供給した。また、反応槽２を６０℃に保ち、エチレンを１６．３ｋｇ／時間，水素ガスを４５０リットル／時間で連続的に供給し、全圧を１．６ＭＰａに保った。生産量は４０ｋｇ／ｈｒであった。
（３）造粒
得られたブロックポリプロピレンパウダーに造核剤としてアデカスタブＮＡ−１１を０．０５重量％，中和剤として、ステアリン酸カルシウムを１０００ｐｐｍ、ＤＨＴ−４Ａ（協和化学工業（株）製：マグネシウム・アルミニウム・ハイドロオキサイド・カーボネート・ハイドレート）を５００ｐｐｍ、酸化防止剤としてＰ−ＥＰＱ（旭電化工業（株）製：テトラキス（２，４−ジターシャルブチルフェニル４，４−ビスフェニレンジフォスフォナイト））を７５０ｐｐｍ、イルガノックス１０１０（チバスペシャリティケミカルズ社製：フェノール系酸化防止剤）を１５００ｐｐｍ加えよく混合させた後、連続的に造粒し、ペレットを作成した。ペレットの一部につき、前記した試験方法により所定の構造解析を行い、残りのペレットを射出成形して各種試験片を作成し物性測定を実施した。構造解析の結果と物性測定の結果を表１に示す。
（４）スプールの製造
また、得られたペレットを用い５００トンの射出成形機にて、下記のスプールを製造した。
【００７０】
スプールは、それぞれフランジ外径２７０ｍｍ、フランジ厚さは胴体部に接する部分が５ｍｍで外周方向へ徐々に薄くなり外周の最小部は３．５ｍｍとした。胴体の外径は１４８ｍｍであり、厚さは３．２ｍｍである。胴体にはこれの円周方向に延びるとともにフランジ側面に沿って開口する係止穴を持っている形状とした。前記の試験方法により、スプール試験を行い、得られた結果を表１に示す。
〔参考例１〕
実施例１の（２）プロピレンの気相重合における反応槽２のエチレン量を１５．０ｋｇ／時間，及び造核剤をタルク（平均粒径７ミクロン）０．４重量％に変えたこと以外は実施例１と同様に行った。得られた結果を表１に示す。
〔比較例１〕
出光石油化学（製）のポリプロピレンＪ−３０５３Ｈ（商品名）を用いてスプールを製造したこと以外は実施例１と同様に行った。その結果を表１に示す。
【００７１】
【表１】

【００７２】
【発明の効果】
本発明のプロピレン樹脂製のスプールは、剛性及び耐衝撃性に優れワイヤを整列巻状態で自動的に巻き取ることができるとともに輸送時の破損ならびに乱れをも防止することがでる。
【図面の簡単な説明】
【図１】本発明の一例を示すスプール
【図２】従来のＰＰ樹脂製のスプールにおけるワイヤ固定時の係止穴の変形を示す図。（ａ）、（ｂ）はワイヤ先端折り曲げ部が係止穴から飛び出した様子を示す図。
【図３】従来のＰＰ樹脂製のスプールにおけるワイヤを巻回した場合のフランジ部の広がりを示す図。
【図４】本発明のスプールにおけるワイヤ固定時の係止穴の様子を示す図。（ａ）、（ｂ）はワイヤ先端折り曲げ部が係止穴に固定されている様子を示す図。
【符号の説明】
１：胴
２：フランジ
３：係止穴
４：ワイヤ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a spool used when winding or rewinding a metal wire such as an electric wire, a copper wire, or a welding wire. Specifically, the spool is excellent in rigidity, and disturbs a winding wire during winding or transportation. Propylene resin spool to prevent.
[0002]
[Prior art]
Conventionally, a spool made of a synthetic resin is known as a spool used when winding or rewinding a metal wire such as an electric wire, a copper wire, or a welding wire. Polystyrene has been widely used as a synthetic resin. In recent years, polypropylene has come to be used from the viewpoint of price. Polypropylene has a drawback of low bending strength and hardness, although it has better impact strength than polystyrene. On the other hand, a spool for winding a welding wire made of a propylene resin containing 0.1 to 5.0% by weight of talc is proposed in Japanese Patent Laid-Open No. 5-26259. However, although the bending strength and hardness are improved, since the rigidity and impact resistance are low, the flange portion of the spool expands or cracks when dropped, which is not sufficient.
[0003]
[Problems to be solved by the invention]
The present invention solves the above-described problems, and is a propylene resin that has excellent rigidity and impact resistance, can automatically wind wires in an aligned winding state, and prevents breakage and disturbance during transportation. The object is to provide a spool made of steel.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that a propylene-ethylene block copolymer having specific properties, or a propylene resin spool formed by adding a nucleating agent to the copolymer. Is excellent in rigidity and impact resistance, and there is no deformation of the locking hole or winding of the flange when winding the wire, and there is no breakage or disturbance of the aligned winding during transportation. It came to be completed.
[0005]
That is, the present invention provides the following propylene resin spools.
1. A spool made of propylene resin comprising a propylene-ethylene block copolymer (A) having the properties shown in the following (a), (b) and (c).
(A) Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.01 to 1000 g / 10 minutes,
(B) of room temperature xylene insoluble components¹³The stereoregularity index [mmmm] fraction measured by C-NMR is 98.9% or more,
(C) The room temperature xylene-soluble component satisfies the following (c1), (c2) and (c3) (c1) accounts for 3 to 50% by weight
(C2) T measured by pulse NMR₁The relaxation time component consists of a single relaxation component
(C3)¹³The ethylene content measured by C-NMR was x wt%, and T was measured by pulse NMR.₁Relaxation time y (milliseconds) satisfies the following relational expression
y ≦ 0.0014x^Three-0.0897x²-1.0593x + 231.6 (I)
2. 2. The propylene resin spool according to 1 above, wherein the melt flow rate (MFR) (230 ° C., 2.16 kg load) of (A) is 0.3 to 300 g / 10 min.
3. 3. The propylene resin spool according to 1 or 2 above, wherein 0.01 to 5% by weight of the nucleating agent (B) is added to the propylene-ethylene block copolymer (A).
4). 4. The propylene resin spool as described in 3 above, wherein the nucleating agent (B) is selected from any of talc, organophosphate metal salts and sorbitols.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the propylene resin spool of the present invention will be described in detail.
The propylene resin spool of the present invention is a spool made of a propylene-ethylene block copolymer (A) having the properties shown in the following (a), (b) and (c).
(A) Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.01 to 1000 g / 10 minutes,
(B) of room temperature xylene insoluble components¹³The stereoregularity index [mmmm] fraction measured by C-NMR is 98.9% or more,
(C) The room temperature xylene-soluble component satisfies the following (c1), (c2) and (c3) (c1) accounts for 3 to 50% by weight
(C2) T measured by pulse NMR₁The relaxation time component consists of a single relaxation component
(C3)¹³The ethylene content measured by C-NMR was x wt%, and T was measured by pulse NMR.₁Relaxation time y (milliseconds) satisfies the following relational expression
y ≦ 0.0014x^Three-0.0897x²-1.0593x + 231.6 (I)
The spool of the present invention comprises a propylene-ethylene block copolymer (A) having the above-mentioned properties, and further a propylene resin to which a nucleating agent is added as necessary. Since it has excellent creep properties, there is no deformation of the wire locking hole that occurs at the beginning of winding the wire, or there is no spread of the flange after winding multiple layers, and the wire can be automatically wound in an aligned winding state. There is an advantage that it does not cause cracks during dropping and turbulence during transportation.
[0007]
Here, the advantage of the propylene resin spool (FIG. 1) of the present invention will be specifically described by taking a spool used for a welding wire as an example.
Usually, in order to wind a wire around a spool, first, the wire tip is inserted into a locking hole, bent, and fixed to the spool. Next, the spool is rotated to wind the wire into a plurality of layers. When a conventional PP resin spool is used in the above process, there are the following problems. That is, after the wire tip is fixed to the locking hole, the resin is soft when the spool is rotated. Therefore, the spool locking hole is deformed, and the wire is not fixed firmly to the locking hole, or may be removed. As shown in a) and (b), the bent portion of the wire 4 protrudes from the locking hole 3 and the second and subsequent layers of the wire are not wound up at the correct position, resulting in turbulent winding. Even if a plurality of layers are wound, the rigidity is low when winding the wire or transporting the wire, so that the flange 2 spreads in the X direction as shown in FIG. There is a problem that.
[0008]
On the other hand, FIG. 4 shows an example in which the propylene resin spool of the present invention is used, and the welding wire 4 can be fixed to the locking hole 3 without protruding bent portions. Further, a good aligned winding can be obtained without deformation of the flange.
In the case of propylene resin that does not satisfy the above requirements, the rigidity of the spool is lowered or the impact resistance is lowered, and the wire locking hole is deformed, the flange is spread, or cracks occur when dropped.
The propylene resin in the present invention is the following propylene-ethylene block copolymer (A).
[1] Propylene-ethylene block copolymer (A)
The propylene-ethylene block copolymer (A) in the present invention is the following [propylene-ethylene block copolymer]. An example of the production method is shown in [Propylene-ethylene block copolymer production method].
[Propylene-ethylene block copolymer]
The propylene-ethylene block copolymer in the present invention is a composition comprising a propylene homopolymer as a main component, an ethylene-propylene copolymer and an ethylene homopolymer, typically a propylene-ethylene block copolymer. However, the present invention is not limited to this, and may be a blend of the above polymers.
[0009]
The greatest feature of the propylene-ethylene block copolymer in the present invention is that the ethylene-propylene copolymer part is occupied by a uniform rubber-like elastic body, and as a result, it is particularly impact resistant without impairing rigidity and other physical properties. Is that an improved block copolymer is formed.
In the present invention, the melt flow rate (MFR) (230 ° C., 2.16 kg load) of the propylene-ethylene block copolymer (A) is preferably 0.3 to 300 g / 10 minutes, -100 g / 10 min is more preferable, and 1-60 g / 10 min is particularly preferable. If it is smaller than 0.01 g / 10 min, molding is difficult, and if it is larger than 1000 g / 10 min, the physical property strength is insufficient.
[0010]
Further, the propylene-ethylene block copolymer in the present invention has a room temperature xylene-insoluble component.¹³The stereoregularity index [mmmm] fraction measured by C-NMR is 98.9% or more.
This room temperature xylene insoluble component¹³Details of the C-NMR measurement method will be described later.
The room temperature xylene insoluble component is mainly a propylene homopolymer component, and the stereoregularity index [mmmm] fraction obtained by this measurement method is also called an isotactic pentad fraction, This is the ratio of five consecutive meso-bonded propylene monomer units present in all propylene monomer units. Therefore, the higher the isotactic pentad fraction, the higher the proportion occupied by polypropylene having an isotactic structure. If the stereoregularity index [mmmm] fraction is smaller than 98.9%, the rigidity, surface height and heat resistance are inferior and insufficient.
[0011]
Further, the propylene-ethylene block copolymer in the present invention is required to first occupy 3 to 50% by weight of the soluble component with respect to the normal temperature xylene soluble component. This room temperature xylene-soluble component is mainly an ethylene-propylene copolymer part component. If the amount of the soluble component is less than 3% by weight, the impact resistance is insufficient, and if it is more than 50% by weight, the rigidity, surface height , Heat resistance is inferior and insufficient.
[0012]
Furthermore, the propylene-ethylene block copolymer in the present invention was first measured with pulse NMR for the room temperature xylene soluble component.₁The relaxation time component comprises a single relaxation component; and¹³The ethylene content measured by C-NMR was x wt%, and T was measured by pulse NMR.₁The relaxation time y (milliseconds) satisfies the following relational expression.
y ≦ 0.0014x^Three-0.0897x²-1.0593x + 231.6 (I)
This room temperature xylene-soluble component is mainly an ethylene-propylene copolymer part component and does not contain crystalline polyethylene, and the soluble component was measured by pulse NMR.₁The method of measuring the relaxation time will be described later, but the technical meaning is that the amount of time required for the nuclear magnetic moment of the sample excited by irradiating the electromagnetic wave with a predetermined frequency to return to the original state is small. The level of molecular mobility is shown. T₁A small value corresponds to a low frequency region of the molecular motion of the sample. T₁The high impact resistance of a sample having a small size suggests that the time scale of the impact test measurement is close to the frequency region.
[0013]
T₁That the relaxation time component is a single component means that it has properties close to a uniform component. That is, the meaning of the formula (I) indicates that the ethylene-propylene copolymer part is composed of a rubber-like elastic body having a low molecular motion frequency region with respect to the ethylene concentration and close to a single component.
In the measurement results, the horizontal axis represents variable time τ (irradiation time interval of 180 ° pulse and 90 ° pulse), and the vertical axis represents signal intensity M (τ) after 90 ° pulse irradiation. When (∞) -M (0)} is plotted, T₁Is given by the negative reciprocal value of the slope of the straight line. Where T₁If is small, the slope of the relaxation time is large, and it decays in a shorter time. Furthermore, when the line connecting the plotted points is composed of a plurality of straight lines having different inclinations, it is composed of a plurality of components, so that a single component needs to be composed of a single straight line. .
[0014]
In the propylene-ethylene copolymer of the present invention, the room temperature xylene-soluble component was measured by pulse NMR.₁If there is no single relaxation time component, impact strength is poor. Further, if the formula (I) is not satisfied, the impact strength is reduced.
The propylene-ethylene block copolymer shown above is a polymer in a new area that has never existed before, and its physical characteristics are also rigid and impact strength, Rockwell hardness and impact strength, heat distortion temperature and impact strength. Such physical property balance is balanced at a high level.
[Propylene-ethylene block copolymer production method]
The propylene-ethylene block copolymer in the present invention is not limited to its production method as long as the above properties are satisfied. However, the propylene-ethylene block copolymer has a propylene homopolymer having high stereoregularity and is co-polymerized with ethylene. In order to obtain a polymer having excellent polymerizability, particularly a high molecular weight product having an MFR of about 0.3 to 300 g / 10 min, it is preferable to use a Ziegler type catalyst rather than a metallocene catalyst. Specifically, for example, (A) a solid catalyst component formed from (a) a magnesium compound, (b) a titanium compound, (c) an electron donor, and (d) a silicon compound as necessary, (B And a method of polymerizing using a catalyst comprising an organoaluminum compound and, if necessary, (C) an electron donating compound as a third component. In particular, in the method for preparing a solid catalyst component used in the present invention, a magnesium compound and a titanium compound are contacted at 120 to 150 ° C. in the presence of an electron-donating compound and, if necessary, a silicon compound, and then 100 to It is better to wash with an inert solvent at 150 ° C.
[0015]
Below, each catalyst component, an adjustment method, a polymerization method, etc. are demonstrated concretely.
[I] Each catalyst component
(A) Solid catalyst component
The solid catalyst component is formed from the following (a) titanium compound, (b) magnesium compound, (c) electron donor, and (d) silicon compound as required.
(A) Titanium compound
The titanium compound is not particularly limited, but the general formula (II)
TiX¹ _p(OR¹)_4-p                            ... (II)
The titanium compound represented by can be preferably used.
[0016]
In the above general formula (II), X¹Represents a halogen atom, and among them, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R¹Is a hydrocarbon group, which may be a saturated or unsaturated group, may be linear, branched or cyclic, and may be sulfur, nitrogen, oxygen , Silicon, phosphorus and other heteroatoms may be included. A hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, an alkenyl group, a cycloalkenyl group, an aryl group and an aralkyl group are preferable, and a linear or branched alkyl group is particularly preferable. -OR¹When a plurality of are present, they may be the same as or different from each other. R¹Specific examples of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, and phenethyl group. p shows the integer of 0-4.
[0017]
Specific examples of the titanium compound represented by the general formula (I) include tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetraisobutoxy titanium, Tetraalkoxy titanium such as tetracyclohexyloxy titanium and tetraphenoxy titanium; titanium tetrahalides such as titanium tetrachloride, titanium tetrabromide and titanium tetraiodide; methoxy titanium trichloride, ethoxy titanium trichloride, propoxy titanium trichloride, n -Trihalogenated alkoxytitanium such as butoxytitanium trichloride, ethoxytitanium tribromide; dimethoxytitanium dichloride, diethoxytitanium dichloride, diisopropoxytitanium dichloride, di-n-propoxytitanium dichloride Dihalogenated dialkoxytitanium such as diethoxytitanium dibromide; monohalogen such as trimethoxytitanium chloride, triethoxytitanium chloride, triisopropoxytitanium chloride, tri-n-propoxytitanium chloride, tri-n-butoxytitanium chloride And trialkoxy titanium. Among these, a high halogen-containing titanium compound, particularly titanium tetrachloride is preferable from the viewpoint of polymerization activity. These titanium compounds may be used alone or in combination of two or more.
(B) Magnesium compound
Although there is no restriction | limiting in particular as a magnesium compound, General formula (III)
MgR²R^Three                                      ... (III)
The magnesium compound represented by can be preferably used.
[0018]
In the above general formula (III), R²And R^ThreeIs a hydrocarbon group, OR^FourGroup (R^FourRepresents a hydrocarbon group) or a halogen atom. Where R²And R^ThreeAs the hydrocarbon group, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group and the like are ORed.^FourAs the group, R^FourRepresents an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group, an aralkyl group, and the like, and examples of the halogen atom include chlorine, bromine, iodine, fluorine, and the like. R²And R^ThreeMay be the same or different.
[0019]
Specific examples of the magnesium compound represented by the above general formula (III) include alkyl magnesium such as dimethyl magnesium, diethyl magnesium, diisopropyl magnesium, dibutyl magnesium, dihexyl magnesium, dioctyl magnesium, ethyl butyl magnesium, diphenyl magnesium, dicyclohexyl magnesium, Aryl magnesium; alkoxy magnesium such as dimethoxymagnesium, diethoxymagnesium, dipropoxymagnesium, dibutoxymagnesium, dihexyloxymagnesium, dioctoxymagnesium, diphenoxymagnesium, dicyclohexyloxymagnesium, allyloxymagnesium; ethylmagnesium chloride, butyl Magnesium chloride, hexyl magnesium Alkyl magnesium halides such as muchloride, isopropylmagnesium chloride, isobutylmagnesium chloride, t-butylmagnesium chloride, phenylmagnesium bromide, benzylmagnesium chloride, ethylmagnesium bromide, butylmagnesium bromide, phenylmagnesium chloride, butylmagnesium iodide, arylmagnesium halides; Alkoxymagnesium halides such as butoxymagnesium chloride, cyclohexyloxymagnesium chloride, phenoxymagnesium chloride, ethoxymagnesium bromide, butoxymagnesium bromide, ethoxymagnesium iodide; allyloxymagnesium halides; magnesium chloride, magnesium bromide, magnesium iodide, etc. Halogenated magnesium, and the like can be mentioned.
[0020]
Among these magnesium compounds, magnesium halide, alkoxymagnesium, alkylmagnesium, and alkylmagnesium halides can be suitably used from the viewpoint of polymerization activity and stereoregularity.
The magnesium compound can be prepared from magnesium metal or a compound containing magnesium.
[0021]
As an example, a metal magnesium halide and a general formula X² _mM (OR^Five)_nmAn alkoxy group-containing compound represented by the formula:²Represents a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms, M represents a boron, carbon, aluminum, silicon or phosphorus atom, and R^FiveRepresents a hydrocarbon group having 1 to 20 carbon atoms. n represents the valence of M, and n> m ≧ 0. ).
[0022]
Here, examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride and the like. Of these, silicon tetrachloride is preferred. X above²And R^FiveAs the hydrocarbon group, alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group and octyl group; alkenyl group such as cyclohexyl group, allyl group, propenyl group and butenyl group Aryl groups such as phenyl group, tolyl group and xylyl group; aralkyl groups such as phenethyl group and 3-phenylpropyl group; Among these, an alkyl group having 1 to 10 carbon atoms is particularly preferable.
As another example, Mg (OR⁶)₂ A magnesium alkoxy compound represented by the formula:⁶Represents a hydrocarbon group having 1 to 20 carbon atoms. And a method of bringing a halide into contact therewith.
[0023]
Examples of the halide include silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, hydrogen chloride and the like. Among these, silicon tetrachloride is preferable from the viewpoint of polymerization activity and stereoregularity. R above⁶As an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, and an octyl group; an alkenyl group such as a cyclohexyl group, an allyl group, a propenyl group, and a butenyl group; Aryl groups such as tolyl group and xylyl group; and aralkyl groups such as phenethyl and 3-phenylpropyl group. Among these, an alkyl group having 1 to 10 carbon atoms is particularly preferable.
[0024]
These Mg compounds may be used alone or in combination of two or more. Further, it may be used by being supported on a support such as silica, alumina or polystyrene, or may be used as a mixture with halogen or the like.
(C) electron donor
Electron donors include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, esters of organic or inorganic acids, ethers such as monoethers, diethers or polyethers. And nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate. Among these, esters of polyvalent carboxylic acids are preferable, and esters of aromatic polyvalent carboxylic acids are more preferable. From the viewpoint of polymerization activity, aromatic monocarboxylic acid monoesters and / or diesters are particularly preferred. In addition, an aliphatic hydrocarbon having a linear, branched or cyclic organic group in the ester portion is preferable.
[0025]
Specifically, phthalic acid, naphthalene-1,2-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, 5,6,7,8-tetrahydronaphthalene-1,2-dicarboxylic acid, 5,6,7, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl of dicarboxylic acids such as 8-tetrahydronaphthalene-2,3-dicarboxylic acid, indane-4,5-dicarboxylic acid, indane-5,6-dicarboxylic acid, t-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1-ethylbutyl 2-ethylbutyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, 2-methylhexyl And dialkyl esters such as syl, 3-methylhexyl, 4-methylhexyl, 2-ethylhexyl, 3-ethylhexyl, 4-ethylhexyl, 2-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 3-ethylpentyl, etc. . Of these, phthalic acid diesters are preferred.
[0026]
Specific examples thereof include di-n-butyl phthalate, diisobutyl phthalate, di-n-heptyl phthalate, diethyl phthalate and the like. In addition, these compounds may be used alone or in combination of two or more.
(D) Silicon compound
In the preparation of the solid catalyst component, in addition to the components (a), (b) and (c), the component (d) is optionally added as a general formula (IV)
Si (OR⁷)_qX^Three _4-q  ... (IV)
The silicon compound represented by these can be used. By using a silicon compound, catalytic activity and stereoregularity may be improved and the amount of fine powder in the produced polymer may be reduced.
[0027]
In the above general formula (IV), X^ThreeRepresents a halogen atom, and among these, a chlorine atom and a bromine atom are preferable, and a chlorine atom is particularly preferable. R⁷Is a hydrocarbon group, which may be a saturated or unsaturated group, may be linear, branched or cyclic, and may be sulfur, nitrogen, oxygen , Silicon, phosphorus and other heteroatoms may be included. A hydrocarbon group having 1 to 10 carbon atoms, particularly an alkyl group, alkenyl group, cycloalkenyl group, aryl group and aralkyl group are preferred. -OR⁷When a plurality of are present, they may be the same as or different from each other. R⁷Specific examples of methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-heptyl group, n- Examples include octyl group, n-decyl group, allyl group, butenyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, phenyl group, tolyl group, benzyl group, and phenethyl group. q represents an integer of 0 to 3.
[0028]
Specific examples of the silicon compound represented by the general formula (IV) include silicon tetrachloride, methoxytrichlorosilane, dimethoxydichlorosilane, trimethoxychlorosilane, ethoxytrichlorosilane, diethoxydichlorosilane, triethoxychlorosilane, and propoxytrichlorosilane. , Dipropoxydichlorosilane, tripropoxychlorosilane, and the like. Of these, silicon tetrachloride is particularly preferred. These silicon compounds may be used alone or in combination of two or more.
(B) Organoaluminum compound
The organoaluminum compound (B) used in the present invention is not particularly limited, but an alkyl group, a halogen atom, a hydrogen atom, an alkoxy group-containing compound, an aluminoxane and a mixture thereof can be preferably used. Specifically, trialkylaluminum such as trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, and trioctylaluminum; dialkyl such as diethylaluminum monochloride, diisopropylaluminum monochloride, diisobutylaluminum monochloride, dioctylaluminum monochloride Examples include aluminum monochloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride; chain aluminoxanes such as methylaluminoxane. Among these organoaluminum compounds, trialkylaluminum having a lower alkyl group having 1 to 5 carbon atoms, particularly trimethylaluminum, triethylaluminum, tripropylaluminum and triisobutylaluminum are preferable. In addition, these organoaluminum compounds may be used alone or in combination of two or more.
(C) Electron donating compound as the third component
In this invention, in order to manufacture the said polymer, the electron donating compound as (C) 3rd component is added at the time of superposition | polymerization as needed. As the electron donating compound as the third component (C), an organosilicon compound having a Si—O—C bond, a nitrogen-containing compound, a phosphorus-containing compound, and an oxygen-containing compound can be used. Among these, from the viewpoint of polymerization activity and stereoregularity, it is preferable to use an organosilicon compound having an Si—O—C bond, ethers and esters, and particularly an organosilicon compound having an Si—O—C bond. It is preferable.
[0029]
Specific examples of the organosilicon compound having a Si—O—C bond include tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraisobutoxysilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane. , Ethylisopropyldimethoxysilane, propylisopropyldimethoxysilane, diisopropyldimethoxysilane, diisobutyldimethoxysilane, isopropylisobutyldimethoxysilane, di-t-butyldimethoxysilane, t-butylmethyldimethoxysilane, t-butylethyldimethoxysilane, t-butylpropyl Dimethoxysilane, t-butylisopropyldimethoxysilane, t-butylbutyldimethoxysilane, t-butylisobutyldi Toxisilane, t-butyl (s-butyl) dimethoxysilane, t-butylamyldimethoxysilane, t-butylhexyldimethoxysilane, t-butylheptyldimethoxysilane, t-butyloctyldimethoxysilane, t-butylnonyldimethoxysilane, t- Butyldecyldimethoxysilane, t-butyl (3,3,3-trifluoromethylpropyl) dimethoxysilane, cyclohexylmethyldimethoxysilane, cyclohexylethyldimethoxysilane, cyclohexylpropyldimethoxysilane, cyclopentyl-t-butyldimethoxysilane, cyclohexyl-t- Butyldimethoxysilane, dicyclopentyldimethoxysilane, dicyclohexyldimethoxysilane, bis (2-methylcyclopentyl) dimethoxysilane, bis ( , 3-dimethylcyclopentyl) dimethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, isobutyltrimethoxysilane, t- Butyltrimethoxysilane, s-butyltrimethoxysilane, amyltrimethoxysilane, isoamyltrimethoxysilane, cyclopentyltrimethoxysilane, cyclohexyltrimethoxysilane, norbornanetrimethoxysilane, indenyltrimethoxysilane, 2-methylcyclopentyltrimethoxysilane , Cyclopentyl (t-butoxy) dimethoxysilane, isopropyl (t-butoxy) dimethoxysilane, t-butyl (Isobutoxy) dimethoxysilane, t-butyl (t-butoxy) dimethoxysilane, texyltrimethoxysilane, texylisopropoxydimethoxysilane, texyl (t-butoxy) dimethoxysilane, texylmethyldimethoxysilane, texylethyldimethoxysilane Texyl isopropyl dimethoxy silane, texyl cyclopentyl dimethoxy silane, texyl myristyl dimethoxy silane, texyl cyclohexyl dimethoxy silane and the like. These organosilicon compounds may be used alone or in combination of two or more.
[0030]
Specific examples of nitrogen-containing compounds include 2,6-disubstituted piperidines such as 2,6-diisopropylpiperidine, 2,6-diisopropyl-4-methylpiperidine, N-methyl2,2,6,6-tetramethylpiperidine. 2,5-diisopropyl azolidine such as 2,5-diisopropylazolidine, N-methyl 2,2,5,5-tetramethylazolidine; N, N, N ′, N′-tetramethylmethylenediamine, N , N, N ′, N′-tetraethylmethylenediamine and the like; substituted imidazolidines such as 1,3-dibenzylimidazolidine and 1,3-dibenzyl-2-phenylimidazolidine, and the like.
[0031]
Specific examples of phosphorus-containing compounds include triethyl phosphite, tri n-propyl phosphite, triisopropyl phosphite, tri n-butyl phosphite, triisobutyl phosphite, diethyl n-butyl phosphite, diethyl phenyl phosphite and the like. Phosphites and the like.
Specific examples of the oxygen-containing compound include 2,6-substituted tetrahydrofurans such as 2,2,6,6-tetramethyltetrahydrofuran and 2,2,6,6-tetraethyltetrahydrofuran; 1,1-dimethoxy-2,3 , 4,5-tetrachlorocyclopentadiene, 9,9-dimethoxyfluorene, dimethoxymethane derivatives such as diphenyldimethoxymethane, and the like.
[II] Preparation of solid catalyst component
As the method for preparing the solid catalyst component (A), the above-mentioned (a) titanium compound, (b) magnesium compound, (c) an electron donor, and (d) a silicon compound, if necessary, are subjected to contact temperature conditions. Except for, the contact method may be performed by a normal method, and the contact procedure is not particularly limited. For example, each component may be contacted in the presence of an inert solvent such as a hydrocarbon, or each component may be previously contacted after being diluted with an inert solvent such as a hydrocarbon. Examples of the inert solvent include aliphatic hydrocarbons such as octane, decane, and ethylcyclohexane, alicyclic hydrocarbons, and mixtures thereof.
[0032]
Here, a titanium compound is 0.5-100 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 1-50 mol is used. When this molar ratio deviates from the above range, the catalyst activity may be insufficient. Moreover, said electron donor is 0.01-10 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 0.05-1.0 mol is used. When this molar ratio deviates from the above range, catalyst activity and stereoregularity may be insufficient. Furthermore, when using a silicon compound, it is 0.001-100 mol normally with respect to 1 mol of magnesium of said magnesium compound, Preferably, 0.005-5.0 mol is used. When this molar ratio deviates from the above range, the effect of improving the catalytic activity and stereoregularity may not be sufficiently exhibited, and the amount of fine powder in the produced polymer may increase.
[0033]
Contact of said (a)-(d) component is performed in the temperature range of 120-150 degreeC after adding all the components, Preferably it is 125-140 degreeC. When the contact temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited. The contact is usually performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. In this case, when the solvent is used, the range varies depending on the type, contact temperature, etc., but usually 0-50 kg / cm.²G, preferably 0-10 kg / cm²Perform in G range. Further, during the contact operation, stirring is preferably performed from the viewpoint of contact uniformity and contact efficiency.
[0034]
Further, it is preferable that the titanium compound is contacted twice or more and is sufficiently supported on the magnesium compound that serves as a catalyst carrier.
When a solvent is used in the contact operation, the solvent is usually used in an amount of 5000 ml or less, preferably 10 to 1000 ml, with respect to 1 mole of the titanium compound. If this ratio deviates from the above range, contact uniformity and contact efficiency may deteriorate.
[0035]
The solid catalyst component obtained by the above contact is washed with an inert solvent at a temperature of 100 to 150 ° C, preferably 120 to 140 ° C. When the washing temperature is outside the above range, the effect of improving the catalytic activity and stereoregularity is not sufficiently exhibited. Examples of the inert solvent include aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as methylcyclohexane and ethylcyclohexane, aromatic hydrocarbons such as toluene and xylene, tetrachloroethane, and chlorofluorocarbons. And halogenated hydrocarbons or mixtures thereof. Of these, aliphatic hydrocarbons are preferably used.
[0036]
There are no particular restrictions on the cleaning method, but methods such as decantation and filtration are preferred. Although there is no restriction | limiting in particular about the usage-amount of an inert solvent, washing | cleaning time, and the frequency | count of washing | cleaning, Usually, 100-100000 milliliters with respect to 1 mol of magnesium compounds, Preferably, 1000-50000 milliliters of solvent are used, It is performed for 1 minute to 24 hours, preferably 10 minutes to 6 hours. If this ratio deviates from the above range, cleaning may be incomplete.
[0037]
The range of the pressure at this time varies depending on the type of solvent, the washing temperature, etc., but is usually 0 to 50 kg / cm.²G, preferably 0-10 kg / cm²Perform in G range. Further, during the cleaning operation, it is preferable to perform stirring from the viewpoint of cleaning uniformity and cleaning efficiency.
Furthermore, it is effective to repeat the washing preferably 5 times or more.
[0038]
The obtained solid catalyst component can be stored in a dry state or in an inert solvent such as hydrocarbon.
[III] Polymerization
Although there is no restriction | limiting in particular about the usage-amount of the component of the catalyst in this invention, The solid catalyst component of (A) component is the range of 0.00005-1 mmol normally per liter of reaction volume converted into a titanium atom. The amount of the organoaluminum compound (B) used is such that the aluminum / titanium atomic ratio is usually in the range of 1 to 1000, preferably 10 to 500. When this atomic ratio deviates from the above range, the catalyst activity may be insufficient. When (C) an electron donating compound such as an organosilicon compound is used as the third component, the (C) electron donating compound / (B) organoaluminum compound molar ratio is usually 0.001 to 5.0, The amount is preferably 0.01 to 2.0, more preferably 0.05 to 1.0. If this molar ratio is outside the above range, sufficient catalytic activity and stereoregularity may not be obtained. However, when prepolymerization is performed, it can be further reduced.
[0039]
In the block copolymerization of propylene and ethylene in the present invention, from the viewpoints of polymerization activity, stereoregularity and polymer powder form, first, prepolymerization of propylene may be performed as desired, followed by main polymerization. In this case, propylene is usually 1 in the presence of a catalyst obtained by mixing (A) the solid catalyst component, (B) the organoaluminum compound, and if necessary, (C) the electron donating compound at a predetermined ratio. Normal pressure to 50 kg / cm at temperatures in the range of ~ 100 ° C²Prepolymerization is performed at a pressure of about G, and then propylene and ethylene are main-polymerized in the presence of a catalyst and a prepolymerized product. There is no particular limitation on the polymerization mode in this main polymerization, and any of solution polymerization, slurry polymerization, gas phase polymerization, bulk polymerization, etc. can be applied, and further, both batch polymerization and continuous polymerization can be applied, Two-stage polymerization and multistage polymerization under different conditions are also applicable.
[0040]
In the production method of the block copolymer in the present invention, either a batch method or a continuous method is generally used in which a propylene homopolymerized portion is first prepared and then a copolymerized portion is prepared.
For example, in the case of producing by a continuous method, a propylene homopolymerization part is produced by supplying a raw material propylene gas to a raw material propylene gas and a molecular weight adjusting agent hydrogen gas and a catalyst, controlling the polymerization amount by the polymerization time, and then the latter stage It moves to a polymerization tank, ethylene, hydrogen gas, and a catalyst as needed are further added to raw material propylene gas, a copolymer part can be manufactured, and a block copolymer can be obtained.
[0041]
Furthermore, with respect to the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to 80 kg / cm from the viewpoint of polymerization activity.²G, preferably 2-50 kg / cm²G and the polymerization temperature are appropriately selected in the range of usually 0 to 200 ° C, preferably 30 to 100 ° C. The polymerization time is usually about 5 minutes to 20 hours, preferably about 10 minutes to 10 hours.
[0042]
The molecular weight can be adjusted by adding a chain transfer agent, preferably hydrogen. Further, an inert gas such as nitrogen may be present.
Moreover, about the catalyst component in this invention, after mixing (A) component, (B) component, and (C) component in a predetermined ratio and making it contact, you may introduce | transduce propylene immediately and may superpose | polymerize. Then, after contact, after aging for about 0.2 to 3 hours, polymerization may be carried out by introducing propylene and ethylene. Further, the catalyst component can be supplied in a suspended state in an inert solvent or propylene.
[0043]
In the present invention, the post-treatment after polymerization can be performed by a conventional method. That is, in the gas phase polymerization method, after polymerization, a nitrogen gas stream or the like may be passed through the polymer powder derived from the polymerization vessel in order to remove propylene or ethylene contained therein, If desired, it may be pelletized by an extruder. In this case, a small amount of water, alcohol or the like may be added in order to completely deactivate the catalyst. In the bulk polymerization method, after polymerization, the monomer is completely separated from the polymer derived from the polymerization vessel, and then pelletized.
In the present invention, the case where the nucleating agent (B) is added to the propylene-ethylene block copolymer (A) is preferable because the rigidity of the spool is improved. The addition amount of the nucleating agent (B) is usually 0.01 to 5% by weight, but 0.01 to 1.0% by weight is more preferable because the weight of the spool is reduced. 5% by weight is particularly preferred. Although there is no restriction | limiting in particular as said nucleating agent (B), Specifically, the following nucleating agents are mentioned.
[2] Nucleating agent (B)
The nucleating agent (B) is not particularly limited, but is preferably selected from (1) talc, (2) organophosphate metal salts and (3) sorbitols.
[0044]
(1) Talc is generally Mg_ThreeSi_FourO_Ten(OH)₂It is a phyllosilicate containing the component represented by these. As talc, it is preferable that an average particle diameter is 0.1-15 micrometers.
(2) Examples of the organic phosphate metal salt include metal salts represented by the following general formula (1).
[0045]
[Chemical 1]

[0046]
(Wherein R¹Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R²And R^ThreeEach represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, an aryl group or an aralkyl group. M represents any one of alkali metal, alkaline earth metal, aluminum and zinc. When M is an alkali metal, m represents 0, n represents 1, and when M is an alkaline earth metal or zinc, n represents 1 or 2; when n is 1, m is 1, when n is 2, m is 0, when M is aluminum, m is 1, and n is 2. )
Specific examples of the organic phosphate metal salt include ADK STAB NA-11 and ADK STAB NA-21 (Asahi Denka Co., Ltd.).
[0047]
(3) Examples of sorbitols include benzylidene sorbitols. The benzylidene sorbitols are condensates of aromatic aldehydes and pentahydric or higher polyhydric alcohols. Here, as aromatic aldehydes, benzaldehyde, a benzaldehyde substituted product substituted with 1 to 5 alkyl groups having 1 to 3 carbon atoms, a benzaldehyde substituted product substituted with 1 to 5 halogen atoms, and an alkoxy having 1 to 3 carbon atoms are used. Examples thereof include benzaldehyde-substituted products in which 1 to 5 groups are substituted, and mixtures in any ratio thereof. In addition, examples of the polyhydric alcohol include sugar alcohols such as sorbit and xylit, and a mixture of any ratio thereof. Condensates obtained by condensing them, that is, benzylidene sorbitols, are different in the type and number of each aromatic substituent in benzaldehyde, or the position of the substituent is different from the ortho, meta, and para positions. Non-target benzaldehydes that may be isomers, target benzaldehydes having the same aromatic substituents, and mixtures thereof may be used. For example, the benzylidene group may be one monobenzylidene sorbitol, two dibenzylidene sorbitols, three tribenzylidene sorbitols, or more benzylidene sorbitols. For example, asymmetric benzylidene sorbitols obtained by using a mixture of benzaldehyde and cumylaldehyde as a raw material as benzaldehydes may be used.
[0048]
The polyhydric alcohol as one raw material is not limited to sugar alcohols such as sorbit and xylit and mixtures of any ratio thereof, but also includes sorbite derivatives, xylit derivatives and any mixture of these derivatives.
In the present invention, dibenzylidene sorbitols are preferable as sorbitols, and in particular, the following general formula (2) disclosed in Japanese Patent No. 2631652
[0049]
[Chemical 2]

[0050]
(Where X¹, X²Each represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen atom, and may be the same. m and n are integers of 0 to 5, and p is 0 or 1. )
The dibenzylidene sorbitol represented by these is more preferable. Examples of the alkyl group having 1 to 3 carbon atoms in the general formula (2) include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxy group having 1 to 3 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Examples of the halogen atom include chlorine, fluorine, iodine and bromine.
[0051]
Furthermore, in the present invention, the dibenzylidene sorbitols represented by the general formula (2) are those obtained by adding a specific stabilizer to a purified product obtained by washing with a specific solvent. When used as a nucleating agent, thermal stability is improved, which is preferable. Specific examples of the washing solvent for purifying the dibenzylidene sorbitols include saturated hydrocarbons having 6 to 12 carbon atoms such as n-hexane, cyclohexane, etc. in addition to aliphatic lower alcohols having 1 to 3 carbon atoms. Illustrative of one or more selected from the group consisting of alicyclic hydrocarbons and aromatic hydrocarbons such as toluene, aliphatic lower alcohols such as methanol, ethanol, isopropanol, and acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. Examples thereof include a mixed solvent consisting of one or more selected from the group consisting of ketones.
[0052]
Stabilizers added to purified dibenzylidene sorbitols include alkaline compounds and / or radical inhibitors. Specific examples of alkaline compounds include inorganic alkalis such as sodium hydroxide and potassium hydroxide, citric acid, lactic acid, lactic acid dimer stearate, succinic acid, benzoic acid, stearic acid, hydroxystearic acid, oleic acid, and beheenoic acid. Examples include fatty acid, alkali metal salts such as sodium and potassium of organic acids such as ethylenediaminetetraacetic acid, and alkaline earth metal salts such as calcium and magnesium.
[0053]
Similarly, as the radical inhibitor, bisphenol A, butylhydroxyanisole (also known as BHA), 2,6-di-tert-butylhydroxytoluene (also known as BHT), 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-phenol, 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 2, , 6-di-tert-butyl-p-ethylphenol, 2,4,6-tri-tert-butylphenol, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tris [β- ( 3.5-tert-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanurate, 1,3,5-trimethyl-2,4,6-tris (3.5- -Tert-butyl-4-hydroxybenzyl) benzene, 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 6- (4-hydroxy-3 , 5-Di-tert-butylanilino) -2,4-bisoctyl-thio-1,3,5-triazine, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] Methane (also known as Irganox 10101), n-octadecyl-3- (3,5-di tert-butyl-4-hydroxy phe) propionate, N 2, N′-hexamethylene bis (3,5-di-tert-butyl-4 -Hydroxy-hydrocinnamamide, 3.5-di-tert-butyl-4-hydroxy-benzylphosphonate diethyl ester, 2,2- Phenolic compounds such as polymeric hindered phenols exemplified by o-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (nonylphenyl) phosphite, etc. Phosphorus compounds are exemplified.
[0054]
The above alkaline compound or radical inhibitor is used alone or in combination of two or more, and the amount added to the purified dibenzylidene sorbitol is an alkaline compound and 100 parts by weight of the purified product. What is necessary is just to add 50-10,000 ppm of radical inhibitor in the whole quantity.
Furthermore, in the present invention, as disclosed in JP-A-8-239386, the dibenzylidene sorbitols represented by the general formula (2) have a crystal structure as measured by X-ray diffraction method. Of these, crystals other than hexagonal crystals such as hexagonal crystals and / or cubic crystals are particularly preferred. In hexagonal crystals and cubic crystals, hexagonal crystals have better dispersion rate and dissolution rate in molten polyolefin resin, and are superior in performance as crystal nucleating agents. It may be a mixture of The ratio of the mixture is 19 parts by weight or less, preferably 0.05 to 19 parts by weight, particularly preferably 0.05 parts by weight of crystals other than hexagonal crystals such as cubic crystals with respect to 1 part by weight of hexagonal crystals. -5.7 parts by weight. In the present invention, as described above, preferred dibenzylidene sorbitols for use in the form of a hexagonal crystal alone or in the form of a mixture of a hexagonal crystal and a non-hexagonal crystal such as a cubic crystal as described above, For example, the following compounds are mentioned.
1,3: 2,4-bis (O-3,4-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis (Op-methylbenzylidene) -D-sorbitol, 1,3: 2,4-bis (Op-ethylbenzylidene) -D-sorbitol, 1,3- (O-dimethylbenzylidene) -2,4- (O-benzylidene) -D-sorbitol, 1,3- (O— Benzylidene) -2,4- (O-dimethylbenzylidene) -D-sorbitol, 1,3: 2,4-bis (O-benzylidene) -D-sorbitol, 1,3: 2,4-bis (Op) -Chlorobenzylidene) -D-sorbitol, 1,3- (Op-chlorobenzylidene) -2,4- (OP-methylbenzylidene) -D-sorbitol, and 1,3- (Op-methyl) Benzylidene) -2,4 (O-p-chlorobenzylidene)-D-sorbitol.
[0055]
Specific examples of sorbitols include New Japan Rika (manufactured) Gelall MD, Gelall MD-R (trade name), and the like.
In the present invention, in addition to the component (B), an inorganic or organic filler may be added to the component (A) in order to improve the rigidity of the spool. Examples of the inorganic or organic filler include mica, calcium carbonate, basic magnesium sulfate, calcium titanate whisker, aluminum borate whisker, glass fiber, carbon fiber, and boron fiber. The addition amount is 0.1 to 50 parts by weight, preferably 0.1 to 30 parts by weight.
[0056]
Furthermore, various coupling agents may be added in order to improve the dispersibility of the nucleating agent and the inorganic or organic filler. Examples of the coupling agent include titanate coupling agents, silane coupling agents, saturated or unsaturated fatty acid compounds, fatty acid metal salts, fatty acid esters, and fatty acid amides.
Moreover, you may add various additives as needed. Additives include additives for surface functions such as antistatic agents and antifogging agents, anti-blocking agents, antioxidants, weathering agents, heat stabilizers, neutralizing agents, lubricants, nucleating agents, colorants, inorganic Or an organic filler etc. are mention | raise | lifted. These additives may be used alone or in combination of two or more. For example, examples of the antioxidant include phosphorus antioxidants, phenolic antioxidants, sulfur antioxidants, and the like.
[0057]
As a specific example of phosphorus antioxidant,
Trisnonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, bis ( 2,6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, tetrakis (2,4-di-t -Butylphenyl) -4,4-biphenylene-di-phosphonite, ADK STAB 1178 (Asahi Denka (manufactured by Asahi Denka)), Sumilizer TNP (manufactured by Sumitomo Chemical), JP-135 (manufactured by Johoku Chemical (manufactured)), ADK STAB 2112 (Asahi) Electrification (manufactured)), JPP-2000 (Johoku Chemical (manufactured)), Weston 618 (manufactured by GE (manufactured)) , ADK STAB PEP-24G (Asahi Denka (manufactured)), ADK STAB PEP-36 (Asahi Denka (manufactured)), ADK STAB HP-10 (Asahi Denka (manufactured)), Sandstab P-EPQ (Sand (manufactured)), Phosfight 168 (Ciba-Geigy (made)).
[0058]
As a specific example of a phenolic antioxidant,
2,6-di-t-butyl-4-methylphenol, n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate, tetrakis [methylene-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4,4'-butylidenebis- (3-methyl- 6-t-butylphenol), triethylene glycol-bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-t- Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] unde , Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Yoshinox BHT (Yoshitomi Pharmaceutical Co., Ltd.), Antage BHT (Kawaguchi Chemical Co., Ltd.), Irganox 1076 (Ciba Geigy (produced)), Irganox 1010 (Ciba Geigy (manufactured)), Adeka Stub AO-60 (Asahi Denka (manufactured)), Smither BP-101 (Sumitomo Chemical (manufactured)), Tominox TT (Yoshitomi Pharmaceutical (manufactured)), TTHP (Toray (manufactured)), Iruga Knox 3114 (Ciba-Geigy (manufactured)), Adeka Stub AO-20 (Asahi Denka (manufactured)), Adeka Stub AO-40 (Asahi Denka (manufactured)), Sumilyzer BBM-S (Sumitomo Chemical (manufactured)), Yoshinox BB ( Yoshitomi Pharmaceutical Co., Ltd.), Antage W-300 (Kawaguchi Chemical Co., Ltd.), Irganox 245 (Ciba Geigy Co., Ltd.), Adeka Stub AO 70 (Asahi Denka (Ltd.)), Tominox 917 (Yoshitomi Pharmaceutical (Ltd.)), ADK STAB AO-80 (Asahi Denka (Ltd.)), Sumilizer GA-80 (Sumitomo Chemical (Co., Ltd.)), and the like.
[0059]
As a specific example of the sulfur-based antioxidant,
Dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), Sumilizer TPL (Sumitomo Chemical Co., Ltd.), Yoshinox DLTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix L (Nippon Yushi Co., Ltd.), Sumilizer TPM (Sumitomo Chemical Co., Ltd.), Yoshinox DMTP (Yoshitomi Pharmaceutical Co., Ltd.) Antix M (Nippon Yushi Co., Ltd.), Sumilizer TPS (Sumitomo Chemical Co., Ltd.), Yoshinox DSTP (Yoshitomi Pharmaceutical Co., Ltd.), Antix S (Nippon Yushi Co., Ltd.), ADK STAB AO-412S (Asahi Denka) (Manufactured)), SEENOX 412S (Cipro Kasei (manufactured)), Sumilizer TDP (Sumitomo Chemical (manufactured)) Etc. The.
[0060]
In the present invention, when an antioxidant is used, about 0.001 to 1 part by weight of the antioxidant may be added to the component (A). Thereby, yellowing etc. can be prevented and it is preferable.
[0061]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited at all by the following Examples.
The test methods used in the text and examples are as follows.
(1) Measurement of melt flow rate (MFR)
Measured according to JIS K7210 at 230 ° C. and 2.16 kg load.
(2) Measurement of intrinsic viscosity [η]
According to ASTM D1601, it is taken as a value measured at 135 ° C. by dissolving in decalin.
(3) Measurement of the amount of soluble components in normal temperature xylene
A normal temperature (25 ° C.) xylene-soluble component and an insoluble component were obtained as follows.
(1) Precisely weigh 5 ± 0.05 g of the sample, put it in a 1000 ml eggplant type flask, add 1 ± 0.05 g of BHT (antioxidant), and then add 700 ± 10 ml of rotor and paraxylene. To do.
(2) Next, a condenser is attached to the eggplant-shaped flask, and the sample is dissolved in paraxylene by heating the flask in an oil bath at 140 ± 5 ° C. for 120 ± 30 minutes while operating the rotor. (3) Next, after pouring the contents of the flask into a 1000 ml beaker, the solution in the beaker was allowed to cool to room temperature (25 ° C.) while stirring with a stirrer (8 hours or longer), and then the precipitate was removed. Filter with a wire mesh.
(4) The filtrate is further filtered with a filter paper, and then the filtrate is poured into 2000 ± 100 ml of methanol contained in a 3000 ml beaker, and this liquid is stirred with a stirrer at room temperature (25 ° C.). Leave for more than 2 hours.
(5) Next, the precipitate is filtered with a wire mesh, air-dried for 5 hours or more, and then dried in a vacuum dryer at 100 ± 5 ° C. for 240 to 270 minutes to recover 25 ° C. xylene-soluble components.
(6) On the other hand, the precipitate collected by the wire mesh in (3) above is dissolved again in paraxylene according to the methods (1) and (2) above, and then methanol 2000 ± 100 contained in a 3000 ml beaker. Transfer quickly to milliliters while still hot, stir with a stirrer for more than 2 hours, and leave overnight at room temperature (25 ° C.).
(7) Next, the precipitate is filtered through a wire mesh, air-dried for 5 hours or longer, and then dried in a vacuum dryer at 100 ± 5 ° C. for 240 to 270 minutes to recover 25 ° C. xylene-insoluble components.
[0062]
The content (w) of the soluble component with respect to xylene at 25 ° C. is as follows. If the sample weight is Ag and the weight of the soluble component recovered in the above (5) is Cg,
w (% by weight) = 100 × C / A
The content of the insoluble component is represented by (100-w) wt%.
(4) of room temperature xylene soluble components¹³Measurement of ethylene content by C-NMR
¹³All C-NMR measurements are carried out by the following method.
[0063]
That is, 220 mg of a sample is collected in an NMR sample tube, and 3 ml of 1,2,4-trichlorobenzene / heavy benzene mixed solvent (volume ratio 90/10) is added thereto, and then the cap is capped and uniformly applied at 130 ° C. After dissolution¹³C-NMR measurement is performed under the following measurement conditions.
Device: JNM-EX400 manufactured by JEOL Ltd.
Pulse width: 9μs (45 °)
Pulse repetition time: 4 seconds
Spectral width: 20000Hz
Measurement temperature: 130 ° C
Integration count: 1000-10000 times
Moreover, the ethylene unit content of the soluble component with respect to 25 degreeC xylene and the ethylene unit content of an insoluble component are the values calculated | required with the following method.
[0064]
That is, the sample¹³The C-NMR was measured, and from the seven peak intensities in the 35 to 21 ppm [tetramethylsilane (TMS) chemical shift standard] region in the spectrum, first, the triad chain fraction (mol) of ethylene (E) and propylene (P) %) Is calculated by the following equation.
f_EPE= [K (Tδδ) / T] × 100
f_PPE= [K (Tβδ) / T] × 100
f_EEE= [K (Sγδ) / 4T + K (Sδδ) / 2T] × 100
f_PPP= [K (Tββ) / T] × 100
f_PEE= [K (Sβδ) / T] × 100
f_PEP= [K (Sββ) / T] × 100
However, T = K (Tδδ) + K (Tβδ) + K (Sγδ) / 4 + K (Sδδ) / 2 + K (Tββ) + K (Sβδ) + K (Sββ)
Here, for example, f_EPERepresents the EPEtriad chain fraction (mol%), and K (Tδδ) represents the integrated intensity of the peak attributed to the Tδδ carbon.
[0065]
Next, ethylene unit content (x (weight%)) is calculated by following Formula using the said triad chain fraction.
Ethylene unit content (% by weight) = 28 {3f_EEE+2 (f_PEE+ F_EPE) + F_PPE+ F_PEP} × 100 / [28 {3f_EEE+2 (f_PEE+ F_EPE) + F_PPE+ F_PEP} +42 {3f_PPP+2 (f_PPE+ F_PEP) + F_EPE+_PEE}]
(5) of room temperature xylene insoluble components¹³Measurement of stereoregularity index by C-NMR
The stereoregularity index is a value obtained by the following method.
[0066]
That is, the insoluble component in xylene at 25 ° C¹³In the C-NMR spectrum, the methyl carbon signal splits into nine peaks of mmmm, mmr, rmmr, mmrr, mmrm + rrrmr, rmrm, rrrr, mrrr, mrrm from the low magnetic field to the high magnetic field due to the effect of stereoregularity. Observed. Of these nine, paying attention to the six peaks of mmmm, mmmr, mmrr, mmrm + rrrmr, rrrr, mrrm having strong peak intensity, the stereoregularity index of the insoluble component is calculated by the following equation.
[0067]
Stereoregularity index (%) = L_mmmm× 100 / (L_mmmm+ L_mmmr+ L_mmrr+ L_{mmrm + rrmr}+ L_rrrr+ L_mrrm)
Where L_mmmm, L_mmmr, L_mmrr, L_{mmrm + rrmr}, L_rrrrAnd L_mrrmRespectively¹³It is the height from the baseline of the peak of mmmm, mmmr, mmrr, mmrm + rrrmr, rrrr, and mrrm in the C-NMR spectrum. However, the mmmm peak is composed of a plurality of discrete points with different chemical shifts and peak heights, and the mmmr peak is on the tailing of the mmmm main peak. The height of is corrected according to a conventional method.
(6) T measured by pulse NMR of soluble components at room temperature xylene₁Measurement of relaxation time
T₁Is the time constant for recovery of longitudinal magnetization, and the most common measurement method is the reversal recovery method (180 ° -τ-90 ° pulse method). First, magnetization is applied in the −z ′ direction by a pulse of t = 0 and θ = 180 °, and then the thermal equilibrium value M₀Recovery to begin. When a 90 ° pulse is applied after elapse of τ time, the magnetization rotates in the y′-axis direction, and an FID signal proportional to the magnitude of the magnetization is observed. If τ is continuously changed, a recovery curve of the signal intensity M (τ) can be obtained. Based on Bloch's equation, M (0) = − M₀Depending on the initial conditions, the recovery of longitudinal magnetization is
M = M₀{1-2exp (-τ / T₁)}
It is represented by Furthermore, practically, ln {M (∞) −M (τ)} = ln {2M (∞)} − τ / T₁And the slope of the straight line obtained from the plot of ln {M (∞) −M (τ)} ˜τ is T₁Can be determined.
[0068]
In addition, when performing a series of measurements including repeated experiments of integration, it is necessary to wait until the magnetization returns to the thermal equilibrium state, and at least 5 T₁More waiting time (5T₁Therefore, M (∞) is τ> 5T.₁The M (τ) value for τ that satisfies the above is adopted.
Measurement was carried out under the following conditions using a Bruker pulse NMR apparatus CXP-90.
Measurement nucleus: Hydrogen nucleus
Measurement frequency: 90MHZ
Measurement temperature: 30 ° C
Measurement method: Inversion recovery method (180 ° -τ-90 ° pulse method)
180 °: 180 ° pulse
90 °: 90 ° pulse
τ: Variable time, 90 ° pulse width: 2.3 to 2.4 μsec
(7) Impact resistance measurement
In accordance with JIS K7110, notched Izod impact strength at 23 ° C. and −20 ° C. is measured using an injection molded product.
(8) Measurement of flexural modulus
Based on JIS K7203, a bending elastic modulus is measured using an injection molded product.
(9) Drop test measurement
In the drop test, 20 kg (1 layer, 74 rows, 51 layers) of a solid wire for welding with a wire diameter of 1.2 mm of YGW11 specified in JIS Z3312 was automatically wound up by 25 coils (wire: 500 kg) each. The spool was inspected for breakage by dropping the wire 8 times based on the starting end blind hole. The dropped height was 60 cm at 23 ° C. and 30 cm at −20 ° C. The number of samples was n = 3.
[0069]
As a result, if you drop it 8 times, it will not break ◎ If you drop it 5 times or more and less than 8 times and break it, ○ If you drop it 3 times or more and less than 5 times and destroy it △ Drop it less than 3 times ×
(10) Flange breaking strength
The flange breaking strength was determined by attaching a hook having a width of 30 cm to the flange portion and obtaining a load when the winding drum portion flange portion was broken.
(11) Winding test
A solid wire for welding having a wire diameter of 1.2 mm of YGW11 defined in JIS Z3312 was automatically wound around the spool by 20 kg (1 layer 74 rows, 51 layers), each with 25 coils (wire: 500 kg). The number of defects at the beginning of winding and the number of turbulent windings in the upper layer were examined, and the test examples which were both good were transported on a pallet by 500 km on a truck, and the state of damage to the spool and the state of turbulence of the aligned winding wires were examined.
[Example 1]
(Preparation of polymerization catalyst)
(1) Preparation of catalyst A
(Preparation of solid catalyst component)
4.0 kg of diethoxymagnesium is put into a stainless steel reactor with an internal volume of 80 liters substituted with nitrogen. Further, 20 liters of dehydrated decane was added. The mixture was heated to 40 ° C., 0.6 liters of silicon tetrachloride was added and stirred for 20 minutes, and 0.4 liters of diethyl phthalate was added. The solution was heated to 80 ° C. and subsequently 19.2 liters of titanium tetrachloride was added. The internal temperature was set to 125 ° C. for 2 hours. Then, stirring was stopped, solid was settled, and the supernatant liquid was extracted. 2.6 liters of dehydrated decane was added, and the temperature was raised to 135 ° C. while stirring and held for 1 minute. Then, stirring was stopped, the solid was allowed to settle, and the supernatant was extracted. This washing operation was repeated 7 times. Further, 30.5 liters of titanium tetrachloride was added, the internal temperature was set to 135 ° C., and contacted for 2 hours. Thereafter, washing with dehydrated decane at 135 ° C. was repeated 6 times to obtain a solid catalyst component.
(Preliminary polymerization)
3.8 kg of the solid catalyst component [A] and 32 liters of dehydrated heptane were added to the 80 liter reactor. The mixture was heated to 40 ° C., and 0.16 liter of triethylaluminum and 0.5 liter of dicyclopentyldimethoxysilane were added. This was reacted for 2 hours while continuously supplying propylene gas at 0.12 to 0.18 MPa. Thereafter, the solid component was sufficiently washed with dehydrated heptane to obtain Catalyst A.
(2) Vapor phase polymerization of propylene
The polymer was produced using a 10 liter gas phase continuous polymerization apparatus. That is, the reactor 1 was kept at 85 ° C., propylene pressure of 3.0 MPa, triethylaluminum 4 mmol / kg PP, dicyclopentyldimethoxysilane 0.4 mmol / kg PP, the catalyst A 0.02 mmol / kg PP, hydrogen Gas was continuously supplied at a rate of 650 liters / hour. The reaction tank 2 was kept at 60 ° C., ethylene was continuously supplied at 16.3 kg / hour, hydrogen gas was continuously supplied at 450 liter / hour, and the total pressure was kept at 1.6 MPa. The production amount was 40 kg / hr.
(3) Granulation
The resulting block polypropylene powder has 0.05% by weight of Adeka Stub NA-11 as a nucleating agent, 1000 ppm of calcium stearate as a neutralizing agent, DHT-4A (manufactured by Kyowa Chemical Industry Co., Ltd .: magnesium aluminum hydroxide) Carbonate hydrate) is 500 ppm, and P-EPQ (Asahi Denka Kogyo Co., Ltd .: Tetrakis (2,4-ditertiary butylphenyl 4,4-bisphenylene diphosphonite)) as an antioxidant is 750 ppm, After adding 1500 ppm of Irganox 1010 (manufactured by Ciba Specialty Chemicals Co., Ltd .: phenolic antioxidant) and mixing them well, the mixture was granulated continuously to prepare pellets. Predetermined structural analysis was performed on a part of the pellets by the test method described above, and the remaining pellets were injection-molded to produce various test pieces and measured for physical properties. Table 1 shows the result of the structural analysis and the result of the physical property measurement.
(4) Manufacture of spool
Moreover, the following spool was manufactured with the 500-ton injection molding machine using the obtained pellet.
[0070]
  Each of the spools had a flange outer diameter of 270 mm and a flange thickness of 5 mm at the portion in contact with the body portion and gradually decreased in the outer peripheral direction, and the minimum outer peripheral portion was 3.5 mm. The outer diameter of the fuselage is 148 mm and the thickness is 3.2 mm. The body has a shape that has a locking hole extending in the circumferential direction of the body and opening along the side surface of the flange. A spool test was performed by the above test method, and the results obtained are shown in Table 1.
[Reference example 1]
  Except that the amount of ethylene in the reaction vessel 2 in the gas phase polymerization of propylene in Example 1 was changed to 15.0 kg / hour, and the nucleating agent was changed to 0.4% by weight of talc (average particle size: 7 microns). The same operation as in Example 1 was performed. The obtained results are shown in Table 1.
[Comparative Example 1]
  The same procedure as in Example 1 was carried out except that a spool was produced using Idemitsu Petrochemical (manufactured) polypropylene J-3053H (trade name). The results are shown in Table 1.
[0071]
[Table 1]

[0072]
【The invention's effect】
The spool made of propylene resin of the present invention is excellent in rigidity and impact resistance, and can automatically wind the wire in an aligned winding state, and can prevent breakage and disturbance during transportation.
[Brief description of the drawings]
FIG. 1 shows a spool showing an example of the present invention.
FIG. 2 is a view showing deformation of a locking hole when a wire is fixed in a conventional PP resin spool. (A), (b) is a figure which shows a mode that the wire front end bending part protruded from the latching hole.
FIG. 3 is a view showing the spread of a flange portion when a wire is wound in a conventional spool made of PP resin.
FIG. 4 is a view showing a state of a locking hole when a wire is fixed in the spool of the present invention. (A), (b) is a figure which shows a mode that the wire tip bending part is being fixed to the locking hole.
[Explanation of symbols]
1: Torso
2: Flange
3: Locking hole
4: Wire

Claims (4)

To the propylene-ethylene block copolymer (A) having the properties shown in the following (a), (b) and (c), 0.01 to 1.0% by weight of the organophosphate metal salt (B) is added. Propylene resin spool.
(A) Melt flow rate (MFR) (230 ° C., 2.16 kg load) is 0.01 to 1000 g / 10 minutes,
(B) The stereoregularity index [mmmm] fraction measured by ¹³ C-NMR of the room temperature xylene-insoluble component is 98.9% or more,
(C) The room temperature xylene-soluble component satisfies the following (c1), (c2) and (c3) (c1) occupies 3 to 50% by weight (c2) Single T ₁ relaxation time component measured by pulse NMR (C3) The ethylene content measured by ¹³ C-NMR is x wt%, and the T ₁ relaxation time y (millisecond) measured by pulse NMR satisfies the following relational expression: y ≦ 0.0014x ^{3 -0.0897x 2 -1.0593x + 231.6 ··· (} I)   The propylene resin spool according to claim 1, wherein the propylene-ethylene block copolymer (A) has a melt flow rate (MFR) (230 ° C, 2.16 kg load) of 0.3 to 300 g / 10 min.   The spool made of propylene resin according to claim 1 or 2, wherein a normal temperature xylene-soluble component of the propylene-ethylene block copolymer (A) is 11.5 to 50% by weight.   The spool made of propylene resin according to any one of claims 1 to 3, wherein the ethylene content of the normal temperature xylene-soluble component of the propylene-ethylene block copolymer (A) is 37.2 to 40.5 wt%.

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