JP5345276B2 - Polypropylene composition having excellent impact resistance, flexural modulus and transparency and products made from the composition - Google Patents

Polypropylene composition having excellent impact resistance, flexural modulus and transparency and products made from the composition Download PDF

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JP5345276B2
JP5345276B2 JP2006125587A JP2006125587A JP5345276B2 JP 5345276 B2 JP5345276 B2 JP 5345276B2 JP 2006125587 A JP2006125587 A JP 2006125587A JP 2006125587 A JP2006125587 A JP 2006125587A JP 5345276 B2 JP5345276 B2 JP 5345276B2
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ソン ソク チェ
スン ヨル ハン
テ クン イ
テ ウ ウ
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SK Geo Centric Co Ltd
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/10—Applications used for bottles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst

Description

本発明は、優れた耐衝撃性、曲げ弾性率および透明性を有するポリプロピレン組成物ならびに該組成物から製造された製品に関し、より具体的には、エチレン−プロピレンランダム共重合体またはポリプロピレン−ブテン−１ランダム共重合体とエチレン−プロピレンエラストマー共重合体との溶融指数比を調節し、且つエチレン−プロピレンエラストマー共重合体のエチレンおよびプロピレンのモル比を調節することにより、前記エチレン−プロピレンエラストマー共重合体が１μｍ未満の粒径の粒子として非常に微細に分散している、優れた耐衝撃性、曲げ弾性率および透明性を有するポリプロピレン組成物と該組成物から製造された製品とに関する。   The present invention relates to a polypropylene composition having excellent impact resistance, flexural modulus and transparency, and to a product produced from the composition, and more specifically, ethylene-propylene random copolymer or polypropylene-butene- The ethylene-propylene elastomer copolymer is prepared by adjusting the melt index ratio of 1 random copolymer and ethylene-propylene elastomer copolymer and adjusting the molar ratio of ethylene and propylene of the ethylene-propylene elastomer copolymer. The present invention relates to a polypropylene composition having excellent impact resistance, flexural modulus and transparency, and a product produced from the composition, in which the coalescence is very finely dispersed as particles having a particle size of less than 1 μm.

プロピレン−エチレンブロック共重合体は、その優れた衝撃特性により車両部品、家電器具、工業部品、日常生活用品および包装容器といった射出成形品、包装用フィルムおよびシートなどに広範囲に用いられてきた。プロピレン−エチレンブロック共重合体から製造された成形物は優れた耐衝撃性を有しているが、透明性には非常に劣っているため、透明な食品包装用射出成形品や中空成形品、フィルム、シートなどへの使用には限界がある。一方、エチレン−プロピレンランダム共重合体は、優れた透明性を持つため、食品包装容器、フィルム、シート、中空成形物などに用いられる。しかし、これらのランダム共重合体は、耐衝撃性に劣っており、冷凍または冷蔵などの低温での使用が困難であり、用途に限界がある。   Propylene-ethylene block copolymers have been widely used for injection molded products such as vehicle parts, home appliances, industrial parts, daily life products and packaging containers, packaging films and sheets because of their excellent impact properties. Molded articles produced from a propylene-ethylene block copolymer have excellent impact resistance, but are very inferior in transparency, so transparent injection molded articles for food packaging and hollow molded articles, There is a limit to the use for films and sheets. On the other hand, ethylene-propylene random copolymers have excellent transparency and are therefore used in food packaging containers, films, sheets, hollow molded products and the like. However, these random copolymers have poor impact resistance, are difficult to use at low temperatures such as freezing or refrigeration, and have limited applications.

プロピレン−エチレンブロック共重合体の利点である優れた衝撃性および曲げ弾性率と共に透明性を示すために、幾つかの方法が提案されている。その中でも、特許文献１には、エチレン−プロピレンランダム共重合体に、メタロセン触媒を用いて製造されたエチレン−アルファオレフィン共重合体エラストマーを溶融混合させる方法が開示されている。しかし、前記特許は、エチレン−プロピレンランダム共重合体にエラストマーを微細に分布させることが難しく、優れた透明性の製品を得ることが難しいという欠点がある。また、エチレン−プロピレンランダム共重合体にエラストマーを分散させる後続工程の押出工程が追加されるため製造コストが増加し、また、均一な物性の製品を得ることが難しいという欠点がある。さらに、延伸工程が用いられる場合には、延伸の際に相分離が起こって所望の透明性を持ち難いという欠点がある。   Several methods have been proposed to show transparency along with the excellent impact and flexural moduli that are the advantages of propylene-ethylene block copolymers. Among them, Patent Document 1 discloses a method in which an ethylene-alpha olefin copolymer elastomer produced using a metallocene catalyst is melt mixed with an ethylene-propylene random copolymer. However, the above patents have the disadvantages that it is difficult to finely distribute the elastomer in the ethylene-propylene random copolymer and it is difficult to obtain an excellent transparency product. Moreover, since the subsequent extrusion process for dispersing the elastomer in the ethylene-propylene random copolymer is added, the production cost increases, and it is difficult to obtain a product having uniform physical properties. Further, when a stretching process is used, there is a disadvantage that phase separation occurs during stretching and it is difficult to have a desired transparency.

また、特許文献２には、エチレン−プロピレンランダム共重合体および弾性エチレン−プロピレン共重合体の固有粘度比を調節する方法が開示されている。しかし、この方法で得られた組成物は、透明性の改善が不十分であるうえ、厚い製品に適用すると、不透明な曇り現象が見られ、厚い製品への適用が難しいという欠点がある。   Patent Document 2 discloses a method for adjusting the intrinsic viscosity ratio of an ethylene-propylene random copolymer and an elastic ethylene-propylene copolymer. However, the composition obtained by this method has insufficient transparency improvement, and has a drawback that when applied to a thick product, an opaque clouding phenomenon is observed, making it difficult to apply to a thick product.

特許文献３には、エチレン−プロピレンエラストマー共重合体の固有粘度値が開示されている。しかし、高透明性を得るためには、高溶融指数の製品と低溶融指数の製品で求められるエチレン−プロピレンレンエラストマー共重合体の溶融指数が互いに異なっていなければならない。また、エチレン−プロピレンランダム共重合体とエチレン−プロピレンエラストマー共重合体の溶融指数比、およびエチレン−プロピレンエラストマー共重合体のエチレン／プロピレンの組成比を同時に調節して、組成物内のエチレン−プロピレンエラストマー共重合体の分散した粒子の粒径および２つの相間の屈折率の差を調節できるようにしなければならない。また、高耐衝撃性の組成物を製造するためには、組成物内のエチレン−プロピレンエラストマー共重合体の分散粒子の粒径を極めて微細なレベルで調節することが非常に重要である。しかし、前記特許では、その粒径の調節方法および屈折率差の調節のための方法の提示が全く不十分である。
韓国登録特許第３６１５５０号明細書 韓国登録特許第１５６５６０号明細書 韓国公開特許第２００４−００４１７２７号公報 Patent Document 3 discloses an intrinsic viscosity value of an ethylene-propylene elastomer copolymer. However, in order to obtain high transparency, the melt indexes of the ethylene-propylene elastomer copolymer required for the high melt index product and the low melt index product must be different from each other. In addition, by adjusting simultaneously the melt index ratio of the ethylene-propylene random copolymer and the ethylene-propylene elastomer copolymer and the ethylene / propylene composition ratio of the ethylene-propylene elastomer copolymer, the ethylene-propylene in the composition It must be possible to adjust the particle size of the dispersed particles of the elastomeric copolymer and the difference in refractive index between the two phases. In order to produce a high impact resistance composition, it is very important to adjust the particle size of the dispersed particles of the ethylene-propylene elastomer copolymer in the composition at a very fine level. However, in the above patent, the method for adjusting the particle size and the method for adjusting the refractive index difference are completely insufficient.
Korean Registered Patent No. 361550 Specification Korean registered patent No. 156560 Korean Published Patent No. 2004-0041727

したがって、本発明者らは、上述した問題点を解決するための広範囲な研究を鋭意行った。その結果、エチレン−プロピレンまたはプロピレン−ブテン−１ランダム共重合体とエチレン−プロピレンエラストマー共重合体との溶融指数比を調節し、かつエチレン−プロピレンエラストマー共重合体のエチレン−プロピレンの組成比を調節することにより、前記ランダム共重合体にエチレン−プロピレンエラストマー共重合体が微細に分散している、耐衝撃性、透明性および曲げ弾性率に優れたポリプロピレン樹脂を製造した。本発明はこの知見に基づいて完成されたものである。
従って、本発明の目的は、優れた耐衝撃性、透明性および曲げ弾性率を有するポリプロピレン樹脂組成物を提供することにある。 Therefore, the present inventors have conducted extensive research to solve the above-described problems. As a result, the melt index ratio between the ethylene-propylene or propylene-butene-1 random copolymer and the ethylene-propylene elastomer copolymer is adjusted, and the ethylene-propylene composition ratio of the ethylene-propylene elastomer copolymer is adjusted. Thus, a polypropylene resin excellent in impact resistance, transparency, and flexural modulus in which an ethylene-propylene elastomer copolymer is finely dispersed in the random copolymer was produced. The present invention has been completed based on this finding.
Accordingly, an object of the present invention is to provide a polypropylene resin composition having excellent impact resistance, transparency and flexural modulus.

上記目的を達成するため、本発明は、耐衝撃性、曲げ弾性率および透明性に優れたポリプロピレン樹脂組成物であって、
（ａ）１〜５重量％のエチレンを含有するエチレン−プロピレンランダム共重合体および２〜１２重量％のブテン−１を含有するプロピレン−ブテン−１ランダム共重合体から選択される高結晶性ランダム共重合体、８０〜９５重量％；ならびに
（ｂ）３０〜５０重量％のエチレンを含有するエチレン−プロピレンエラストマー共重合体、５〜２０重量％
を含み、前記成分（ａ）の溶融指数に対する前記成分（ｂ）の溶融指数の比が、１．５〜３５である組成物を提供するものである。
また、本発明は、前記ポリプロピレン樹脂組成物の、射出成形、押出成形又は中空成形により製造される製品を提供するものである。 In order to achieve the above object, the present invention is a polypropylene resin composition excellent in impact resistance, flexural modulus and transparency,
(A) Highly crystalline random selected from ethylene-propylene random copolymers containing 1 to 5 wt% ethylene and propylene-butene-1 random copolymers containing 2 to 12 wt% butene-1 Copolymer, 80-95 wt%; and (b) an ethylene-propylene elastomer copolymer containing 30-50 wt% ethylene, 5-20 wt%
And the ratio of the melt index of the component (b) to the melt index of the component (a) is 1.5 to 35.
The present invention also provides a product produced by injection molding, extrusion molding or hollow molding of the polypropylene resin composition.

本発明にしたがって、成分ａおよび成分ｂの溶融指数比を調節し、成分ｂのエチレン含量を調節することにより、優れた曲げ弾性率、透明性および耐衝撃性を有するポリプロピレン組成物を製造することができる。本発明のポリプロピレン組成物は、冷蔵容器、冷凍容器、食品包装容器、押出成形物、中空成形物、フィルム、シートおよび瓶栓などの様々な製品の製造に適するものと期待される。   According to the present invention, a polypropylene composition having excellent flexural modulus, transparency and impact resistance is prepared by adjusting the melt index ratio of component a and component b and adjusting the ethylene content of component b. Can do. The polypropylene composition of the present invention is expected to be suitable for production of various products such as refrigerated containers, frozen containers, food packaging containers, extruded products, hollow molded products, films, sheets and bottle stoppers.

本発明は、耐衝撃性、曲げ弾性率および透明性に優れたポリプロピレン樹脂組成物であって、
（ａ）８０〜９５重量％の、１〜５重量％のエチレンを含有するエチレン−プロピレンランダム共重合体および２〜１２重量％のブテン−１を含有するプロピレン−ブテン−１ランダム共重合体から選択される高結晶性ランダム共重合体；ならびに
（ｂ）５〜２０重量％の、３０〜５０重量％のエチレンを含有するエチレン−プロピレンエラストマー共重合体を含む組成物を提供する。 The present invention is a polypropylene resin composition excellent in impact resistance, flexural modulus and transparency,
(A) From 80 to 95% by weight of an ethylene-propylene random copolymer containing 1 to 5% by weight of ethylene and a propylene-butene-1 random copolymer containing 2 to 12% by weight of butene-1. Provided is a composition comprising a selected highly crystalline random copolymer; and (b) an ethylene-propylene elastomer copolymer containing 5-20 wt%, 30-50 wt% ethylene.

前記１〜５重量％のエチレンを含有する高結晶性エチレン−プロピレンランダム共重合体、および２〜１２重量％のブテン−１を含有するプロピレン−ブテン−１ランダム共重合体は、当分野で知られている慣用の方法によって製造することができる。例えば、プロピレン、エチレンまたはブテン−１とトリエチルアルミニウム、チーグラー−ナッタ系触媒、およびシラン系電子供与体を反応装置内で混合し、６０〜８０℃の反応温度および３０〜３５気圧で、スラリーバルク重合を行ってプロピレン−ブテン−１ランダム共重合体およびエチレン−プロピレンランダム共重合体を製造することができる。前記ランダム共重合体の製造の際、高立体規則性（または高結晶性）のポリプロピレンを製造することが可能な高結晶性のチーグラー−ナッタ系触媒を使用すると、より高い曲げ弾性率を与えることができるが、本発明は前記触媒の使用に限定されるものではない。   The highly crystalline ethylene-propylene random copolymer containing 1-5 wt% ethylene and the propylene-butene-1 random copolymer containing 2-12 wt% butene-1 are known in the art. Can be produced by conventional methods. For example, propylene, ethylene or butene-1 and triethylaluminum, a Ziegler-Natta catalyst, and a silane electron donor are mixed in a reactor, and slurry bulk polymerization is performed at a reaction temperature of 60 to 80 ° C. and 30 to 35 atm. To produce a propylene-butene-1 random copolymer and an ethylene-propylene random copolymer. In the production of the random copolymer, when a highly crystalline Ziegler-Natta catalyst capable of producing highly stereoregular (or highly crystalline) polypropylene is used, a higher flexural modulus is given. However, the present invention is not limited to the use of the catalyst.

本発明の高結晶性エチレン−プロピレンランダム共重合体は、前記ランダム共重合体を基準として１〜５重量％のエチレンを含有するように製造することが好ましい。このエチレン含量が１重量％未満であると透明性が不十分であり、５重量％を超えると優れた透明性は得られるが、得られる組成物の曲げ弾性率が低下し前記ランダム共重合体の製造が不可能になる。また、本発明によれば、ポリプロピレン−ブテン−１ランダム共重合体は、好ましくは前記ランダム共重合体を基準として２〜１２重量％のブテン−１を含有する。このブテン−１の含量が２重量％未満であれば、透明性が不十分であり、１２重量％を超えると、優れた透明性は得られるが、前記ランダム共重合体の製造が不可能になる。   The highly crystalline ethylene-propylene random copolymer of the present invention is preferably produced so as to contain 1 to 5% by weight of ethylene based on the random copolymer. When the ethylene content is less than 1% by weight, the transparency is insufficient. When the ethylene content exceeds 5% by weight, excellent transparency can be obtained, but the bending elastic modulus of the resulting composition is lowered and the random copolymer is obtained. It becomes impossible to manufacture. Also, according to the present invention, the polypropylene-butene-1 random copolymer preferably contains 2 to 12% by weight of butene-1 based on the random copolymer. If the butene-1 content is less than 2% by weight, the transparency is insufficient, and if it exceeds 12% by weight, excellent transparency can be obtained, but the production of the random copolymer becomes impossible. Become.

一方、本発明におけるエチレン−プロピレンエラストマー共重合体は、前記エチレン−プロピレンランダム共重合体およびポリプロピレン−ブテン−１ランダム共重合体の重合完了の後に未反応プロピレンを除去し、エチレンおよびプロピレンを反応器に注入して連続的に重合する。
本発明におけるエチレン−プロピレンエラストマー共重合体は、透明性の向上のために、エチレン含量が３０〜５０重量％であることが好ましい。すなわち、前記エチレン−プロピレンエラストマー共重合体の製造の際にエチレン／（エチレン＋プロピレン）のモル比を０．２５〜０．４０に維持することが好ましい。 On the other hand, the ethylene-propylene elastomer copolymer in the present invention removes unreacted propylene after completion of the polymerization of the ethylene-propylene random copolymer and the polypropylene-butene-1 random copolymer, and the ethylene and propylene are reacted in a reactor. And continuously polymerized.
The ethylene-propylene elastomer copolymer in the present invention preferably has an ethylene content of 30 to 50% by weight in order to improve transparency. That is, it is preferable to maintain the ethylene / (ethylene + propylene) molar ratio at 0.25 to 0.40 during the production of the ethylene-propylene elastomer copolymer.

本発明の組成物において、前記ランダム共重合体の含量は８０〜９５重量％であることが好ましく、エチレン−プロピレンエラストマー共重合体の含量は５〜２０重量％であることが好ましい。前記ランダム共重合体の含量が８０重量％未満であると透明性が不十分となり、９５重量％を超えると衝撃強度の改善が不十分となる。ここで、前記エチレン−プロピレンエラストマー共重合体の溶融指数（ＭＩ−ａ）に対するランダム共重合体の溶融指数（ＭＩ−ｂ）の比（ＭＩ−ｂ／ＭＩ−ａ）は、１．５〜３５であることが好ましい。溶融指数の比が前記の範囲から外れると、透明性と衝撃強度との均衡が悪くなり得る。   In the composition of the present invention, the content of the random copolymer is preferably 80 to 95% by weight, and the content of the ethylene-propylene elastomer copolymer is preferably 5 to 20% by weight. When the content of the random copolymer is less than 80% by weight, the transparency is insufficient, and when it exceeds 95% by weight, the impact strength is not sufficiently improved. Here, the ratio (MI-b / MI-a) of the melt index (MI-b) of the random copolymer to the melt index (MI-a) of the ethylene-propylene elastomer copolymer is 1.5 to 35. It is preferable that When the ratio of the melt index is out of the above range, the balance between transparency and impact strength can be deteriorated.

本発明の組成物の機械的強度および透明性をさらに改善するためには、核剤をさらに添加する。この核剤としては、ジベンジリデンソルビトール、ジ（ｐ−メチルベンジリデン）ソルビトール、ジメチルベンジリデンソルビトール、アルキル安息香酸アルミニウム塩（an aluminum salt of alkylbenzoic acid）、および有機リン金属塩よりなる群から選択される１種または２種以上の混合物を使用することができる。核剤は、５００ｐｐｍ〜３，０００ｐｐｍの量で使用されることが好ましい。   In order to further improve the mechanical strength and transparency of the composition of the present invention, a nucleating agent is further added. The nucleating agent is 1 selected from the group consisting of dibenzylidene sorbitol, di (p-methylbenzylidene) sorbitol, dimethyl benzylidene sorbitol, an aluminum salt of alkylbenzoic acid, and an organophosphorus metal salt. A seed or a mixture of two or more can be used. The nucleating agent is preferably used in an amount of 500 ppm to 3,000 ppm.

このように製造された本発明のポリプロピレン組成物は、前記ランダム共重合体とエチレン−プロピレンエラストマー共重合体の溶融指数比、およびエチレン−プロピレンエラストマー共重合体のエチレン／プロピレンの組成比が同時に調節されているので、前記エチレン−プロピレンエラストマー共重合体がランダム共重合体に１μｍ未満の粒径の粒子として非常に微細に分散して光の乱反射が最小化され、透明性、アイゾッド衝撃強度および曲げ弾性率が向上するという利点がある。したがって、本発明の組成物は、冷蔵および冷凍容器、食品包装容器、押出成形物、中空成形物、フィルム、シートおよび瓶栓などの様々な製品に使用できるものと期待される。   The polypropylene composition of the present invention thus prepared has the melt index ratio of the random copolymer and the ethylene-propylene elastomer copolymer and the ethylene / propylene composition ratio of the ethylene-propylene elastomer copolymer simultaneously adjusted. As a result, the ethylene-propylene elastomer copolymer is very finely dispersed as a particle having a particle size of less than 1 μm in the random copolymer, minimizing irregular reflection of light, transparency, Izod impact strength and bending. There is an advantage that the elastic modulus is improved. Therefore, it is expected that the composition of the present invention can be used for various products such as refrigerated and frozen containers, food packaging containers, extruded products, hollow molded products, films, sheets and bottle stoppers.

以下、実施例によって本発明をより具体的に説明する。しかし、本発明の範囲はこれらの実施例に限定されるものではない。
本発明の実施例および比較例で製造されたポリプロピレン組成物の物性は、以下の方法で測定された。
１）溶融指数：ＡＳＴＭ Ｄ１２３８にしたがって、２３０℃、２．１６ｋｇ荷重で測定した。
２）透明性：ＡＳＴＭ Ｄ１２０４にしたがって、厚さ１ｍｍの射出試片のヘイズ値を測定して決定した。
３）曲げ弾性率：ＡＳＴＭ Ｄ７９０にしたがって、射出試片につき測定した。
４）アイゾッド(Izod)衝撃強度：ＡＳＴＤ Ｄ２５６にしたがって、２３℃で射出試片につき測定した。
５）キシレン溶融試片部分：重合で得られた一定量の試料を一定量のキシレンと共に丸底フラスコに仕込んで沸騰点まで昇温して約１時間溶融させた。室温まで徐々に冷却して再結晶し、キシレンに溶融した部分を抽出した。キシレンを蒸発させて残った試料の百分率を測定した。
６）電子顕微鏡撮影：試片を液体窒素に浸漬し、冷却した。冷却した試片をミクロトームで切断してシクロヘキサン溶液に入れ、超温波洗浄機内に１時間放置して試料内のエチレン−プロピレンエラストマーを溶出させた。溶融した試片に金を蒸着させてＺＥＯＬ社の電子顕微鏡で試料内のエチレン−プロピレンエラストマー共重合体の分散を観察した。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the scope of the present invention is not limited to these examples.
The physical properties of the polypropylene compositions produced in the examples and comparative examples of the present invention were measured by the following methods.
1) Melting index: Measured at 230 ° C. and 2.16 kg load according to ASTM D1238.
2) Transparency: According to ASTM D1204, the haze value of an injection specimen having a thickness of 1 mm was measured and determined.
3) Flexural modulus: measured for injection specimens according to ASTM D790.
4) Izod impact strength: measured on injection specimens at 23 ° C. according to ASTD D256.
5) Xylene melting specimen part: A certain amount of sample obtained by polymerization was charged into a round bottom flask together with a certain amount of xylene, heated to the boiling point and melted for about 1 hour. The solution was gradually cooled to room temperature and recrystallized to extract a portion melted in xylene. The percentage of sample left after evaporation of xylene was measured.
6) Electron micrograph: The specimen was immersed in liquid nitrogen and cooled. The cooled specimen was cut with a microtome, placed in a cyclohexane solution, and left in an ultra warm wave washer for 1 hour to elute the ethylene-propylene elastomer in the sample. Gold was vapor-deposited on the melted specimen, and the dispersion of the ethylene-propylene elastomer copolymer in the sample was observed with an electron microscope of ZEOL.

実施例１
エチレン、プロピレン、トリエチルアルミニウム、高活性チーグラーナッタ系触媒、シラン系電子供与体を反応装置で混合し、このスラリーを６０〜８０℃の反応温度および３０〜３５気圧の下でバルク重合を行い、プロピレン含量９６．７重量％、エチレン含量３．３重量％のエチレン−プロピレンランダム共重合体（成分ａ）を製造した。このランダム共重合体の溶融指数は水素の量で調節した。 Example 1
Ethylene, propylene, triethylaluminum, a highly active Ziegler-Natta catalyst, and a silane electron donor are mixed in a reactor, and this slurry is subjected to bulk polymerization at a reaction temperature of 60 to 80 ° C. and 30 to 35 atm. An ethylene-propylene random copolymer (component a) having a content of 96.7% by weight and an ethylene content of 3.3% by weight was produced. The melt index of this random copolymer was adjusted by the amount of hydrogen.

前記エチレン−プロピレンランダム共重合体の重合完了の後、未反応プロピレンを除去し、反応装置内の圧力を大気圧に下げた。その後、モノマーとしてエチレン及びプロピレンと溶融指数調節剤として水素とを、７０〜８０℃の反応温度および１０〜１５気圧の反応装置に注入して気相状態で連続的に重合させ、エチレン含量４８重量％のエチレン−プロピレンエラストマー重合体（成分ｂ）を製造した。このエラストマー重合体のエチレン−プロピレン組成比は、エチレン／（エチレン＋プロピレン）のモル比で調節し、このエラストマー重合体の溶融指数は水素／エチレンのモル比で調節した。   After completion of the polymerization of the ethylene-propylene random copolymer, unreacted propylene was removed, and the pressure in the reactor was lowered to atmospheric pressure. Thereafter, ethylene and propylene as monomers and hydrogen as a melt index modifier are injected into a reactor at a reaction temperature of 70 to 80 ° C. and 10 to 15 atm to polymerize continuously in a gas phase, and an ethylene content of 48 wt. % Ethylene-propylene elastomer polymer (component b) was produced. The ethylene-propylene composition ratio of the elastomer polymer was adjusted by the ethylene / (ethylene + propylene) molar ratio, and the melt index of the elastomer polymer was adjusted by the hydrogen / ethylene molar ratio.

前記エチレン−プロピレンエラストマー共重合体の製造後、エチレン−プロピレンランダム共重合体の含量が９０．１重量％であり、エチレン−プロピレンエラストマー共重合体の含量が９．９重量％である本発明の組成物を得た。
このように得られた前記ポリプロピレン組成物に、酸化防止剤、中和剤および造核剤を添加した。混合物をツインスクリュー押出機によりペレットとした後、１５０トン射出機（東信油圧製、韓国）でＡＳＴＭ規格の射出試片を製造して物性を測定した。測定結果を下記表１に示す。 After the production of the ethylene-propylene elastomer copolymer, the ethylene-propylene random copolymer content is 90.1% by weight, and the ethylene-propylene elastomer copolymer content is 9.9% by weight. A composition was obtained.
An antioxidant, a neutralizing agent, and a nucleating agent were added to the polypropylene composition thus obtained. After the mixture was pelletized with a twin screw extruder, ASTM standard injection specimens were manufactured with a 150-ton injection machine (manufactured by Toshin Hydraulic Co., Ltd., Korea) and the physical properties were measured. The measurement results are shown in Table 1 below.

実施例２〜５、７〜１０および比較例１〜５
下記表１および２に示すように、成分および含量を代えた以外は、実施例１と同様にしてポリプロピレン組成物を製造した。 Examples 2-5, 7-10 and Comparative Examples 1-5
As shown in Tables 1 and 2 below, a polypropylene composition was produced in the same manner as in Example 1 except that the components and contents were changed.

実施例６
下記表１に示すように、成分ａの製造の際にモノマーとしてプロピレンおよびブテン−１を用いた以外は、実施例１と同様にしてポリプロピレン組成物を製造した。
表１から分かるように、成分ａと成分ｂの溶融指数の比を調節して製造されたポリプロピレン組成物は、透明性においてのみならず、衝撃強度および曲げ弾性率に優れていた。
また、図１〜３に示すように、実施例２（図１）の場合、比較例２（図３）および３（図２）と比較して、エチレン−プロピレンエラストマー共重合体（成分ｂ）が小さい粒径の粒子として分散しており、透明性が著しく改善されたことを示している。すなわち、本発明の組成物においては、前記成分ａと前記成分ｂとの溶融指数比が調節されており、前記成分ｂの粒径が、光の乱反射を最小化するため好ましくは１μｍ未満程度に小さいため、透明性およびアイゾッド衝撃強度が改善されている。 Example 6
As shown in Table 1 below, a polypropylene composition was produced in the same manner as in Example 1 except that propylene and butene-1 were used as monomers in the production of Component a.
As can be seen from Table 1, the polypropylene composition produced by adjusting the ratio of the melt index of component a and component b was excellent not only in transparency but also in impact strength and flexural modulus.
In addition, as shown in FIGS. 1 to 3, in the case of Example 2 (FIG. 1), an ethylene-propylene elastomer copolymer (component b) is compared with Comparative Examples 2 (FIG. 3) and 3 (FIG. 2). Are dispersed as small-diameter particles, indicating that the transparency has been remarkably improved. That is, in the composition of the present invention, the melt index ratio between the component a and the component b is adjusted, and the particle size of the component b is preferably less than about 1 μm in order to minimize irregular reflection of light. Since it is small, transparency and Izod impact strength are improved.

註１）Ｃ2はエチレンを示し、Ｈ2は水素を示す。
註２）ＭＩ−ａは成分ａの溶融指数であり、ＭＩ−ｂは成分ｂの溶融指数である。 註 1) C 2 represents ethylene and H 2 represents hydrogen.
2) MI-a is the melting index of component a, and MI-b is the melting index of component b.

一方、表１および図４に示すように、プロピレン−ブテン−１ランダム共重合体を用いた実施例６の場合も、エチレン−プロピレンエラストマー共重合体が１μｍ未満の粒径の粒子として分散しており、実施例６の組成物が衝撃強度および透明性のみでなく、曲げ弾性率にも優れていることを示している。実施例６のように、プロピレン−ブテン−１ランダム共重合体を用いた場合、エチレン−プロピレンランダム共重合体を用いた場合より、優れた曲げ弾性率が得られた。従って、薄くて大きい成形物を製造する場合には、プロピレン−ブテン−１ランダム共重合体を用いることがより有利であると考えられる。   On the other hand, as shown in Table 1 and FIG. 4, in the case of Example 6 using a propylene-butene-1 random copolymer, the ethylene-propylene elastomer copolymer was dispersed as particles having a particle size of less than 1 μm. This indicates that the composition of Example 6 is excellent not only in impact strength and transparency but also in flexural modulus. As in Example 6, when the propylene-butene-1 random copolymer was used, an excellent bending elastic modulus was obtained as compared with the case where the ethylene-propylene random copolymer was used. Therefore, it is considered that it is more advantageous to use a propylene-butene-1 random copolymer when producing a thin and large molded product.

下記表２に示すように、本発明によって成分ｂのエチレン含量を調節した実施例７〜１０は、比較例４および５に比べて優れた透明性を有していた。特に、エチレン含量が少なくなるほどヘイズ値で表わすことができない明瞭度および透明度が現れ、非常に美麗な光学的特性を示した。
したがって、エチレン−プロピレンエラストマー共重合体のエチレン／（エチレン＋プロピレン）のモル比を、０．２５〜０．４０に調節して、成分ｂのエチレン含量を３０〜５０重量％に維持することにより、優れた光学的特性および機械的物性を有する製品を得ることができる。 As shown in Table 2 below, Examples 7 to 10 in which the ethylene content of component b was adjusted according to the present invention had superior transparency compared to Comparative Examples 4 and 5. In particular, as the ethylene content decreased, clarity and transparency that cannot be expressed by haze values appeared, and very beautiful optical characteristics were exhibited.
Therefore, by adjusting the ethylene / (ethylene + propylene) molar ratio of the ethylene-propylene elastomer copolymer to 0.25 to 0.40 and maintaining the ethylene content of component b at 30 to 50% by weight. A product having excellent optical properties and mechanical properties can be obtained.

註１）Ｃ2はエチレンを示し、Ｃ3はプロピレンを示す。
註２）ＭＩ−ａは成分ａの溶融指数であり、ＭＩ−ｂは成分ｂの溶融指数である。 1) C 2 represents ethylene and C 3 represents propylene.
2) MI-a is the melting index of component a, and MI-b is the melting index of component b.

本発明の一実施例によって製造されたポリプロピレン組成物の射出試片を電子顕微鏡で撮影した写真である。1 is a photograph of an injection specimen of a polypropylene composition manufactured according to an embodiment of the present invention, taken with an electron microscope. 本発明の一比較例によって製造されたポリプロピレン組成物の射出試片を電子顕微鏡で撮影した写真である。It is the photograph which image | photographed the injection specimen of the polypropylene composition manufactured by one comparative example of this invention with the electron microscope. 別の比較例によって製造されたポリプロピレン組成物の射出試片を電子顕微鏡で撮影した写真である。It is the photograph which image | photographed the injection specimen of the polypropylene composition manufactured by another comparative example with the electron microscope. 別の実施例によって製造されたポリプロピレン組成物の射出試片を電子顕微鏡で撮影した写真である。It is the photograph which image | photographed the injection specimen of the polypropylene composition manufactured by another Example with the electron microscope.

Claims (4)

１〜５重量％のエチレンを含有するエチレン−プロピレンランダム共重合体および２〜１２重量％のブテン−１を含有するプロピレン−ブテン−１ランダム共重合体から選択される高結晶性ランダム共重合体（成分（ａ））に、モノマーとしてエチレンおよびプロピレンを注入し、溶融指数調節剤として水素を注入して、重合を連続的に行い、３０〜５０重量％のエチレンを含有するエチレン−プロピレンエラストマー共重合体（成分（ｂ））を製造する段階を含むポリプロピレン組成物の製造方法であって、
前記ポリプロピレン組成物は８０〜９５重量％の成分（ａ）および５〜２０重量％の成分（ｂ）を含み、前記成分（ａ）の溶融指数に対する前記成分（ｂ）の溶融指数の比が、１．５〜３５であり、前記成分（ｂ）が１μｍ未満の粒径の粒子として微細分散していることを特徴とする方法。 Highly crystalline random copolymer selected from ethylene-propylene random copolymer containing 1-5 wt% ethylene and propylene-butene-1 random copolymer containing 2-12 wt% butene-1 (Component (a)) is injected with ethylene and propylene as monomers, and hydrogen is injected as a melt index modifier to carry out polymerization continuously, and an ethylene-propylene elastomer copolymer containing 30 to 50% by weight of ethylene. A method for producing a polypropylene composition comprising the step of producing a polymer (component (b)),
The polypropylene composition comprises 80 to 95% by weight of component (a) and 5 to 20% by weight of component (b), wherein the ratio of the melt index of component (b) to the melt index of component (a) is: 1.5 to 35, and the component (b) is finely dispersed as particles having a particle size of less than 1 μm . 請求項１に記載の方法により製造されたポリプロピレン組成物。A polypropylene composition produced by the method according to claim 1. 請求項２に記載のポリプロピレン組成物の、射出成形、押出成形又は中空成形により製造された製品。A product produced by injection molding, extrusion molding or hollow molding of the polypropylene composition according to claim 2. 前記製品が冷蔵容器、冷凍容器、食品包装容器、押出中空成形物、フィルム、シートおよび瓶栓からなる群から選択される、請求項３に記載の製品。 4. The product of claim 3, wherein the product is selected from the group consisting of refrigerated containers, frozen containers, food packaging containers, extruded hollow moldings, films, sheets and bottle stoppers.
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