JP3564492B2 - Polyolefin resin composition - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明は剛性、成形収縮率および耐衝撃性のバランスが優れたポリオレフィン樹脂組成物に関する。
【０００２】
【従来の技術】
プロピレンホモポリマーから成るポリプロピレン樹脂は比較的に安価で、その優れた特性の為にこれまで多岐の分野に渡り使用されている。しかし、一般にプロピレンホモポリマーから成るポリプロピレン樹脂は高い剛性を有する反面、耐衝撃性が劣るという課題が残っていた。プロピレンホモポリマーから成るポリプロピレン樹脂の耐衝撃性を向上させる為にこれまで多くの提案がなされてきている。例えば、まず最初にプロピレンホモポリマー成分を生成し、その後にエチレン−プロピレンランダム共重合体成分を導入する製造方法を用いたプロピレン系ブロック共重合体から成るポリプロピレン樹脂、または、プロピレンホモポリマーまたはプロピレン系ブロック共重合体にエチレン−プロピレン−ラバー（ＥＰＲ）を添加した組成物から成るポリプロピレン樹脂等が提案がなされてきている。該ポリプロピレン樹脂はプロピレンホモポリマーから成るポリプロピレン樹脂に比べて耐衝撃性が優れているが、剛性が劣り、更に成形収縮率が大きい等の課題が残る。該課題を改善させる方法としては特開平０３−０５３９７９号公報に示される様に該ポリプロピレン樹脂にタルクを添加した組成物よりなるポリプロピレン樹脂の提案がなされてきているが、剛性および成形収縮率は向上するものの耐衝撃性が著しく低下するという課題が残り、剛性、成形収縮率及び耐衝撃性の向上を同時に図ることは困難であった。
【０００３】
【発明が解決しようとする課題】
本発明者らは前記の課題を解決することを目的に鋭意検討を行った結果、チタン含有固体触媒成分と有機アルミニウム化合物との組み合わせからなる立体規則性触媒を用いて得られるプロピレン系ブロック共重合体において、エチレン−プロピレン共重合体のコポリマー成分のエチレン含有量およびその極限粘度をある一定の範囲に制御し、更にタルクの粒径および添加量をも制御することにより剛性および成形収縮率に優れると共に０℃以上の温度においての耐衝撃性に優れたポリオレフィン樹脂組成物を発明するに至った。本発明はプロピレン系ブロック共重合体にタルクを添加した系において剛性、成形収縮率および０℃以上の温度において耐衝撃性も向上するポリオレフィン樹脂組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明のポリオレフィン樹脂組成物は、
（１）プロピレンホモポリマー成分ならびに極限粘度（［η］ＲＣ）が１．０〜２．５ｄｌ／ｇおよびエチレン含量が２５〜６０重量％のエチレン−プロピレンコポリマー成分から成るプロピレン系ブロック共重合体１００重量部、ならびに平均粒子径が５μｍ以下の超微粒子タルク３〜４０重量部から成るポリオレフィン樹脂組成物。
【０００５】
（２）前記１項記載のプロピレン系ブロック共重合体がエチレン−プロピレンコポリマー成分が１５〜６０重量％から成る前記１項記載のポリオレフィン樹脂組成物。
【０００６】
（３）前記１項記載のプロピレン系ブロック共重合体のメルトフローレートが０．１〜１００ｇ／１０分である前記１項のポリオレフィン樹脂組成物。
【０００７】
（４）前記１項記載のプロピレンホモポリマー成分がアイソタクチックペンタット分率が０．９５以上である前記１項記載のポリオレフィン樹脂組成物。
【０００８】
（５）前記１項記載のエチレン−プロピレンコポリマー成分が気相重合で製造された前記１項記載のポリオレフィン樹脂組成物。
【０００９】
（６）前記１項記載のプロピレン系ブロック共重合体がチタン含有固体触媒成分（Ａ）と一般式ＡｌＲ１ ＭＲ２ ＮＸ３−（Ｍ＋Ｎ）（式中Ｒ１およびＲ２は炭化水素基またはアルコール基を示し、Ｘはハロゲンを示し、ＭおよびＮは０＜Ｍ＋Ｎ≦３の任意の数を表す。）で表される有機アルミニウム化合物（Ｂ）と必要に応じて用いられる一般式Ｒ３ ＸＲ４ ＹＳｉ（ＯＲ５）Ｚ（式中Ｒ３ Ｘ、Ｒ５は炭化水素基、Ｒ４は炭化水素基あるいはヘテロ原子を含む炭化水素基を示し、Ｘ＋Ｙ＋Ｚ＝４、０≦Ｘ≦２、１≦Ｙ≦３、１≦Ｚ≦３である）で表される有機ケイ素化合物（Ｃ）とを組み合わせた立体規則性触媒を用いて製造された前記１項記載のポリオレフィン樹脂組成物。
【００１０】
（７）前記６項記載のチタン含有個体触媒成分（Ａ）がマグネシウム化合物およびシリカにチタン化合物を担時したものであることを特徴とする前記６項記載のポリオレフィン樹脂組成物。
【００１１】
本発明を以下詳細に説明する。
本発明に用いるプロピレン系ブロック共重合体は、プロピレンホモポリマー成分ならびに極限粘度（［η］ＲＣ）が１．０〜２．５ｄｌ／ｇ、より好ましくは得られるポリオレフィン樹脂組成物の剛性、耐衝撃性の点で１．３〜２．５ｄｌ／ｇおよびエチレン含量が２５〜６０重量％、より好ましくは得られるポリオレフィン樹脂組成物の剛性、耐衝撃性の点で３０〜５５重量％のエチレン−プロピレンコポリマー成分から成るプロピレン系ブロック共重合体である。更に得られるポリオレフィン樹脂組成物の剛性、耐衝撃性の点でプロピレンホモポリマー成分４０〜８５重量％及びエチレン−プロピレンコポリマー成分１５〜６０重量％から成るプロピレン系ブロック共重合体が好ましい。又、得られるポリオレフィン樹脂組成物の耐衝撃性、成形時の成形性の点で該プロピレン系ブロック共重合体のメルトフローレートが０．１〜１００ｇ／１０分が好ましく、０．５〜７０ｇ／１０分が更に好ましい。
該極限粘度は、下記式（１）より求めらる。
【００１２】
【式１】
即ち、本発明に用いるプロピレン系ブロック共重合体の製造を、結晶性のプロピレンホモポリマー成分をまず生成し、続いてエチレン−プロピレンコポリマー成分を生成する製造方法を用いた場合、該プロピレンホモポリマー成分を生成した時点で該プロピレンホモポリマー成分の極限粘度（［η］ＰＰ）は直接測定できるが、続いて生成される該プロピレン−エチレンコポリマー成分の極限粘度（［η］ＲＣ）は直接測定することは困難である。そこで、得られる該プロピレン系ブロック共重合体の極限粘度（［η］ＷＨＯＬＥ）から、該プロピレンホモポリマー成分の重量分率に極限粘度［η］ＰＰをかけた積を引いて、この値をコポリマー成分の分率で割り、該エチレン−プロピレンコポリマー成分の極限粘度［η］ＲＣが求められる。
【００１４】
式中、エチレン−プロピレンコポリマー成分の分率（ＷＲＣ／１００）は従来より知られている赤外線分析法などで求めることができる。
【００１５】
更に、剛性に優れる成型品が得られる点で、プロピレンホモポリマー成分がアイソペンタット分率が０．９５以上である該プロピレン系ブロック共重合体を用いる事が好ましい。アイソタクチックペンタット分率は、分子内立体規則性の指標であり、ＮＭＲにより測定することが例示できる。
【００１６】
本発明に用いるプロピレン系ブロック共重合体は、いかなる方法によって得えることができる。例えば、チタン担持触媒を用いて重合した本発明で規定した極限粘度およびエチレン含量を有するエチレン−プロピレンランダム共重合体をプロピレンホモポリマーに添加しする方法が例示できる。しかし、該方法はエチレン−プロピレンランダム共重合体の製造コストが高い。
【００１７】
また、プロピレンホモポリマー成分及びエチレン−プロピレンコポリマー成分を連続的に重合する方法も例示でき、該方法は製造コストが低く、該プロピレンホモポリマー成分中に該エチレン−プロピレンコポリマー成分が均一に分散し品質（剛性、耐衝撃性、寸法安定性）の安定化が図れている点でより好ましい。
【００１８】
以下に該連続的に重合する方法を詳細に説明する。
本発明に用いるプロピレン系ブロック共重合体のプロピレンホモポリマー成分の重合はチタン含有固体触媒等を用いてスラリー重合法、塊状重合法や気相重合法のいずれの方法でもよいが、後段のエチレン−プロピレンコポリマー成分の重合方法は気相重合法が好ましい。気相重合方法はエチレン−プロピレンコポリマー成分が溶液中に溶出する等の問題が発生せず、安定運転の継続が容易であるためである。
【００１９】
重合条件は重合形式で異なるが、気相重合法の場合、一定量のパウダーを混合攪拌しながらチタン含有触媒成分、有機アルミニウム成分および有機ケイ素化合物を重合温度２０〜１２０℃、好ましくは４０〜１００℃の条件下、重合圧力大気圧〜１０ＭＰａ、好ましくは０．５〜５ＭＰａの条件下で供給してプロピレンホモポリマー成分を重合する。プロピレンホモポリマー成分の分子量の調節は重合時に水素のような分子量調節剤を加えると効果的である。プロピレンホモポリマー成分を重合後、生成したパウダーの一部を抜き出し、極限粘度の測定および触媒単位当たりの重合収量を求めるのに供する。プロピレンホモポリマー成分の重合に引き続いてエチレン−プロピレンコポリマー成分を重合温度２０〜１２０℃、好ましくは４０〜１００℃の条件下、重合圧力大気圧〜１０ＭＰａ、好ましくは０．５〜５ＭＰａの条件下で重合することによりプロピレン系ランダム共重合体が生成される。エチレン−プロピレンコポリマー成分中のエチレン含量はコモノマーガス中のエチレンモノマーとプロピレンモノマーのガスモル比をコントロールすることにより、エチレン−プロピレンコポリマー成分中のエチレン含量が２５〜６０ｗｔ％になるように調節される。さらに、コポリマー成分の分子量はコポリマー成分の極限粘度が本発明の要件を満たすように水素のような分子量調節剤をコポリマー重合時に加えて調節される。重合は、回分式、半連続式または連続式のいずれでもよいが、工業的には連続式重合が好ましい。
【００２０】
本重合の終了後には、重合系からモノマーを除去させて粒子状ポリマーを得ることができる。得られたポリマーは極限粘度の測定、エチレン含量の測定、メルトフローレートの測定および触媒単位重量当たりの重合収量を求めるのに供される。
【００２１】
本発明のプロピレン系ブロック共重合体の製造で用いられるチタン含有固体触媒成分（Ａ）はオレフィン重合で用いられることが公知のチタン化合物ならどの様なものでも使用できる。例えば、マグネシウム化合物、シリカおよびアルミナ等の無機担体やポリスチレン等の有機担体にチタン化合物を担時したもの、また必要に応じてエーテル類、エステル類の電子供与化合物を担時したものなら公知のどの様なものでも使用できる。例えば、特開昭６２−１０４８１０、特開昭６２ー１０４８１１、特開昭６２−１０４８１２等に記載のマグネシウム化合物にＴｉＣｌ４を担時した、チタン、マグネシウム、ハロゲンおよび電子供与体を必須成分とするチタン含有担時型触媒成分が用いられる。また、マグネシウム化合物ーアルコール溶液をスプレーし、該固体成分を部分乾燥し、しかる後該乾燥固体触媒成分をハロゲン化チタンおよび電子供与性化合物で処理してなるチタン含有固体触媒成分（特開平３ー１１９００３）が挙げられる。また、マグネシウム化合物をテトラヒドロフラン／アルコール／電子供与性に溶解させ、ＴｉＣｌ４単独または電子供与体の組み合わせで析出させたマグネシウム担体をハロゲン化チタンおよび電子供与性化合物で処理してなるチタン含有固体触媒成分（特開平４ー１０３６０４）が挙げられる。 また、特開昭４７ー３４４７８、特開昭５２ー３５２８３等に記載のα、βまたはγー三塩化チタンも挙げられる。より好ましくはマグネシウム化合物、シリカおよびアルミナ等の無機担体やポリスチレン等の有機担体にチタン化合物を担時したもの、また必要に応じてエーテル類、エステル類の電子供与化合物を担時したものである。
【００２２】
本発明のプロピレン系ブロック共重合体の製造に用いられる有機アルミニウム化合物（Ｂ）としては、一般式ＡｌＲ１ ＭＲ２ ＮＸ３−（Ｍ＋Ｎ）（式中Ｒ１およびＲ２は炭化水素基またはアルコール基を示し、Ｘはハロゲンを示し、ＭおよびＮは０＜Ｍ＋Ｎ≦３の任意の数を表す。）で表される有機アルミニウム化合物を用いることができる。
【００２３】
具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリーｎープロピルアルミニウム、トリーｎーブチルアルミニウム、トリーｉーブチルアルミニウム、ジメチルアルミニウムクロライド、ジエチルアルミニウムクロライド、メチルアルミニウムセスキクロライド、エチルアルミニウムジクロリド、ヂエチルアルミニウムアイオダイド、エトキシジエチルアルミニウム等を挙げることができる。
【００２４】
これら有機アルミニウム化合物は単独あるいは２種類以上を混合して使用することができる。
本発明のプロピレン系ブロック共重合体の製造において必要に応じて用いられる有機ケイ素化合物（Ｃ）としては、一般式Ｒ３ ＸＲ４ ＹＳｉ（ＯＲ５）Ｚ（式中Ｒ３ Ｘ、Ｒ５は炭化水素基、Ｒ４は炭化水素基あるいはヘテロ原子を含む炭化水素基を示し、Ｘ＋Ｙ＋Ｚ＝４、０≦Ｘ≦２、１≦Ｙ≦３、１≦Ｚ≦３である）で表される有機ケイ素化合物が使用できる。
【００２５】
具体的にはメチルトリメトキシシラン、ｔ−ブチルトリメトキシシラン、ｔ−ブチルトリエトキシシラン、フェニルトリエトキシシラン、メチルエチルジメトキシシラン、メチルフェニルジエトキシシラン、ジメチルジメトキシシラン、ジエチルジエトキシシラン、ジイソプロピルジメトキシシラン、ジイソブチルジメトキシシラン、ジーｔ−ブチルジメトキシシラン、ジフェニルジメトキシシラン、トリメチルメトキシシラン、トリメチルエトキシシラン等を挙げることができる。好ましくは、ジイソブチルジメトキシシラン、ジイソプロピルジメトキシシラン、ジーｔ−ブチルジメトキシシランおよびジフェニルジメトキシシランである。
これらの有機ケイ素化合物は単独あるいは２種類以上を混合して使用することができる。
【００２６】
本発明に用いる超微粒子タルクは、得られるポリオレフィン樹脂組成物の耐衝撃性及び剛性の点で平均粒子径が５μｍ以下あり、好ましくは平均粒子径が３μｍ以下の超微粒子タルクである。
【００２７】
上記の該平均粒子径および該粒子径は島津製作所（株）製ＳＡ−ＣＰ２−２０型を用い、遠心沈降法により測定した。
本発明のポリオレフィン樹脂組成物は、耐衝撃性、剛性、外観の点で本発明に用いるプロピレン系ブロック共重合体１００重量部及び本発明に用いる超微粒子タルク３〜４０重量部からなり、好ましくは該プロピレン系ブロック共重合体１００重量部及び該超微粒子タルク５〜３５重量部である。
【００２８】
本発明のポリオレフィン樹脂組成物は、射出成形、押出し成形など各種成形法により種々の形状を有する成形品にすることができる。成形に際しては、本発明のポリオレフィン樹脂組成物に、必要に応じて従来のポリオレフィンに用いられている公知の酸化防止剤、中和剤、帯電防止剤、耐候剤、造核剤、顔料等を添加することができる。
【００２９】
【実施例】
以下、本発明を実施例および比較例を挙げて説明するが、本発明はこれらの実施例に限定されるものではない。
実施例および比較例において用いた測定方法について以下説明する。
【００３０】
極限粘度は、本発明の場合には、１３５℃の温度条件下、溶媒としてテトラリン（テトラクロロナフタレン）を用い、三井東圧社製自動粘度測定装置ＡＶＳ２型を使用して求めた。（単位 ｄｌ／ｇ）
【００３１】
アイソタクチックペンタット分率はｍａｃｒｏｍｏｌｅｃｕｌｅｓ ８６８７（１９７５）に基づいて測定した。Ｃ１２−ＮＭＲを使用して、ポリプロピレン分子鎖中のペンタット単位でのアイソタクチックペンタット分率である。
【００３２】
剛性は、実施例、比較例で成形した試験片の曲げ弾性率と標準試験片の曲げ弾性率の差（ΔＦＭ）を剛性の指標とした。曲げ弾性率はＪＩＳ Ｋ７２０３に準じて測定した。
【００３３】
耐衝撃性は、実施例、比較例で成形した試験片のアイゾット衝撃値と標準試験片のアイゾット衝撃値の差（ΔＩＩ）を耐衝撃性の指標とした。又、標準品、実施例共に破断しない場合はＮＢを記した。アイゾット衝撃値はＪＩＳ Ｋ６７５８に準じて、０℃、２３℃の条件で測定した。（単位 Ｊ／ｍ）
【００３４】
メルトフローレートはＪＩＳ Ｋ６７１０に準じて、２３０℃の条件で測定した。（単位 ｇ／１０分）（以下ＭＦＲと略称することがある。）
【００３５】
成形収縮率は成形機の金型の全長から上記条件で調整した引っ張り試験片（ＪＩＳ Ｋ７１１３引っ張り試験片）の全長の長さを減じた長さと金型の長さの比を１００倍した下記式（２）より求めた。
【００３６】
【式２】
標準試験片の作成は、各実施例、比較例それぞれに用いる後述の表１に示したプロピレン系ブロック共重合体９９．８重量％、フェノール系酸化防止剤０．１重量％及びステアリン酸カルシウム０．１重量％を配合し高速攪拌式混合機（註、ヘンシェルミキサー、商品名）で室温下に１０分混合し、その後スクリュー口径４０ｍｍの押し出し造粒機を用いて造粒し、ペレット状の組成物を得た。ついで、該組成物を射出成形機で溶融樹脂温度２３０℃、金型温度５０℃でＪＩＳ型の試験片を成形し、湿度５０％、室温２３℃の条件下で７２時間状態調整し、各評価に用いた。
【００３８】
（実施例１〜８、比較例１〜４）
後述の表１に示したプロピレン系ブロック共重合体、タルク、フェノール系酸化防止剤及びステアリン酸カルシウムを表１に示す配合率で配合し高速攪拌式混合機（註、ヘンシェルミキサー、商品名）で室温下に１０分混合し、その後スクリュー口径４０ｍｍの押し出し造粒機を用いて造粒し、ペレット状の組成物を得た。ついで、該組成物を射出成形機で溶融樹脂温度２３０℃、金型温度５０℃でＪＩＳ型の試験片を成形し、湿度５０％、室温２３℃の条件下で７２時間状態調整し、各評価に用いた。
【００３９】
実施例１〜８は成形収縮率が小さく、剛性及び耐衝撃性も標準試験片より優れる値を示しているのに対し、比較例１〜４は成形収縮率が大きく、耐衝撃性が優れない。
【００４０】
【表１】
【発明の効果】
本発明のポリオレフィン樹脂組成物は剛性、成形収縮率および耐衝撃性が優れた成形品が得られるため、工業用部品、家電用部品、自動車用部品用等の材料として極めて有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a polyolefin resin composition having an excellent balance between rigidity, molding shrinkage and impact resistance.
[0002]
[Prior art]
Polypropylene resins composed of propylene homopolymer are relatively inexpensive and have been used in a wide variety of fields because of their excellent properties. However, while a polypropylene resin composed of a propylene homopolymer generally has high rigidity, there remains a problem that the impact resistance is poor. Many proposals have been made to improve the impact resistance of a polypropylene resin composed of a propylene homopolymer. For example, a propylene homopolymer component is first produced, and then a polypropylene resin comprising a propylene-based block copolymer using a production method of introducing an ethylene-propylene random copolymer component, or a propylene homopolymer or a propylene-based Proposals have been made for a polypropylene resin or the like made of a composition obtained by adding ethylene-propylene-rubber (EPR) to a block copolymer. The polypropylene resin is superior in impact resistance to a polypropylene resin composed of a propylene homopolymer, but has problems such as poor rigidity and a large molding shrinkage. As a method for solving this problem, a polypropylene resin comprising a composition obtained by adding talc to the polypropylene resin has been proposed as disclosed in JP-A-03-053979, but the rigidity and molding shrinkage are improved. However, there remains a problem that the impact resistance is significantly reduced, and it has been difficult to simultaneously improve rigidity, molding shrinkage, and impact resistance.
[0003]
[Problems to be solved by the invention]
The present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, have found that a propylene-based block copolymer obtained using a stereoregular catalyst comprising a combination of a titanium-containing solid catalyst component and an organoaluminum compound is obtained. In the coalescence, the ethylene content of the copolymer component of the ethylene-propylene copolymer and its intrinsic viscosity are controlled within a certain range, and the talc particle size and the amount added are also controlled to thereby provide excellent rigidity and molding shrinkage. In addition, the inventors have invented a polyolefin resin composition having excellent impact resistance at a temperature of 0 ° C. or higher. An object of the present invention is to provide a polyolefin resin composition in which rigidity, molding shrinkage and impact resistance at a temperature of 0 ° C. or more are improved in a system in which talc is added to a propylene-based block copolymer.
[0004]
[Means for Solving the Problems]
The polyolefin resin composition of the present invention,
(1) A propylene homopolymer component and a propylene-based block copolymer 100 comprising an ethylene-propylene copolymer component having an intrinsic viscosity ([η] RC ) of 1.0 to 2.5 dl / g and an ethylene content of 25 to 60% by weight. A polyolefin resin composition comprising parts by weight and 3 to 40 parts by weight of ultrafine talc having an average particle diameter of 5 μm or less.
[0005]
(2) The polyolefin resin composition according to (1), wherein the propylene-based block copolymer according to (1) comprises 15 to 60% by weight of an ethylene-propylene copolymer component.
[0006]
(3) The polyolefin resin composition according to (1), wherein the propylene-based block copolymer according to (1) has a melt flow rate of 0.1 to 100 g / 10 minutes.
[0007]
(4) The polyolefin resin composition according to (1), wherein the propylene homopolymer component according to (1) has an isotactic pentat fraction of 0.95 or more.
[0008]
(5) The polyolefin resin composition according to (1), wherein the ethylene-propylene copolymer component according to (1) is produced by gas phase polymerization.
[0009]
(6) the formula AlR 1 propylene block copolymer of 1 wherein the titanium-containing solid catalyst component (A) M R 2 N X 3- (M + N) ( wherein R 1 and R 2 is a hydrocarbon group Or an alcohol group, X represents a halogen, and M and N each represent an arbitrary number of 0 <M + N ≦ 3.) And an organic aluminum compound (B) represented by the general formula R 3 used if necessary. X R 4 Y Si (oR 5 ) Z ( wherein R 3 X, R 5 is a hydrocarbon group, R 4 represents a hydrocarbon group containing a hydrocarbon group or a hetero atom, X + Y + Z = 4,0 ≦ X ≦ 2 2. The polyolefin resin composition according to claim 1, which is produced using a stereoregular catalyst in combination with an organosilicon compound (C) represented by the formula: 1 ≦ Y ≦ 3, 1 ≦ Z ≦ 3.
[0010]
(7) The polyolefin resin composition according to (6), wherein the titanium-containing solid catalyst component (A) according to (6) is a magnesium compound and silica supporting a titanium compound.
[0011]
The present invention will be described in detail below.
The propylene-based block copolymer used in the present invention has a propylene homopolymer component and an intrinsic viscosity ([η] RC ) of 1.0 to 2.5 dl / g, more preferably the rigidity and impact resistance of the obtained polyolefin resin composition. Ethylene-propylene having 1.3 to 2.5 dl / g in terms of properties and ethylene content of 25 to 60% by weight, more preferably 30 to 55% by weight in terms of rigidity and impact resistance of the obtained polyolefin resin composition. It is a propylene-based block copolymer composed of a copolymer component. Further, a propylene block copolymer composed of 40 to 85% by weight of a propylene homopolymer component and 15 to 60% by weight of an ethylene-propylene copolymer component is preferable in terms of rigidity and impact resistance of the obtained polyolefin resin composition. Further, the melt flow rate of the propylene-based block copolymer is preferably from 0.1 to 100 g / 10 minutes, and from 0.5 to 70 g / m in terms of impact resistance of the obtained polyolefin resin composition and moldability at the time of molding. 10 minutes is more preferred.
The intrinsic viscosity is determined by the following equation (1).
[0012]
(Equation 1)
That is, when the production method of the propylene-based block copolymer used in the present invention is such that a crystalline propylene homopolymer component is first produced and then an ethylene-propylene copolymer component is produced, the propylene homopolymer component is produced. Although the intrinsic viscosity ([η] PP ) of the propylene homopolymer component can be directly measured at the time when the propylene homopolymer is produced, the intrinsic viscosity ([η] RC ) of the subsequently produced propylene-ethylene copolymer component must be directly measured. It is difficult. Therefore, the product of the intrinsic viscosity [η] PP and the weight fraction of the propylene homopolymer component is subtracted from the intrinsic viscosity ([η ] WHOLE ) of the obtained propylene-based block copolymer, and this value is calculated as the copolymer. The intrinsic viscosity [η] RC of the ethylene-propylene copolymer component is determined by dividing by the fraction of the component.
[0014]
In the formula, the fraction ( WRC / 100) of the ethylene-propylene copolymer component can be determined by a conventionally known infrared analysis method or the like.
[0015]
Further, from the viewpoint that a molded article having excellent rigidity can be obtained, it is preferable to use the propylene-based block copolymer in which the propylene homopolymer component has an isopentat fraction of 0.95 or more. The isotactic pentat fraction is an index of intramolecular stereoregularity, and can be exemplified by measurement by NMR.
[0016]
The propylene-based block copolymer used in the present invention can be obtained by any method. For example, a method of adding an ethylene-propylene random copolymer having an intrinsic viscosity and an ethylene content defined in the present invention, which is polymerized by using a titanium-supported catalyst, to a propylene homopolymer can be exemplified. However, this method has a high production cost for an ethylene-propylene random copolymer.
[0017]
Also, a method of continuously polymerizing a propylene homopolymer component and an ethylene-propylene copolymer component can be exemplified. This method has a low production cost, and the ethylene-propylene copolymer component is uniformly dispersed in the propylene homopolymer component. (Rigidity, impact resistance, dimensional stability) are more preferable because they can be stabilized.
[0018]
Hereinafter, the method of continuous polymerization will be described in detail.
Polymerization of the propylene homopolymer component of the propylene-based block copolymer used in the present invention may be any of a slurry polymerization method, a bulk polymerization method and a gas phase polymerization method using a titanium-containing solid catalyst or the like. The polymerization method of the propylene copolymer component is preferably a gas phase polymerization method. This is because the gas phase polymerization method does not cause a problem such as elution of the ethylene-propylene copolymer component into the solution, and facilitates continuation of stable operation.
[0019]
The polymerization conditions differ depending on the polymerization mode. In the case of the gas phase polymerization method, a titanium-containing catalyst component, an organoaluminum component and an organosilicon compound are polymerized at a polymerization temperature of 20 to 120 ° C., preferably 40 to 100 while mixing and stirring a fixed amount of powder. The propylene homopolymer component is polymerized by supplying at a temperature of 10 ° C. under a polymerization pressure of atmospheric pressure to 10 MPa, preferably 0.5 to 5 MPa. The molecular weight of the propylene homopolymer component is effectively adjusted by adding a molecular weight modifier such as hydrogen during polymerization. After polymerization of the propylene homopolymer component, a part of the produced powder is extracted and used for measuring the intrinsic viscosity and determining the polymerization yield per catalyst unit. Subsequent to the polymerization of the propylene homopolymer component, the ethylene-propylene copolymer component is polymerized at a polymerization temperature of 20 to 120 ° C, preferably 40 to 100 ° C, under a polymerization pressure of atmospheric pressure to 10 MPa, preferably 0.5 to 5 MPa. Polymerization produces a propylene-based random copolymer. The ethylene content in the ethylene-propylene copolymer component is adjusted by controlling the gas molar ratio of the ethylene monomer and the propylene monomer in the comonomer gas so that the ethylene content in the ethylene-propylene copolymer component becomes 25 to 60 wt%. Further, the molecular weight of the copolymer component is adjusted by adding a molecular weight modifier such as hydrogen during copolymerization so that the intrinsic viscosity of the copolymer component meets the requirements of the present invention. The polymerization may be of a batch type, a semi-continuous type or a continuous type, but industrially, a continuous type polymerization is preferred.
[0020]
After completion of the main polymerization, the monomer can be removed from the polymerization system to obtain a particulate polymer. The resulting polymer is used to determine the intrinsic viscosity, the ethylene content, the melt flow rate, and the polymerization yield per unit weight of the catalyst.
[0021]
As the titanium-containing solid catalyst component (A) used in the production of the propylene-based block copolymer of the present invention, any titanium compound known to be used in olefin polymerization can be used. For example, a magnesium compound, an inorganic carrier such as silica and alumina or an organic carrier such as polystyrene carrying a titanium compound, or, if necessary, ethers and esters, and any known carrier provided with an electron donating compound such as an ester. Anything can be used. For example, titanium, magnesium, halogen, and an electron donor, in which TiCl 4 is supported on a magnesium compound described in JP-A-62-104810, JP-A-62-104811, and JP-A-62-104812, are essential components. A titanium-containing supported catalyst component is used. Also, a magnesium compound-alcohol solution is sprayed, the solid component is partially dried, and then the dried solid catalyst component is treated with a titanium halide and an electron donating compound to obtain a titanium-containing solid catalyst component (JP-A-3-119003). ). Further, a magnesium-containing solid catalyst component obtained by dissolving a magnesium compound in tetrahydrofuran / alcohol / electron-donating property and treating a magnesium carrier precipitated with TiCl4 alone or in combination with an electron donor with a titanium halide and an electron-donating compound ( JP-A-4-103604). Also, α, β or γ-titanium trichloride described in JP-A-47-34478, JP-A-52-35283 and the like can be mentioned. More preferably, a titanium compound is supported on an inorganic carrier such as a magnesium compound, silica and alumina, or an organic carrier such as polystyrene, and, if necessary, an electron-donating compound such as ethers or esters is supported.
[0022]
As the organoaluminum compound used for the production of the propylene block copolymer of the present invention (B), the general formula AlR 1 M R 2 N X 3- (M + N) ( wherein R 1 and R 2 is a hydrocarbon group or X represents an alcohol group, X represents a halogen, and M and N each represent an arbitrary number of 0 <M + N ≦ 3.) Can be used.
[0023]
Specifically, trimethyl aluminum, triethyl aluminum, tree n-propyl aluminum, tree n-butyl aluminum, tree i-butyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum sesquichloride, ethyl aluminum dichloride, and diethyl aluminum ion Dyed, ethoxydiethylaluminum and the like can be mentioned.
[0024]
These organoaluminum compounds can be used alone or in combination of two or more.
The propylene block copolymer organosilicon compound optionally used in the preparation of the present invention (C), the general formula R 3 X R 4 Y Si ( OR 5) Z ( wherein R 3 X, R 5 Represents a hydrocarbon group, R 4 represents a hydrocarbon group or a hydrocarbon group containing a hetero atom, and is represented by X + Y + Z = 4, 0 ≦ X ≦ 2, 1 ≦ Y ≦ 3, 1 ≦ Z ≦ 3) Organosilicon compounds can be used.
[0025]
Specifically, methyltrimethoxysilane, t-butyltrimethoxysilane, t-butyltriethoxysilane, phenyltriethoxysilane, methylethyldimethoxysilane, methylphenyldiethoxysilane, dimethyldimethoxysilane, diethyldiethoxysilane, diisopropyldimethoxysilane Examples thereof include silane, diisobutyldimethoxysilane, di-tert-butyldimethoxysilane, diphenyldimethoxysilane, trimethylmethoxysilane, and trimethylethoxysilane. Preferred are diisobutyldimethoxysilane, diisopropyldimethoxysilane, di-tert-butyldimethoxysilane and diphenyldimethoxysilane.
These organosilicon compounds can be used alone or in combination of two or more.
[0026]
The ultrafine talc used in the present invention is an ultrafine talc having an average particle diameter of 5 μm or less, preferably 3 μm or less, in terms of impact resistance and rigidity of the obtained polyolefin resin composition.
[0027]
The above average particle diameter and the particle diameter were measured by a centrifugal sedimentation method using SA-CP2-20 manufactured by Shimadzu Corporation.
The polyolefin resin composition of the present invention comprises 100 parts by weight of a propylene block copolymer used in the present invention and 3 to 40 parts by weight of ultrafine talc used in the present invention in terms of impact resistance, rigidity, and appearance, and is preferably used. 100 parts by weight of the propylene-based block copolymer and 5 to 35 parts by weight of the ultrafine talc.
[0028]
The polyolefin resin composition of the present invention can be formed into molded articles having various shapes by various molding methods such as injection molding and extrusion molding. During molding, a known antioxidant, a neutralizing agent, an antistatic agent, a weathering agent, a nucleating agent, a pigment, and the like used in conventional polyolefins are added to the polyolefin resin composition of the present invention as needed. can do.
[0029]
【Example】
Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
The measurement methods used in the examples and comparative examples will be described below.
[0030]
In the case of the present invention, the intrinsic viscosity was determined under the temperature condition of 135 ° C. using tetralin (tetrachloronaphthalene) as a solvent and using an automatic viscosity meter AVS2 manufactured by Mitsui Toatsu. (Unit dl / g)
[0031]
The isotactic pentat fraction was measured based on macromolecules 8687 (1975). The isotactic pentat fraction in pentat units in the polypropylene molecular chain using C 12 -NMR.
[0032]
For the rigidity, the difference (ΔFM) between the flexural modulus of the test specimen formed in the example and the comparative example and the flexural modulus of the standard test specimen was used as an index of the rigidity. The flexural modulus was measured according to JIS K7203.
[0033]
For the impact resistance, the difference (ΔII) between the Izod impact value of the test piece molded in each of the examples and the comparative examples and the Izod impact value of the standard test piece was used as an index of the impact resistance. In addition, when neither the standard product nor the embodiment was broken, NB was described. The Izod impact value was measured at 0 ° C. and 23 ° C. according to JIS K6758. (Unit J / m)
[0034]
The melt flow rate was measured at 230 ° C. according to JIS K6710. (Unit: g / 10 minutes) (hereinafter sometimes abbreviated as MFR)
[0035]
The molding shrinkage is obtained by subtracting the total length of the tensile test piece (JIS K7113 tensile test piece) adjusted from the total length of the mold of the molding machine under the above conditions from the total length, and multiplying the ratio of the mold length by 100 by the following formula. (2) Determined from:
[0036]
[Equation 2]
The standard test piece was prepared by using 99.8% by weight of a propylene-based block copolymer, 0.1% by weight of a phenolic antioxidant, and 0.1% by weight of calcium stearate shown in Table 1 below, which are used in each of Examples and Comparative Examples. 1% by weight and mixed at room temperature for 10 minutes with a high-speed stirring mixer (Note: Henschel mixer, trade name), and then granulated using an extrusion granulator with a screw diameter of 40 mm to obtain a pellet-shaped composition. Got. Then, a JIS-type test piece was molded from the composition using an injection molding machine at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C., and the state was adjusted for 72 hours under the conditions of 50% humidity and 23 ° C. room temperature. It was used for.
[0038]
(Examples 1 to 8, Comparative Examples 1 to 4)
The propylene block copolymer, talc, phenolic antioxidant, and calcium stearate shown in Table 1 below are blended at the blending ratio shown in Table 1, and mixed with a high-speed stirring mixer (Note, Henschel mixer, trade name) at room temperature. The mixture was mixed for 10 minutes below, and then granulated using an extrusion granulator having a screw diameter of 40 mm to obtain a pellet-shaped composition. Then, a JIS-type test piece was molded from the composition using an injection molding machine at a molten resin temperature of 230 ° C. and a mold temperature of 50 ° C., and the state was adjusted for 72 hours under the conditions of 50% humidity and 23 ° C. room temperature. It was used for.
[0039]
Examples 1 to 8 have a small molding shrinkage, and the stiffness and impact resistance also show values superior to the standard test pieces, whereas Comparative Examples 1 to 4 have a large molding shrinkage and poor impact resistance. .
[0040]
[Table 1]
【The invention's effect】
Since the polyolefin resin composition of the present invention can provide a molded article having excellent rigidity, molding shrinkage and impact resistance, it is extremely useful as a material for industrial parts, home electric parts, automobile parts and the like.
Claims (7)
Priority Applications (1)
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|---|---|---|---|
| JP26208395A JP3564492B2 (en) | 1995-09-13 | 1995-09-13 | Polyolefin resin composition |
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| Application Number | Priority Date | Filing Date | Title |
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| JP26208395A JP3564492B2 (en) | 1995-09-13 | 1995-09-13 | Polyolefin resin composition |
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| JP3934734B2 (en) * | 1997-04-18 | 2007-06-20 | 三甲株式会社 | Injection molded product made of polypropylene resin |
| JP4532084B2 (en) * | 2003-08-21 | 2010-08-25 | サンアロマー株式会社 | Method for producing polypropylene resin composition |
| JP2005125775A (en) * | 2003-09-30 | 2005-05-19 | Dainippon Ink & Chem Inc | Laminate sheet for molding |
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