JP2004182955A - Propylene resin composition and use of the same - Google Patents

Propylene resin composition and use of the same Download PDF

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JP2004182955A
JP2004182955A JP2002355220A JP2002355220A JP2004182955A JP 2004182955 A JP2004182955 A JP 2004182955A JP 2002355220 A JP2002355220 A JP 2002355220A JP 2002355220 A JP2002355220 A JP 2002355220A JP 2004182955 A JP2004182955 A JP 2004182955A
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resin composition
ethylene
propylene
cap
weight
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Isao Wada
功 和田
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Mitsui Chemicals Inc
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Mitsui Chemicals Inc
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Priority to JP2002355220A priority Critical patent/JP2004182955A/en
Priority to KR1020030083906A priority patent/KR100619484B1/en
Priority to CNB2003101182210A priority patent/CN1249158C/en
Publication of JP2004182955A publication Critical patent/JP2004182955A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D41/00—Caps, e.g. crown caps or crown seals, i.e. members having parts arranged for engagement with the external periphery of a neck or wall defining a pouring opening or discharge aperture; Protective cap-like covers for closure members, e.g. decorative covers of metal foil or paper
    • B65D41/02—Caps or cap-like covers without lines of weakness, tearing strips, tags, or like opening or removal devices
    • B65D41/04—Threaded or like caps or cap-like covers secured by rotation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Closures For Containers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition having excellent rigidity, impact resistance, and moldability, exhibiting tremendously excellent cap closing and opening properties, when formed into a cap, and having high sliding properties, and to provide a molded product of the same. <P>SOLUTION: This polypropylene resin composition comprises (A) an ethylene-propylene block copolymer in an amount of 85-95 pts.wt. and (B) a high-density polyethylene in an amount of 5-15 pts.wt., wherein the ethylene-propylene block copolymer (A) has a melt flow rate of 2-20 g/10 min, a homogeneous part stereoregularity of ≥0.960, and a total ethylene content of 6-12 wt%, and the high-density polyethylene (B) has a melt flow rate of 30-60 g/10 min at 190°C and a density of 0.957-0.966 g/cm<SP>3</SP>. The resin cap is obtained by subjecting the resin composition to compression molding. When a nucleating agent, such as a metal salt of an organic phosphate ester, is added to the composition, its effect is more improved, and all of quality requirements as the cap are satisfied. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【０００１】
【発明の属する技術分野】
本発明は、プロピレン樹脂組成物およびその組成物からなる容器用キャップに関する。更に詳しくは、剛性と耐衝撃性、成形性に優れ、且つキャップとした時のクロージング性、開栓性が飛躍的に優れ、かつ高い摺動性を有する樹脂組成物、およびその成形体を提供することに関する。
【０００２】
【発明の技術的背景】
一般にプロピレン樹脂は化学的特性および物理的特性に優れ、しかも、優れた成形加工性を有するため、食品容器、医療容器、キャップ、自動車部品等の成形品製造に幅広く利用されている。これら用途向けの樹脂では、剛性、耐衝撃性、成形加工性が共に高いことが望ましいが、すべての性能を一律に目標レベルに合わせることは難しかった。
【０００３】
また、プロピレン樹脂成形品を最も生産性の高い圧縮成形（コンプレッション成形）する際、製造ラインでのキャップネジ部の無理抜き（ネジ部を回して抜くのではなく、無理やり引き抜く工程）におけるネジ不具合や削れによって生じるダストが品質上悪い影響を与える。高密度ポリエチレン樹脂は摺動性が高く開栓トルクは低いが、高温充填される飲料には耐熱性即ち変形に伴う密閉性の問題があり使用できない。また、近年のいたずらに対する防止対策、身体能力低下に伴うキャップ開栓力の低下によって、キャップに求められる性能が一定トルクに至るまでのキャップの締り角度が大きく且つ開栓時に生じるトルク即ち開栓力は低いキャップが近年要望されており、耐熱性を含めたこれら全てを満足するキャップは存在しない。
【０００４】
そこでこれらの問題を改良するために、プロピレン樹脂にステアリルアミドやエルシルアミド等の滑剤と総称される脂肪酸アミドや、帯電防止剤と総称される脂肪酸モノグリセライド、脂肪酸モノエタノールアミン、脂肪酸ジエタノールアミン、脂肪酸ジエタノールアミド、脂肪酸アルコール等の化合物を配合し、動摩擦係数の低下を図り、ネジ不具合やダスト削減を行っているが、キャップの締り角度及び開栓トルクは要求される高密度ポリエチレン並には至っておらず、更なる改良の為に多量の滑剤を添加する事は内容物の臭気に悪い影響を与えてしまう。
【０００５】
【発明が解決しようとする課題】
本発明は、従来技術に伴う前記の問題点全てを解決しようとするものであって、剛性と耐衝撃性、成形性に優れ、且つキャップとした時のクロージング性、開栓性が飛躍的に優れ、かつ高い摺動性、耐熱性を有する樹脂組成物、およびその成形体を提供することを目的としている。
【０００６】
【課題を解決するための手段】
すなわち本発明は、（Ａ）２３０℃におけるメルトフローレートが２〜２０（ｇ／１０分）でホモ部立体規則性が０．９６０以上で且つ全エチレン含有量が６〜１２（重量％）であるエチレン−プロピレンブロック共重合体８５〜９５重量部と、（Ｂ）１９０℃におけるメルトフローレートが３０〜６０（ｇ／１０分）、密度０．９５７〜０．９６６（ｇ／ｃｍ３）である高密度ポリエチレン５〜１５重量部とからなることを特徴とするプロピレン樹脂組成物および該樹脂組成物を配合して圧縮成形された樹脂キャップに関する。
【０００７】
また本発明は、前記のプロピレン樹脂組成物にさらに造核剤を、（Ａ）エチレン−プロピレンブロック共重合体１００重量部に対して、０．０５〜０．３重量部を配合したプロピレン樹脂組成物に関し、その造核剤としては、有機リン酸エステル金属塩であることが好ましい。
【０００８】
また本発明は、前記の樹脂組成物に、１９０℃におけるメルトフローレートが５〜５０（ｇ／１０分）、密度が０．９５７〜０．９６６（ｇ／ｃｍ３）である高密度ポリエチレン１０〜８０重量％を含有する顔料マスターバッチをブレンドしたプロピレン樹脂組成物に関する。
【０００９】
さらに本発明は、前記のいずれかのプロピレン樹脂組成物から圧縮成形してなることを特徴とする樹脂キャップに関する。
【００１０】
【発明の具体的説明】
次に本発明を詳細に説明する。本発明に係わるプロピレン樹脂組成物は、（Ａ）エチレン−プロピレンブロック共重合体、（Ｂ）高密度ポリエチレン（Ｃ）造核剤とからなっている。
【００１１】
（Ａ）エチレン−プロピレンブロック共重合体
エチレン−プロピレンブロック共重合体は、ポリプロピレンセグメントとエチレン・プロピレン共重合体セグメントとから基本的に構成された重合体であって、必要に応じてさらにポリエチレンセグメントが共存していてもよい。ポリプロピレンセグメントは結晶性であって、主にブロック共重合体の剛性等の機械強度付与に寄与している。エチレン・プロピレン共重合体セグメントはゴム的な性質を有しており、ブロック共重合体のゴム部分を形成し、耐衝撃性の付与に寄与している。
【００１２】
ブロック共重合体中に占めるポリプロピレンセグメントは、８０〜９５、好ましくは８６〜９１重量％であって、エチレン・プロピレン共重合体セグメントは５〜２０、好ましくは９〜１４重量％であって、この範囲にあると樹脂組成物の諸機械的な物性向上に適している。必要に応じて共存するポリエチレンセグメントは、０〜１０重量％の範囲が好ましい。
【００１３】
また、ブロック共重合体中のエチレン含有量は、６〜１２、好ましくは６〜９（重量％）であって、この範囲にあると樹脂組成物の耐衝撃性に適している。ブロック共重合体のメルトフローレート（ＭＦＲ）は、ＡＳＴＭ Ｄ−１２３８に準拠して２３０℃、２．１６ｋｇ荷重下で測定した値が、２〜２０、好ましくは６〜１１（ｇ／１０分）であって、この範囲にあると樹脂組成物の剛性と耐衝撃性、成形温度に由来する高生産速度に適した樹脂組成物を与える。
【００１４】
このようなブロック共重合体は、オレフィンの立体規則性重合触媒の存在下に、プロピレンの単独重合、次いでプロピレンとエチレンとの共重合、必要に応じてエチレンの単独重合を行う、いわゆる多段重合法を採用することによって製造することができる。また、プロピレン単独重合体、プロピレンとエチレンとの共重合体、必要に応じてエチレン単独重合体を機械的に溶融混練りすることによっても製造することができる。
【００１５】
（Ｂ）高密度ポリエチレン
（Ｂ）成分となる高密度ポリエチレンの重合体は、エチレン単独重合体が好ましいが、必要に応じ、エチレンと全モノマー単位の０．５モル％以下、好ましくは０．２モル％以下、特に好ましくは０．１モル％以下の他のα−オレフィンとを共重合させた重合体である。他のα−オレフィンの例としては、エチレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、３−メチル−１−ペンテン、１−ヘプテン、１−オクテン、１−デセン等を挙げることができるが、ポリエチレンの密度（ＡＳＴＭ Ｄ１５０５）として０．９５７〜０．９６６（ｇ／ｃｍ３）である事。
【００１６】
高密度ポリエチレンは、そのメルトフローレート（ＭＦＲ）をＡＳＴＭ Ｄ−１２３８に準拠し１９０℃、２．１６ｋｇ荷重下で測定した値が、３０〜６０、好ましくは３５〜４５（ｇ／１０分）である。この範囲内にあると、樹脂組成物の機械強度を犠牲にすることなく、且つエチレン−プロピレンブロック共重合体とバラス効果を発現し、成形加工性及びキャップ性能を高めることができ、かつ摺動性をも高めることができる。このような高密度ポリエチレン、オレフィンの立体規則性重合触媒を用い、分子量調整を図りつつエチレンおよび必要に応じて他のα−オレフィンを共存させて重合することによって、製造することができる。
【００１７】
造核剤
本発明に係わるプロピレン樹脂組成物には、必要に応じて造核剤（以下の説明では単に核剤とも云う）を添加配合することができる。使用できる造核剤としては、（ａ）ｐ−ｔｅｒｔ−ブチル安息香酸アルミニウム等のカルボン酸金属塩、（ｂ）ジベンジリデンソルビトール、ビス（４−メチルベンジリデン）ソルビトール等の多価アルコール誘導体、（ｃ）ナトリウム−２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート等の有機リン酸エステル金属塩、（ｄ）分岐状オレフィン、例えば３−メチル−１−ブテン、３，３−ジメチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、３−メチル−１−ペンテン等の単独重合体または共重合体等のポリマー核剤、等々を挙げることができる。
【００１８】
これらの中でも有機リン酸エステル金属塩が好ましく、その添加によってプロピレン樹脂組成物の剛性と耐衝撃性との良好なバランスを図り、かつ優れた摺動性を付与することができる。有機リン酸エステル金属塩として、（１）式で表されるナトリウム−２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ホスフェート、（２）式で表されるアルミニウム化合物等を例示することができる。特に、（１）式で表される化合物の効果が高い。
【００１９】
【化１】

Figure 2004182955
ここで、ｔ−Ｂｕは、ｔｅｒｔ−ブチル基を示す。
【００２０】
【化２】
Figure 2004182955
【００２１】
（２）式において、Ｒ１およびＲ２は、各々独立して水素原子またはアルキル基である。アルキル基としては、メチル、エチル、プロピル、イソプロピル、ブチル、イソブチル、ｔｅｒｔ−ブチル、アミル、ｔｅｒｔ−アミル、ヘキシル、ヘプチル、オクチル、ノニル、２−エチルヘキシル等の基を例示することができる。Ｘはアルキレン基であって、メチレン、エチレン、プロピレン基等を挙げることができる。
【００２２】
具体的には、Ｘがメチレン基であって、Ｒ１がｔｅｒｔ−ブチル基、Ｒ２がメチル基の化合物、またＸがメチレン基であって、Ｒ１およびＲ２がｔｅｒｔ−ブチル基の化合物、さらにＸがメチレン基であって、Ｒ１およびＲ２がｔｅｒｔ−アミル基の化合物を例示することができる。
【００２３】
プロピレン樹脂組成物
本発明に係わる樹脂組成物は、（Ａ）エチレン−プロピレンブロック共重合体が８５〜９５、好ましくは９０〜９５重量部、（Ｂ）高密度ポリエチレンが５〜１５、好ましくは５〜１０重量部とからなっている。この範囲内であると、製品であるキャップの寸法を現行金型で現行寸法のままにすることができ、且つキャップとした時のクロージング性、開栓性が飛躍的に優れ、かつ高い摺動性を有する樹脂組成物となる。
【００２４】
さらに本発明では、（Ａ）エチレン−プロピレンブロック共重合体１００重量部に対して、造核剤を０．０５〜０．３、好ましくは０．０７〜０．３、さらに好ましくは０．１〜０．３重量部配合することができる。この範囲内であると、プロピレン樹脂組成物の剛性と耐衝撃性、結晶化速度向上による生産性と更なる耐熱性向上といった全てのバランスに優れた組成物を得ることができる。
【００２５】
プロピレン樹脂組成物には、必要に応じてフェノール系、リン系、あるいはチオエーテル系の酸化防止剤、中和剤、光安定剤、耐候性安定剤、難燃剤、顔料、染料、ステアリルアミドやエルシルアミド等の滑剤、充填剤等の添加剤を、本発明の目的を阻害しない範囲で配合することができる。
【００２６】
本発明に係わる樹脂組成物は、（Ａ）エチレン−プロピレンブロック共重合体、および（Ｂ）高密度ポリエチレン、必要に応じて造核剤、その他の添加剤を前記した配合量範囲で、ヘンシェルミキサー、Ｖ−ブレンダー、リボンブレンダー、タンブラーブレンダーなどの混合機を用いて混合した後、一軸押出機、二軸押出機、ニーダー、バンバリーミキサーなどで溶融混練りすることによって、均一組成の組成物を得ることができる。
【００２７】
成形体
前記したプロピレン樹脂組成物に必要に応じ顔料マスターバッチをブレンドし、これを射出成形により、各種の成形品を製造することができるが、キャップにおいて最も生産性の高い圧縮成形が特に好ましい。使用される顔料マスターバッチの顔料成分としては、無機顔料または有機顔料系のマスターバッチのいずれも使用することができる。前者としては各種金属の酸化物、硫化物、硫酸塩、後者はフタロシアニン系、キナクリドン系、ベンジジン系、クロモフタル系、ペリレン系の化合物が挙げられる。上記の顔料成分は、２３０℃におけるメルトフローレートが１０〜１００（ｇ／１０分）、好ましくは３０〜７０（ｇ／１０分）、密度が０．９５７〜０．９６６（ｇ／ｃｍ３）、好ましくは０．９６０ 〜０．９６６（ｇ／ｃｍ３）の高密度ポリエチレン１０〜８０重量％から成る顔料マスターバッチとして通常使用される。本発明では、前記のプロピレン樹脂組成物〔（Ａ）＋（Ｂ）〕に対して、前記マスターバッチを２〜１０重量部、好ましくは４〜９重量部配合することができる。この範囲内であると、プロピレン樹脂組成物の剛性と耐衝撃性、結晶化速度向上による生産性に悪影響も与えず、顔料マスターバッチのコストとのバランスに優れた組成物を得ることができる。成形品は、剛性と耐衝撃性とのバランスに優れており、食品分野、医療分野などのキャップとしての広範囲の産業分野で利用することができる。
【００２８】
特に、食品容器およびそのキャップ、具体的にはＰＥＴボトルキャップへの利用に適しており、高い摺動性を有していることから、内容物の充填工程や充填体の包装工程等の最終商品の製造ラインで円滑に移動、輸送することができる。
【００２９】
【実施例】
次に実施例を通して本発明を説明するが、本発明はそれ等実施例に限定されるものではない。まず実施例および比較例で用いた樹脂および添加剤について説明する。
【００３０】
（Ａ）エチレン−プロピレンブロック共重合体；エチレン含有量 ７ｗｔ％で、メルトフローレート（ＡＳＴＭ Ｄ−１２３８、２３０℃、２．１６ｋｇ荷重）が８（ｇ／１０分）、ホモ部立体規則性は１３Ｃ−ＮＭＲによる測定で０．９７１。
（Ｂ）高密度ポリエチレン；密度（ＡＳＴＭ Ｄ１５０５）０．９６３（ｇ／ｃｍ３）、メルトフローレート（ＡＳＴＭ Ｄ−１２３８，１９０℃、２．１６ｋｇ荷重）が４０（ｇ／１０分）。
【００３１】
（Ｃ）エチレン−プロピレンブロック共重合体：エチレン含有量７ｗｔ％でメルトフローレート（ＡＳＴＭ Ｄ−１２３８、２３０℃、２．１６ｋｇ荷重）が８（ｇ／１０分）、ホモ部立体規則性は１３Ｃ−ＮＭＲによる測定で０．９５５。
（Ｄ）高密度エチレン単独重合体密度（ＡＳＴＭ Ｄ−１５０５）が０．９６３（ｇ／ｃｍ３）、メルトフローレート（ＡＳＴＭＤ−１２３８、１９０℃、２．１６ｋｇ荷重）が５（ｇ／１０分）。
【００３２】
（Ｅ）フェノール系酸化防止剤；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（Ｆ）リン系酸化防止剤；トリス（２，４−ジ−ｔｅｒｔ−ブチルフェノール）フォスファイト（Ｇ）中和剤；ステアリン酸カルシウム（Ｈ）中和剤；ハイドロタルサイト。
【００３３】
（Ｉ）造核剤リン酸２，２−メチレンビス（４，６−ジ−ｔｅｒｔ−ブチルフェニル）ナトリウム（Ｊ）顔料マスターバッチ；顔料としては白を用いた。マスターバッチの組成は、酸化チタンが９ｗｔ％、エルシルアミドを９ｗｔ％、１９０℃でのＭＦＲが４０（ｇ／１０ｍｉｎ）で密度が０．９６３（ｇ／ｃｍ３）の高密度ポリエチレン８２ｗｔ％を含有。
【００３４】
（実施例１〜３）前記した樹脂および添加剤を表１記載の配合割合（重量部）で準備し、その後ヘンシェルミキサー中で均一混合した。次いで、日本製鋼所製ＣＩＭ−５０高速二軸押出機を用いて、樹脂温度２００℃にて溶融混練し、その混練物を押出してペレットを得た。このペレットで結晶化速度、曲げ，アイゾット試験においては（Ｊ）白色顔料マスターバッチをブレンドして射出成形を行い試験片作成した。キャップは、実際の締り角度、開栓トルクをもとめるため、（Ｊ）白色顔料マスターバッチをブレンドして圧縮成形により、樹脂温度２００℃、金型温度２０℃の条件で、キャップを作製した。
【００３５】
このペレット及びキャップを用いて、次の方法で、各種物性を調べた。
（ａ）メルトフローレート（ＭＦＲ）；ＡＳＴＭ Ｄ−１２３８、２３０℃、２．１６ｋｇ荷重、単位は（ｇ／１０分）。
（ｂ）結晶化速度は、ＤＳＣによって測定。方法は２４０℃で６分溶融し、プレスフィルムを厚み２７０μｍにして作成。これを５ｍｇ取りだし、２３０℃１０分溶融し、５００℃／ｍｉｎの速度で温度を１３５℃まで下げ、結晶飽和となる半分の時間、いわゆるｔ１／２（半結晶化時間）をもとめた。単位は分。
（ｃ）曲げ初期弾性率；２３℃にて、ＡＳＴＭ Ｄ−７９０に準じて行った。単位は、（ＭＰａ）。
（ｄ）アイゾット衝撃強度；ノッチ付きの試験片を用い、２３℃にて、ＡＳＴＭ Ｄ−２５６に準じて行った。単位は、（Ｊ／ｍ）。
【００３６】
（ｅ）締り角度：現行ＰＥＴボトルキャップ型において締付けトルク２３ｋｇｆ・ｍに到達するまでの角度をもとめた。単位は度。
（ｆ）開栓トルク；１回転２秒の速度でキャップをまわし、開栓時に生じるトルクをもとめた。単位はｋｇｆ・ｍである。
【００３７】
（比較例１〜５）表１に記載した樹脂および添加剤を用いた以外は実施例１と同様に行い、ペレットおよび試験片を得た。その後、物性試験を行い、その結果を表１に併せて記した。
【００３８】
実施例１および２は、締り角度が比較例１よりも大きくクロージング性が増している。また、開栓トルクは比較例１の１５ｋｇｆ・ｍに比べ、実施例１で１２ｋｇｆ・ｍ、実施例２で１１ｋｇｆ・ｍと遙かに低下しており、易開栓性に優れている。
【００３９】
比較例２では締り角度及び開栓トルクはいいが、結晶化速度が遅いため、高速成形時のネジの捲れという不具合が発生した。
【００４０】
比較例３では、高密度ポリエチレンの表面層への配列（バラス効果）が不充分な為、締り角度及び開栓トルクが改善されない。
【００４１】
表１から明らかなように、実施例１，２で得られた樹脂組成物は、比較例１〜３と比べて、キャップとした時の必要物性を満足し、且つ高速生産性を更に改良できる組成物であることがわかる。
【００４２】
【表１】
Figure 2004182955
【発明の効果】
本発明では、具体例として、ホモ部立体規則性が０．９６０以上で且つ２３０℃でのＭＦＲが８ｇ／１０ｍｉｎのエチレン−プロピレンブロック共重合体に２３０℃でのＭＦＲが６０且つ高密度のポリエチレンを配合したことにより、圧力勾配下における分子量差によって生じるバラス効果でポリエチレン樹脂が表面近傍に存在し、クロージング性と同時に易開栓性、開栓トルク低減を達成し、且つポリプロピレン本来の持つ耐熱性を阻害することなく、剛性と耐衝撃性も兼ね備えた新規性の高い樹脂組成物を得ることができた。
【００４３】
また、造核剤は通常樹脂の透明性を高めたり、時には剛性を高めるために配合されているが、本発明の樹脂組成物では、剛性と耐衝撃性との優れたバランスを実現すると共に、本発明の高立体規則性ポリプロピレンを用いることにより、飛躍的に結晶化速度すなわち生産性向上を大きく改善する事ができた。この事により、生産時のネジ不具合を解消する事ができた。
【００４４】
従って、本樹脂組成物から得られた圧縮成形キャップは、剛性と耐衝撃性、耐熱性、クロージング性、易開栓性が求められる飲料キャップの用途に適しており、現在、キャップに要求されている全ての要求を満たした初の発明であり非常に有用である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a propylene resin composition and a container cap made of the composition. More specifically, the present invention provides a resin composition having excellent rigidity, impact resistance, moldability, remarkably excellent closing and opening properties when used as a cap, and high slidability, and a molded article thereof. About doing.
[0002]
TECHNICAL BACKGROUND OF THE INVENTION
In general, propylene resin has excellent chemical and physical properties and excellent moldability, and is therefore widely used in the production of molded articles such as food containers, medical containers, caps, and automobile parts. It is desirable that resins for these applications have high rigidity, high impact resistance, and high moldability, but it has been difficult to uniformly adjust all performances to target levels.
[0003]
In addition, when the most productive compression molding (compression molding) of a propylene resin molded product is performed, the screw failure in the forcible removal of the cap screw part in the production line (the process of forcibly pulling out instead of turning the screw part and pulling it out) Dust generated by shaving has a bad influence on quality. High-density polyethylene resin has high slidability and low opening torque, but high-temperature filled beverages cannot be used due to the problem of heat resistance, that is, hermeticity due to deformation. In addition, due to recent preventive measures against tampering and a decrease in cap opening force due to a decrease in physical ability, the tightening angle of the cap until the required performance of the cap reaches a certain torque is large, and the torque generated when opening the cap, that is, the opening force. In recent years, low caps have been demanded, and there is no cap that satisfies all of these requirements including heat resistance.
[0004]
Therefore, in order to improve these problems, fatty acid amides generally referred to as lubricants such as stearyl amide and erucyl amide in propylene resin, fatty acid monoglycerides generally referred to as antistatic agents, fatty acid monoethanolamine, fatty acid diethanolamine, fatty acid diethanolamide, Compounds such as fatty acid alcohols are blended to reduce the coefficient of kinetic friction and reduce screw failure and dust.However, the tightening angle and opening torque of the cap are not as high as required high-density polyethylene. The addition of a large amount of lubricant for further improvement will adversely affect the odor of the contents.
[0005]
[Problems to be solved by the invention]
The present invention is intended to solve all of the above problems associated with the prior art, and is excellent in rigidity and impact resistance, excellent in moldability, and has a remarkable improvement in closing and opening properties when used as a cap. It is an object of the present invention to provide an excellent resin composition having high slidability and heat resistance, and a molded product thereof.
[0006]
[Means for Solving the Problems]
That is, the present invention relates to (A) a polymer having a melt flow rate at 230 ° C. of 2 to 20 (g / 10 minutes), a homotactic stereoregularity of 0.960 or more, and a total ethylene content of 6 to 12 (% by weight). 85 to 95 parts by weight of a certain ethylene-propylene block copolymer, (B) a melt flow rate at 190 ° C. of 30 to 60 (g / 10 minutes), and a density of 0.957 to 0.966 (g / cm 3 ) The present invention relates to a propylene resin composition comprising 5 to 15 parts by weight of a high-density polyethylene, and a resin cap obtained by blending the resin composition and compression-molded.
[0007]
Further, the present invention provides a propylene resin composition obtained by further adding a nucleating agent to the propylene resin composition described above and 0.05 to 0.3 parts by weight based on 100 parts by weight of the ethylene-propylene block copolymer (A). The nucleating agent is preferably an organic phosphoric acid ester metal salt.
[0008]
Further, the present invention provides a high-density polyethylene 10 having a melt flow rate at 190 ° C. of 5 to 50 (g / 10 minutes) and a density of 0.957 to 0.966 (g / cm 3 ). It relates to a propylene resin composition blended with a pigment masterbatch containing 〜80% by weight.
[0009]
Furthermore, the present invention relates to a resin cap formed by compression molding from any of the above propylene resin compositions.
[0010]
DETAILED DESCRIPTION OF THE INVENTION
Next, the present invention will be described in detail. The propylene resin composition according to the present invention comprises (A) an ethylene-propylene block copolymer and (B) a high density polyethylene (C) a nucleating agent.
[0011]
(A) Ethylene-propylene block copolymer The ethylene-propylene block copolymer is a polymer basically composed of a polypropylene segment and an ethylene / propylene copolymer segment. Further, a polyethylene segment may coexist. The polypropylene segment is crystalline and mainly contributes to imparting mechanical strength such as rigidity of the block copolymer. The ethylene / propylene copolymer segment has rubber-like properties and forms a rubber portion of the block copolymer, contributing to imparting impact resistance.
[0012]
The content of the polypropylene segment in the block copolymer is 80 to 95, preferably 86 to 91% by weight, and the content of the ethylene / propylene copolymer segment is 5 to 20, preferably 9 to 14% by weight. When it is within the range, it is suitable for improving various mechanical properties of the resin composition. If necessary, the coexisting polyethylene segment is preferably in the range of 0 to 10% by weight.
[0013]
The ethylene content in the block copolymer is 6 to 12, preferably 6 to 9 (% by weight), and within this range, the resin composition is suitable for impact resistance. The melt flow rate (MFR) of the block copolymer is a value measured at 230 ° C. under a load of 2.16 kg in accordance with ASTM D-1238, and is 2 to 20, preferably 6 to 11 (g / 10 minutes). In this range, a resin composition suitable for a high production rate derived from the rigidity and impact resistance of the resin composition and the molding temperature is provided.
[0014]
Such a block copolymer is a so-called multi-stage polymerization method in which, in the presence of an olefin stereoregular polymerization catalyst, homopolymerization of propylene, then copolymerization of propylene and ethylene, and optionally homopolymerization of ethylene are performed. Can be manufactured. It can also be produced by mechanically melt-kneading a propylene homopolymer, a copolymer of propylene and ethylene, and if necessary, an ethylene homopolymer.
[0015]
(B) High- Density Polyethylene The polymer of the high-density polyethylene to be the component (B) is preferably an ethylene homopolymer, but if necessary, ethylene and 0.5 mol% or less of all monomer units, preferably 0.2 mol% or less. It is a polymer obtained by copolymerization with another α-olefin of at most mol%, particularly preferably at most 0.1 mol%. Examples of other α-olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1- Decene and the like can be mentioned, and the density of polyethylene (ASTM D1505) is 0.957 to 0.966 (g / cm 3 ).
[0016]
The high-density polyethylene has a melt flow rate (MFR) measured at 190 ° C. under a load of 2.16 kg according to ASTM D-1238 of 30 to 60, preferably 35 to 45 (g / 10 minutes). is there. When it is within this range, without sacrificing the mechanical strength of the resin composition, and exhibiting a ballistic effect with the ethylene-propylene block copolymer, moldability and cap performance can be improved, and sliding can be achieved. Sex can be enhanced. It can be produced by using such a high-density polyethylene and olefin stereoregular polymerization catalyst and polymerizing in the presence of ethylene and, if necessary, other α-olefins while adjusting the molecular weight.
[0017]
Nucleating <br/> propylene resin composition according to the present invention, (also referred to simply as nucleating agent in the description below) nucleating agent optionally can be added blended. Examples of the nucleating agent that can be used include (a) a metal salt of a carboxylic acid such as aluminum p-tert-butyl benzoate, (b) a polyhydric alcohol derivative such as dibenzylidene sorbitol and bis (4-methylbenzylidene) sorbitol, (c) ) Metal salts of organic phosphoric acid esters such as sodium-2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate, (d) branched olefins such as 3-methyl-1-butene, 3,3- Polymer nucleating agents such as homopolymers or copolymers such as dimethyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene and 3-methyl-1-pentene, and the like can be given. .
[0018]
Among these, organophosphate metal salts are preferable, and the addition thereof can achieve a good balance between the rigidity and impact resistance of the propylene resin composition and provide excellent slidability. Examples of the organic phosphoric acid ester metal salt include sodium-2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate represented by the formula (1) and an aluminum compound represented by the formula (2). can do. Particularly, the effect of the compound represented by the formula (1) is high.
[0019]
Embedded image
Figure 2004182955
Here, t-Bu represents a tert-butyl group.
[0020]
Embedded image
Figure 2004182955
[0021]
In the formula (2), R 1 and R 2 are each independently a hydrogen atom or an alkyl group. Examples of the alkyl group include groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, tert-amyl, hexyl, heptyl, octyl, nonyl, and 2-ethylhexyl. X is an alkylene group, such as methylene, ethylene, and propylene.
[0022]
Specifically, a compound in which X is a methylene group, R 1 is a tert-butyl group and R 2 is a methyl group, and a compound in which X is a methylene group and R 1 and R 2 are tert-butyl groups And X is a methylene group and R 1 and R 2 are tert-amyl groups.
[0023]
Propylene resin composition The resin composition according to the present invention comprises (A) an ethylene-propylene block copolymer of 85 to 95, preferably 90 to 95 parts by weight, and (B) a high density polyethylene of 5 to 15 parts by weight. , Preferably 5 to 10 parts by weight. Within this range, the dimensions of the cap, which is a product, can be maintained at the current dimensions with the current mold, and the closing and opening properties of the cap when used as a cap are extremely excellent, and the sliding is high. It becomes a resin composition having properties.
[0024]
Further, in the present invention, the nucleating agent is used in an amount of 0.05 to 0.3, preferably 0.07 to 0.3, more preferably 0.1 to 100 parts by weight of the ethylene-propylene block copolymer (A). ０．３0.3 parts by weight. When the content is within this range, it is possible to obtain a composition excellent in all balances such as the rigidity and impact resistance of the propylene resin composition, productivity by further improving the crystallization rate, and further improvement in heat resistance.
[0025]
The propylene resin composition may contain phenolic, phosphorus-based, or thioether-based antioxidants, neutralizers, light stabilizers, weathering stabilizers, flame retardants, pigments, dyes, stearylamide, erucylamide, etc., as necessary. Additives such as lubricants and fillers can be blended within a range not to impair the object of the present invention.
[0026]
The resin composition according to the present invention comprises (A) an ethylene-propylene block copolymer, (B) a high-density polyethylene, and, if necessary, a nucleating agent and other additives in the above-mentioned mixing amount range, using a Henschel mixer. , V-blender, ribbon blender, tumbler blender, and the like, and then melt-kneaded with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, or the like, to obtain a composition having a uniform composition. be able to.
[0027]
Molded products Various pigments can be manufactured by blending a pigment masterbatch with the propylene resin composition as required and subjecting it to injection molding. Is particularly preferred. As the pigment component of the pigment masterbatch used, either an inorganic pigment or an organic pigment-based masterbatch can be used. Examples of the former include oxides, sulfides, and sulfates of various metals, and examples of the latter include phthalocyanine, quinacridone, benzidine, chromophthal, and perylene compounds. The above pigment component has a melt flow rate at 230 ° C. of 10 to 100 (g / 10 minutes), preferably 30 to 70 (g / 10 minutes), and a density of 0.957 to 0.966 (g / cm 3 ). , Preferably from 0.960 to 0.966 (g / cm 3 ) of a high density polyethylene of 10 to 80% by weight. In the present invention, 2 to 10 parts by weight, preferably 4 to 9 parts by weight of the master batch can be blended with the propylene resin composition [(A) + (B)]. Within this range, a composition having an excellent balance between the cost of the pigment masterbatch and the rigidity and impact resistance of the propylene resin composition and the productivity due to the improvement of the crystallization rate can be obtained. The molded article has an excellent balance between rigidity and impact resistance, and can be used in a wide range of industrial fields such as a food field and a medical field as a cap.
[0028]
In particular, it is suitable for use in food containers and their caps, specifically, PET bottle caps, and has high slidability, so it is the final product in the filling process of contents and the packing process of fillings. Can be moved and transported smoothly on the production line.
[0029]
【Example】
Next, the present invention will be described through examples, but the present invention is not limited to these examples. First, the resins and additives used in Examples and Comparative Examples will be described.
[0030]
(A) ethylene-propylene block copolymer; ethylene content: 7 wt%, melt flow rate (ASTM D-1238, 230 ° C, 2.16 kg load): 8 (g / 10 min), homo part stereoregularity: 0.971 as measured by 13 C-NMR.
(B) high-density polyethylene; density (ASTM D1505) 0.963 (g / cm 3 ), melt flow rate (ASTM D-1238, 190 ° C, 2.16 kg load) 40 (g / 10 minutes).
[0031]
(C) Ethylene-propylene block copolymer: Melt flow rate (ASTM D-1238, 230 ° C, 2.16 kg load) of 8 (g / 10 min) with ethylene content of 7 wt%, homo-part stereoregularity of 13 0.955 as measured by C-NMR.
(D) High density ethylene homopolymer density (ASTM D-1505) is 0.963 (g / cm 3 ), and melt flow rate (ASTMD-1238, 190 ° C., 2.16 kg load) is 5 (g / 10 min.) ).
[0032]
(E) a phenolic antioxidant; tetrakis [methylene-3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane (F) a phosphorus antioxidant; tris (2,4-di- tert-butylphenol) phosphite (G) neutralizer; calcium stearate (H) neutralizer; hydrotalcite.
[0033]
(I) Nucleating agent sodium 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate (J) pigment masterbatch; white was used as a pigment. The composition of the master batch contains 9 wt% of titanium oxide, 9 wt% of erucylamide, and 82 wt% of high-density polyethylene having an MFR at 190 ° C. of 40 (g / 10 min) and a density of 0.963 (g / cm 3 ).
[0034]
(Examples 1 to 3) The above-mentioned resins and additives were prepared in the mixing ratio (parts by weight) shown in Table 1, and then uniformly mixed in a Henschel mixer. Next, the mixture was melt-kneaded at a resin temperature of 200 ° C. using a CIM-50 high-speed twin-screw extruder manufactured by Japan Steel Works, and the kneaded product was extruded to obtain pellets. In the crystallization speed, bending, and Izod tests, the pellets were blended with (J) a white pigment masterbatch and injection molded to prepare test pieces. The cap was prepared by blending (J) a white pigment masterbatch and compression molding at a resin temperature of 200 ° C. and a mold temperature of 20 ° C. in order to determine the actual tightening angle and opening torque.
[0035]
Using the pellets and the cap, various physical properties were examined by the following methods.
(A) Melt flow rate (MFR); ASTM D-1238, 230 ° C, 2.16 kg load, unit (g / 10 min).
(B) Crystallization rate measured by DSC. The method was prepared by melting at 240 ° C for 6 minutes and making the press film 270 µm thick. 5 mg of this was taken out, melted at 230 ° C. for 10 minutes, the temperature was lowered to 135 ° C. at a rate of 500 ° C./min, and the half time at which the crystal was saturated, that is, t1 / 2 (half crystallization time) was determined. The unit is minute.
(C) Initial flexural modulus: 23 ° C., according to ASTM D-790. The unit is (MPa).
(D) Izod impact strength: A notched test piece was used at 23 ° C. according to ASTM D-256. The unit is (J / m).
[0036]
(E) Tightening angle: The angle required to reach a tightening torque of 23 kgfm in the current PET bottle cap mold was determined. The unit is degree.
(F) Opening torque: The cap was turned at a speed of 2 seconds per rotation to determine the torque generated at the time of opening. The unit is kgfm.
[0037]
(Comparative Examples 1 to 5) Pellets and test pieces were obtained in the same manner as in Example 1 except that the resins and additives described in Table 1 were used. Thereafter, a physical property test was performed, and the results are shown in Table 1.
[0038]
In Examples 1 and 2, the closing angle is larger than that of Comparative Example 1, and the closing property is increased. In addition, the opening torque is 12 kgf · m in Example 1 and 11 kgf · m in Example 2, which is far lower than the opening torque of 15 kgf · m in Comparative Example 1, and is excellent in easy opening property.
[0039]
In Comparative Example 2, the tightening angle and the opening torque were good, but the crystallization speed was low, so that the screw turned up during high-speed molding occurred.
[0040]
In Comparative Example 3, the arrangement (ballistic effect) of the high-density polyethylene on the surface layer was insufficient, so that the tightening angle and the opening torque were not improved.
[0041]
As is clear from Table 1, the resin compositions obtained in Examples 1 and 2 satisfy the required physical properties when used as caps and can further improve high-speed productivity, as compared with Comparative Examples 1 to 3. It turns out that it is a composition.
[0042]
[Table 1]
Figure 2004182955
【The invention's effect】
In the present invention, as a specific example, an ethylene-propylene block copolymer having a homoregular stereoregularity of 0.960 or more and an MFR at 230 ° C. of 8 g / 10 min is a polyethylene having a MFR at 230 ° C. of 60 and a high density polyethylene. The polyethylene resin is present in the vicinity of the surface due to the ballistic effect caused by the difference in molecular weight under a pressure gradient, achieving easy closing, easy opening and reduction of opening torque as well as the inherent heat resistance of polypropylene. , And a highly novel resin composition having both rigidity and impact resistance was obtained.
[0043]
In addition, the nucleating agent is usually compounded to increase the transparency of the resin or sometimes to increase the rigidity.In the resin composition of the present invention, an excellent balance between rigidity and impact resistance is realized, By using the high stereoregularity polypropylene of the present invention, the crystallization rate, that is, the improvement in productivity, could be drastically improved. As a result, it was possible to eliminate screw defects during production.
[0044]
Therefore, the compression molded cap obtained from the present resin composition is suitable for use as a beverage cap in which rigidity and impact resistance, heat resistance, closing property, and easy opening property are required. It is the first invention that satisfies all the requirements, and is very useful.

Claims (5)

（Ａ）２３０℃におけるメルトフローレートが２〜２０（ｇ／１０分）でホモ部立体規則性が０．９６０以上で且つ全エチレン含有量が６〜１２（重量％）であるエチレン−プロピレンブロック共重合体８５〜９５重量部と、（Ｂ）１９０℃におけるメルトフローレートが３０〜６０（ｇ／１０分）、密度０．９５７〜０．９６６（ｇ／ｃｍ３）である高密度ポリエチレン５〜１５重量部とからなることを特徴とするプロピレン樹脂組成物。(A) An ethylene-propylene block having a melt flow rate at 230 ° C. of 2 to 20 (g / 10 minutes), a homo-part stereoregularity of 0.960 or more, and a total ethylene content of 6 to 12 (% by weight). 85 to 95 parts by weight of a copolymer, and (B) a high-density polyethylene 5 having a melt flow rate at 190 ° C. of 30 to 60 (g / 10 minutes) and a density of 0.957 to 0.966 (g / cm 3 ) Propylene resin composition, characterized in that the composition comprises プ ロ ピ レ ン 15 parts by weight. 請求項１記載の樹脂組成物にさらに造核剤を、（Ａ）エチレン−プロピレンブロック共重合体１００重量部に対して、０．０５〜０．３重量部配合をしたことを特徴とするプロピレン樹脂組成物。The propylene, wherein the resin composition according to claim 1 is further blended with a nucleating agent in an amount of 0.05 to 0.3 parts by weight based on 100 parts by weight of the ethylene-propylene block copolymer (A). Resin composition. 請求項２記載の造核剤が、有機リン酸エステル金属塩であることを特徴とする請求項２記載のプロピレン樹脂組成物。3. The propylene resin composition according to claim 2, wherein the nucleating agent according to claim 2 is an organic phosphate metal salt. 請求項１〜３記載の樹脂組成物に、１９０℃におけるメルトフローレートが５〜５０（ｇ／１０分）、密度が０．９５７〜０．９６６（ｇ／ｃｍ３）の高密度ポリエチレン１０〜８０重量％を含有する顔料マスターバッチをブレンドしたことを特徴とする請求項１〜３のいずれかに記載のプロピレン樹脂組成物。4. The high-density polyethylene having a melt flow rate at 190 ° C. of 5 to 50 (g / 10 minutes) and a density of 0.957 to 0.966 (g / cm 3 ). The propylene resin composition according to any one of claims 1 to 3, wherein a pigment master batch containing 80% by weight is blended. 請求項１〜４のいずれかに記載のプロピレン樹脂組成物から圧縮成形してなることを特徴とする樹脂キャップ。A resin cap formed by compression molding from the propylene resin composition according to claim 1.
JP2002355220A 2002-12-06 2002-12-06 Propylene resin composition and use of the same Pending JP2004182955A (en)

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JP2006192889A (en) * 2004-12-14 2006-07-27 Toray Ind Inc Biaxially stretched white polypropylene film and acceptance sheet for heat-sensitive transfer record using it
US8461280B2 (en) 2007-12-05 2013-06-11 Borealis Technology Oy Multi-stage process for producing multimodal linear low density polyethylene polymers
US8759448B2 (en) 2010-01-29 2014-06-24 Borealis Ag Polyethylene moulding composition with improved stress crack/stiffness relationship and impact resistance
US9139709B2 (en) 2007-08-10 2015-09-22 Borealis Technology Oy Article

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JP2007231136A (en) * 2006-02-28 2007-09-13 Kyoraku Co Ltd Blow molded panel composed of propylene-based resin composition, blow molded panel composed of the composition and deck board for automobile composed of the blow molded panel
US7973100B2 (en) * 2006-09-12 2011-07-05 Mitsu Chemicals, Inc. Polypropylene resin and blow molded container
CN101724195B (en) * 2008-10-24 2012-05-30 中国石油化工股份有限公司 Polypropylene composition and preparation method thereof
CN101914262B (en) * 2009-12-28 2012-09-26 上海金发科技发展有限公司 Beta crystal form polypropylene composite for water heater tank and preparation method thereof
CN103554676A (en) * 2013-11-05 2014-02-05 上海紫日包装有限公司 Novel cap shell material of plastic bottle cap and preparation method thereof
CN112239580B (en) * 2019-07-17 2022-09-20 中国石油化工股份有限公司 Polypropylene composition, polypropylene material, application of polypropylene composition and polypropylene material and milk powder cover

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006192889A (en) * 2004-12-14 2006-07-27 Toray Ind Inc Biaxially stretched white polypropylene film and acceptance sheet for heat-sensitive transfer record using it
US9139709B2 (en) 2007-08-10 2015-09-22 Borealis Technology Oy Article
US8461280B2 (en) 2007-12-05 2013-06-11 Borealis Technology Oy Multi-stage process for producing multimodal linear low density polyethylene polymers
US8759448B2 (en) 2010-01-29 2014-06-24 Borealis Ag Polyethylene moulding composition with improved stress crack/stiffness relationship and impact resistance

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