JP6699175B2 - Polyethylene resin composition and medical container comprising the same - Google Patents
Polyethylene resin composition and medical container comprising the same Download PDFInfo
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Description
本発明は、ポリエチレン樹脂及びポリエチレン製医療容器に関する。さらに詳しくは、プラスチックアンプルのような薬液等の充填に好適なポリエチレン製医療容器に関するものである。 The present invention relates to a polyethylene resin and a polyethylene medical container. More specifically, the present invention relates to a polyethylene medical container suitable for filling a drug solution such as a plastic ampoule.
薬液、血液等を充填する医療容器には、滅菌処理等に耐えられる耐熱性、異物の混入や薬剤配合による変化を確認するために透明性や肌荒れが少ないことなどが要求される。 A medical container filled with a drug solution, blood or the like is required to have heat resistance to withstand sterilization and the like, and to have transparency and less rough skin in order to confirm changes due to mixing of foreign substances and drug formulation.
従来、このような性能を満たす医療容器としてガラス製容器が使用されていたが、衝撃や落下による容器の破損、薬液投与時の容器内への外気の浸入による汚染等の問題があるため、耐衝撃性に優れ、柔軟で内容液の排出が容易で廃棄処分も容易なプラスチック製容器が用いられるようになった。プラスチック製容器としては、軟質塩化ビニル樹脂、エチレン−酢酸ビニル共重合体樹脂、ポリプロピレン樹脂および高圧法低密度ポリエチレン、直鎖状低密度ポリエチレン、高密度ポリエチレン等のポリエチレン系樹脂が用いられている。しかし、軟質塩化ビニル樹脂は可塑剤が薬液中に溶出するなど衛生面で問題があり、エチレン−酢酸ビニル共重合体樹脂は耐熱性に劣り、ポリプロピレン樹脂は柔軟性やクリーン性（低微粒子性）が課題となっている。また、ポリエチレン系樹脂においても、透明性を満足するために密度を低くすると耐熱性等が低下するなどの問題がある。 Conventionally, a glass container has been used as a medical container satisfying such performance, but there is a problem such as damage to the container due to impact or drop, contamination due to invasion of outside air into the container at the time of administering a chemical solution, and the like. Plastic containers, which have excellent impact resistance, are flexible, can be easily discharged, and can be easily disposed of, have come to be used. As the plastic container, polyethylene resin such as soft vinyl chloride resin, ethylene-vinyl acetate copolymer resin, polypropylene resin and high-pressure low density polyethylene, linear low density polyethylene, and high density polyethylene are used. However, soft vinyl chloride resin has a problem in hygiene such as the plasticizer being eluted in the chemical liquid, ethylene-vinyl acetate copolymer resin is inferior in heat resistance, and polypropylene resin is flexible and clean (low particle size). Is an issue. Further, polyethylene resins also have a problem that the heat resistance and the like decrease when the density is lowered to satisfy transparency.
医療用のプラスチックアンプルにおいては、優れた加工性のために、高圧法低密度ポリエチレン等のポリエチレン系樹脂が広く用いられ、ブロー成型により生産されている。しかしながら、無菌状態を保つために１１０℃以上の温度での滅菌処理を行う場合、高圧法低密度ポリエチレンを用いると耐熱性が不足して滅菌処理時に変形しやすい問題点があった。比較的密度が高い高圧法低密度ポリエチレンを選定して用いた場合には、耐熱性が良好である一方で、透明性が不十分で内溶液の視認性が悪かった。 In plastic ampules for medical use, polyethylene-based resins such as high-pressure low-density polyethylene are widely used because of their excellent workability and are produced by blow molding. However, when performing sterilization at a temperature of 110° C. or higher in order to maintain the sterility, the use of high-pressure low-density polyethylene has a problem that heat resistance is insufficient and deformation is likely to occur during sterilization. When high-pressure low-density polyethylene having a relatively high density was selected and used, the heat resistance was good, but the transparency was insufficient and the visibility of the inner solution was poor.
近年、いわゆるメタロセン触媒に代表されるシングルサイト系触媒で製造されたエチレン−α−オレフィン共重合体が開発され、それらをブロー成型することで、耐熱性、透明性及びクリーン性を向上した容器（例えば特許文献１〜２参照）が提案されている。しかしながら、高圧法低密度ポリエチレン同等の加工性が得られないため、高圧法低密度ポリエチレン仕様の現行設備での使用が困難である。特に、小口径かつ肉厚が厚い医療用アンプルを生産した場合、肌荒れが生じて内溶液の視認性が劣る場合や、ドローダウンにより厚みが不均一になるなど、成型自体が困難である問題があった。 In recent years, ethylene-α-olefin copolymers produced by single-site catalysts typified by so-called metallocene catalysts have been developed, and by blow molding them, heat resistance, transparency, and a container with improved cleanliness ( For example, refer to Patent Documents 1 and 2). However, since it is not possible to obtain the same processability as that of high-pressure low-density polyethylene, it is difficult to use it in the current equipment of high-pressure low-density polyethylene specifications. In particular, when producing a small-diameter and thick-walled medical ampoule, when the skin is rough and the visibility of the inner solution is poor, or the drawdown makes the thickness uneven, there is a problem that molding itself is difficult. there were.
本発明の目的は、従来両立が困難であった透明性、耐熱性及び加工性に優れ、かつ滅菌処理後も高い透明性が保持されるポリエチレン製医療容器を提供することにある。 An object of the present invention is to provide a medical container made of polyethylene, which has excellent transparency, heat resistance, and processability, which have been difficult to achieve at the same time, and which maintains high transparency even after sterilization.
本発明者らは、鋭意検討を行なった結果、特定の物性を有するエチレン−α−オレフィン共重合体に高圧法低密度ポリエチレンを特定量配合した樹脂組成物を用いて医療容器とすることで、上記課題が解決できることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the present inventors have made a medical container by using an ethylene-α-olefin copolymer having specific physical properties and a resin composition in which a specific amount of high-pressure low-density polyethylene is blended, The inventors have found that the above problems can be solved and have completed the present invention.
すなわち、本発明は、下記特性（ａ）〜（ｄ）を満足するエチレン−α−オレフィン共重合体（Ａ）が５重量％以上３０重量％未満、下記特性（ｅ）〜（ｆ）を満足する高圧法低密度ポリエチレン（Ｂ）が７０重量％を超えて９５重量％未満を含むポリエチレン樹脂組成物およびそれよりなる医療容器に関するものである。
（ａ）密度が９２０〜９５０ｋｇ／ｍ３である。
（ｂ）メルトフローレート（以下ＭＦＲという）が０．１〜１５ｇ／１０分である。
（ｃ）ゲル・パーミエーション・クロマトグラフィーによる分子量測定において２つのピークを示し、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２．０〜７．０の範囲である。
（ｄ）分子量分別した際のＭｎが１０万以上のフラクション中に長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有する。
（ｅ）密度が９１５〜９４０ｋｇ／ｍ３である。
（ｆ）ＭＦＲが０．１〜１５ｇ／１０分である。
That is, in the present invention, the ethylene-α-olefin copolymer (A) satisfying the following characteristics (a) to (d) is 5% by weight or more and less than 30% by weight, and the following characteristics (e) to (f) are satisfied. The present invention relates to a polyethylene resin composition containing the high-pressure low-density polyethylene (B) in an amount of more than 70% by weight and less than 95% by weight, and a medical container comprising the same.
(A) The density is 920 to 950 kg/m 3 .
(B) The melt flow rate (hereinafter referred to as MFR) is 0.1 to 15 g/10 minutes.
(C) Two peaks are shown in the molecular weight measurement by gel permeation chromatography, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 2.0 to 7.0. Is.
(D) 0.15 or more long chain branches per 1000 carbon atoms in the main chain are contained in the fraction having Mn of 100,000 or more when the molecular weight is fractionated.
(E) The density is 915 to 940 kg/m 3 .
(F) MFR is 0.1 to 15 g/10 minutes.
以下に、本発明のポリエチレン樹脂組成物およびそれよりなる医療容器について説明する。
［１］エチレン−α−オレフィン共重合体（Ａ）
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、エチレンとα−オレフィンを共重合したものであればよい。α−オレフィンとしては、例えばプロピレン、１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、３−メチル−１−ブテン等が挙げられ、これらのα−オレフィンを２種類以上併用してもよい。
The polyethylene resin composition of the present invention and a medical container made of the same will be described below.
[1] Ethylene-α-olefin copolymer (A)
The ethylene-α-olefin copolymer (A) according to the present invention may be a copolymer of ethylene and α-olefin. Examples of the α-olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, and the like. Even if two or more of these α-olefins are used in combination. Good.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、ＪＩＳ Ｋ６９２２−１に準拠し、１９０℃、荷重２．１６ｋｇで測定したＭＦＲが０．１〜１５ｇ／１０分、好ましくは０．１〜１０ｇ／１０分、より好ましくは０．１〜５ｇ／１０分である。ＭＦＲが０．１ｇ／１０分未満だと、成形加工時の押出負荷が大きくなると共に、成型時に表面荒れが発生するため好ましくない。また、ＭＦＲが１５ｇ／１０分を超える場合、ドローダウンが大きくなり、成型時の加工性が低下するため好ましくない。 The ethylene-α-olefin copolymer (A) according to the present invention has an MFR measured according to JIS K6922-1 at 190° C. and a load of 2.16 kg of 0.1 to 15 g/10 minutes, preferably 0.1. It is 1 to 10 g/10 minutes, more preferably 0.1 to 5 g/10 minutes. If the MFR is less than 0.1 g/10 min, the extrusion load during molding will be large and the surface will be roughened during molding, which is not preferable. Further, if the MFR exceeds 15 g/10 minutes, the drawdown becomes large and the workability at the time of molding deteriorates, which is not preferable.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、ＪＩＳ Ｋ６９２２−１に準拠した密度が９２０〜９５０ｋｇ／ｍ３の範囲であり、好ましくは９２５〜９４５ｋｇ／ｍ３、特に好ましくは９２５〜９３５ｋｇ／ｍ３の範囲である。密度が９２０ｋｇ／ｍ３未満だと耐熱性が不足し、９５０ｋｇ／ｍ３を超える場合は透明性が低下するため好ましくない。 Ethylene -α- olefin copolymer according to the present invention (A) has a density conforming to JIS K6922-1 ranges from 920~950kg / m 3, preferably 925~945kg / m 3, particularly preferably 925 The range is up to 935 kg/m 3 . If the density is less than 920 kg/m 3 , the heat resistance will be insufficient, and if it exceeds 950 kg/m 3 , the transparency will be reduced, which is not preferable.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、ゲル・パーミエーション・クロマトグラフィー（以下、ＧＰＣという。）による分子量測定において２つのピークを示す。ピークトップ分子量（Ｍｐ）はＧＰＣ測定によって得られた分子量分布曲線を後述の方法で２個のピークに分割し、高分子量側のピークと低分子量側のピークのトップ分子量を評価し、その差が１００，０００以上である場合を２つのＭｐを有するとした。１００，０００未満である場合は、実測された分子量分布曲線のトップ分子量を１つのＭｐとした。 The ethylene-α-olefin copolymer (A) according to the present invention shows two peaks in the molecular weight measurement by gel permeation chromatography (hereinafter, referred to as GPC). The peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described below and evaluating the top molecular weights of the high molecular weight side peak and the low molecular weight side peak, and the difference between them. When it was 100,000 or more, it was determined to have two Mp. When it was less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve was defined as one Mp.
分子量分布曲線の分割方法は以下のとおりに行った。ＧＰＣ測定によって得られた、分子量の対数であるＬｏｇＭに対して重量割合がプロットされた分子量分布曲線のＬｏｇＭに対して、標準偏差が０．３０であり、任意の平均値（ピークトップ位置の分子量）を有する２つの対数分布曲線を任意の割合で足し合わせることによって、合成曲線を作成する。さらに、実測された分子量分布曲線と合成曲線との同一分子量（Ｍ）値に対する重量割合の偏差平方和が最小値になるように、平均値と割合を求める。偏差平方和の最小値は、各ピークの割合がすべて０の場合の偏差平方和に対して０．５％以下にした。偏差平方和の最小値を与える平均値と割合が得られた時に、２つの対数正規分布曲線に分割して得られるそれぞれの対数分布曲線のピークトップの分子量をＭｐとした。 The method for dividing the molecular weight distribution curve was as follows. The standard deviation is 0.30 with respect to LogM of the molecular weight distribution curve in which the weight ratio is plotted against LogM, which is the logarithm of the molecular weight, obtained by GPC measurement, and any standard value (molecular weight at the peak top position ) Is added to create a synthetic curve. Further, the average value and the ratio are calculated so that the sum of squared deviations of the weight ratios with respect to the same molecular weight (M) value of the actually measured molecular weight distribution curve and the synthetic curve becomes the minimum value. The minimum value of the sum of squared deviations was 0.5% or less with respect to the sum of squared deviations when the ratio of each peak was all zero. The molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves when the average value and the ratio giving the minimum value of the sum of squared deviations were obtained was defined as Mp.
ＧＰＣによる分子量測定においてピークが１つのエチレン−α−オレフィン共重合体は、本発明のポリエチレン樹脂組成物を得るための一成分に使用しても、２つのピークを有するエチレン−α−オレフィン共重合体（Ｃ）を配合した場合のように透明性が高く、かつ滅菌処理後も透明性を維持した医療容器が得られない。 The ethylene-α-olefin copolymer having one peak in the molecular weight measurement by GPC has two peaks even if it is used as one component for obtaining the polyethylene resin composition of the present invention. It is not possible to obtain a medical container having high transparency as in the case of blending the combination (C) and maintaining the transparency even after sterilization.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２．０〜７．０、好ましくは２．５〜６．５、さらに好ましくは３．０〜６．０である。Ｍｗ／Ｍｎが２．０未満の場合は、成形加工時の押出負荷が大きいばかりでなく、得られた医療容器の外観（表面肌）が悪化するため好ましくない。Ｍｗ／Ｍｎが７．０を超えると得られた医療容器の強度が低下するばかりか、成形体を医療容器として使用した際に、充填した薬液中の微粒子が増加する恐れがある。 The ethylene-α-olefin copolymer (A) according to the present invention has a ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of 2.0 to 7.0, preferably 2. It is 5 to 6.5, and more preferably 3.0 to 6.0. When Mw/Mn is less than 2.0, not only the extrusion load during molding is large, but also the appearance (surface skin) of the obtained medical container is deteriorated, which is not preferable. When Mw/Mn exceeds 7.0, not only the strength of the obtained medical container is lowered, but also when the molded product is used as a medical container, the amount of fine particles in the filled liquid medicine may increase.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、ＧＰＣにより測定した数平均分子量（Ｍｎ）が１５，０００以上であることが好ましく、さらに好ましくは１５，０００〜１００，０００、特に１５，０００〜５０，０００が好ましい。Ｍｎが１５，０００以上である場合、得られた医療容器の強度が高くなる。 The ethylene-α-olefin copolymer (A) according to the present invention preferably has a number average molecular weight (Mn) measured by GPC of 15,000 or more, more preferably 15,000 to 100,000, particularly 15,000 to 50,000 is preferable. When Mn is 15,000 or more, the strength of the obtained medical container increases.
本発明に関わるエチレン−α−オレフィン共重合体（Ｃ）は、分子量分別で得られたＭｎが１０万以上のフラクションの長鎖分岐数が主鎖１０００炭素数あたり０．１５個以上である。Ｍｎが１０万以上のフラクションの長鎖分岐数が主鎖１０００炭素数あたり０．１５個未満である場合、本発明のポリエチレン樹脂組成物を得るための一成分に使用しても、顕著な透明性改良効果や、滅菌処理後の透明性維持効果は得られない。 In the ethylene-α-olefin copolymer (C) according to the present invention, the number of long chain branches of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is 0.15 or more per 1000 carbon atoms of the main chain. When the number of long chain branches in the fraction having Mn of 100,000 or more is less than 0.15 per 1000 carbon atoms in the main chain, even if it is used as one component for obtaining the polyethylene resin composition of the present invention, it is remarkably transparent. The effect of improving the transparency and the effect of maintaining transparency after sterilization cannot be obtained.
また、本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、分子量分別で得られたＭｎが１０万以上のフラクションの割合が、ポリマー全体の４０％未満であることが好ましい。分子量分別で得られたＭｎが１０万以上のフラクションの割合が、ポリマー全体の４０％未満である場合、成形加工時の押出負荷が大きくなりにくく、外観（表面肌）が平滑な医療容器が得られる。 Further, in the ethylene-α-olefin copolymer (A) according to the present invention, it is preferable that the ratio of the fraction having Mn of 100,000 or more obtained by molecular weight fractionation is less than 40% of the whole polymer. When the ratio of the Mn fraction of 100,000 or more obtained by molecular weight fractionation is less than 40% of the whole polymer, the extrusion load during molding is less likely to increase and a medical container with a smooth appearance (surface skin) is obtained. Be done.
本発明に関わるエチレン−α−オレフィン共重合体（Ａ）は、融点が１１５℃以上であることが好ましい。融点が１１５℃以上である場合は耐熱性に優れ、１１０℃で滅菌をした場合にも医療容器の変形が抑制され、滅菌後においても外観が良好な医療容器が得られる。
［２］高圧法低密度ポリエチレン（Ｂ）
本発明に用いる高圧法低密度ポリエチレン（Ｂ）は、ＪＩＳ Ｋ６９２２−１に準拠し、１９０℃、荷重２．１６ｋｇで測定したＭＦＲが０．１〜１５ｇ／１０分であり、０．１〜１０ｇ／１０分が好ましく、０．１〜５ｇ／１０分がより好ましく、特に０．１〜２ｇ／１０分が好ましい。ＭＦＲが０．１ｇ／１０分未満だと、成形加工時の押出負荷が大きくなると共に、成型時に表面荒れが発生するため好ましくない。また、ＭＦＲが１５ｇ／１０分を超える場合、ドローダウンが大きくなり、成型時の加工性が低下するため好ましくない。
The ethylene-α-olefin copolymer (A) according to the present invention preferably has a melting point of 115°C or higher. When the melting point is 115° C. or higher, heat resistance is excellent, deformation of the medical container is suppressed even when sterilized at 110° C., and a medical container having a good appearance even after sterilization can be obtained.
[2] High pressure low density polyethylene (B)
The high-pressure method low-density polyethylene (B) used in the present invention has an MFR of 0.1 to 15 g/10 min, measured at 190° C. and a load of 2.16 kg, according to JIS K6922-1, and 0.1 to 10 g. /10 minutes is preferable, 0.1-5 g/10 minutes is more preferable, and 0.1-2 g/10 minutes is particularly preferable. If the MFR is less than 0.1 g/10 min, the extrusion load during molding will be large and the surface will be roughened during molding, which is not preferable. Further, if the MFR exceeds 15 g/10 minutes, the drawdown becomes large and the workability at the time of molding deteriorates, which is not preferable.
本発明に関わる高圧法低密度ポリエチレン（Ｂ）は、ＪＩＳ Ｋ６９２２−１に準拠した密度が９１５〜９４０ｋｇ／ｍ３の範囲であり、好ましくは９２０〜９３５ｋｇ／ｍ３、特に好ましくは９２２〜９３２ｋｇ／ｍ３の範囲である。密度が９１５ｋｇ／ｍ３未満だと耐熱性が不足し、９４０ｋｇ／ｍ３を超える場合は透明性が低下するため好ましくない。 High-pressure low-density polyethylene according to the present invention (B) is in the range density conforming to JIS K6922-1 of 915~940kg / m 3, preferably 920~935kg / m 3, particularly preferably 922～932Kg / It is in the range of m 3 . Density insufficient heat resistance is less than 915 kg / m 3, is not preferred to lower the transparency when it exceeds 940 kg / m 3.
本発明に関わる高圧法低密度ポリエチレン（Ｂ）は、１種類のみを用いてもよいが、密度の異なる高圧法低密度ポリエチレン（Ｂ−１）及び高圧法低密度ポリエチレン（Ｂ−２）の２種を混合して使用する方が、透明性と耐熱性のバランスが向上するために好ましい。高圧法低密度ポリエチレン（Ｂ−１）及び高圧法低密度ポリエチレン（Ｂ−２）は、下記（ｉ）を満足する高圧法低密度ポリエチレン（Ｂ−１）と、下記（ｊ）を満足する高圧法低密度ポリエチレン（Ｂ−２）を用いることがより好ましい。
（ｉ）密度が９１５ｋｇ／ｍ３以上で９２５ｋｇ／ｍ３未満である。
（ｊ）密度が９２５ｋｇ／ｍ３以上で９４０ｋｇ／ｍ３以下である。
The high-pressure low-density polyethylene (B) according to the present invention may use only one kind, but it has two types of high-pressure low-density polyethylene (B-1) and high-pressure low-density polyethylene (B-2) having different densities. It is preferable to mix and use the seeds because the balance between transparency and heat resistance is improved. The high-pressure process low-density polyethylene (B-1) and the high-pressure process low-density polyethylene (B-2) are a high-pressure process low-density polyethylene (B-1) satisfying the following (i) and a high pressure satisfying the following (j). It is more preferable to use the method low density polyethylene (B-2).
(I) a density of less than 925 kg / m 3 at 915 kg / m 3 or more.
(J) The density is 925 kg/m 3 or more and 940 kg/m 3 or less.
高圧法低密度ポリエチレン（Ｂ−１）及び高圧法低密度ポリエチレン（Ｂ−２）の比率は、（Ｂ−１）／（（Ｂ−１）＋（Ｂ−２））が０．１〜０．６の範囲にあるのが好ましい。 The ratio of the high-pressure method low-density polyethylene (B-1) and the high-pressure method low-density polyethylene (B-2) is (B-1)/((B-1)+(B-2)) 0.1 to 0. It is preferably in the range of 0.6.
本発明のポリエチレン製医療容器に関わるエチレン−α−オレフィン共重合体（Ａ）は、例えば、特開２０１２−１２６８６２号公報、特開２０１２−１２６８６３号公報、特開２０１２−１５８６５４号公報、特開２０１２−１５８６５６号公報、特開２０１３−２８７０３号公報等に記載の方法により得ることができる。
［３］ポリエチレン樹脂組成物
本発明のポリエチレン製医療容器を製造するための樹脂材料は、エチレン−α−オレフィン共重合体（Ａ）と高圧法低密度ポリエチレン（Ｂ）を配合することにより、耐熱性と加工性を低下させることなく、透明性を高めた医療容器を製造することが可能となる。
Examples of the ethylene-α-olefin copolymer (A) relating to the polyethylene medical container of the present invention include, for example, JP2012-126862A, JP2012-126863A, JP2012-158654A, and JP2012-158654A. It can be obtained by the method described in 2012-158656, JP-A-2013-28703, or the like.
[3] Polyethylene resin composition The resin material for producing the polyethylene medical container of the present invention is heat resistant by blending the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B). It is possible to manufacture a medical container having enhanced transparency without deteriorating the workability and processability.
本発明に用いるエチレン−α−オレフィン共重合体（Ａ）および高圧法低密度ポリエチレン（Ｂ）の配合割合は、エチレン−α−オレフィン共重合体（Ａ）が５重量％以上３０重量％未満、好ましくは１０〜２５重量％、より好ましくは２０〜２５重量％、高圧法低密度ポリエチレン（Ｂ）が７０重量％を超えて９５重量％未満、好ましくは７５〜９０重量％、より好ましくは７５〜８０重量％である。エチレン−α−オレフィン共重合体（Ａ）が５重量％未満だと耐熱性が不足し、３０重量％を超える場合は、ドローダウンが大きくなり加工性が低下するため好ましくない。高圧法低密度ポリエチレン（Ｂ）が７０重量％以下だと加工性が低下し、９５重量％を超える場合は耐熱性が低下するため好ましくない。 The mixing ratio of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) used in the present invention is such that the ethylene-α-olefin copolymer (A) is 5% by weight or more and less than 30% by weight, Preferably 10 to 25% by weight, more preferably 20 to 25% by weight, high-pressure low density polyethylene (B) is more than 70% by weight and less than 95% by weight, preferably 75 to 90% by weight, more preferably 75 to 90% by weight. It is 80% by weight. When the ethylene-α-olefin copolymer (A) is less than 5% by weight, heat resistance is insufficient, and when it exceeds 30% by weight, drawdown becomes large and workability is deteriorated, which is not preferable. If the high-pressure low-density polyethylene (B) is 70% by weight or less, the processability is deteriorated, and if it exceeds 95% by weight, the heat resistance is deteriorated, which is not preferable.
エチレン−α−オレフィン共重合体（Ａ）を前記範囲内で配合した場合は、該エチレン−α−オレフィン共重合体（Ａ）を配合しない場合に比べて医療容器の耐熱性が向上すると共に、滅菌処理後も高いレベルの透明性を維持することが可能となる。 When the ethylene-α-olefin copolymer (A) is blended within the above range, the heat resistance of the medical container is improved as compared with the case where the ethylene-α-olefin copolymer (A) is not blended, It is possible to maintain a high level of transparency even after sterilization.
このような効果が発現する理由は、必ずしも明確ではないが、該エチレン−α−オレフィン共重合体（Ａ）を配合することで、冷却結晶化時に形成される球晶の大きさが著しく小さくなることが確認されており、該エチレン−α−オレフィン共重合体（Ａ）が成形過程および滅菌処理過程の球晶成長を阻害する効果を有するものと考えられる。 The reason why such an effect is exhibited is not always clear, but by blending the ethylene-α-olefin copolymer (A), the size of spherulites formed during cooling and crystallization is significantly reduced. It has been confirmed that the ethylene-α-olefin copolymer (A) has an effect of inhibiting spherulite growth in the molding process and the sterilization process.
これにより、本発明では、滅菌処理後も高いレベルの透明性を維持した医療容器を得ることができる。 Thus, in the present invention, it is possible to obtain a medical container that maintains a high level of transparency even after sterilization.
本発明のポリエチレン樹脂組成物は、エチレン−α−オレフィン共重合体（Ａ）、高圧法低密度ポリエチレン（Ｂ）を、従来公知の方法、例えば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等で混合する方法、あるいはこのような方法で得られた混合物をさらに一軸押出機、二軸押出機、ニーダー、バンバリーミキサー等で溶融混練した後、造粒することによって得ることができる。 The polyethylene resin composition of the present invention is obtained by using the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) in a conventionally known method, for example, a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender and the like. Can be obtained by melt-kneading the mixture obtained by the above method or the mixture obtained by such a method with a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer, etc., and then granulating.
本発明のポリエチレン樹脂組成物は、密度が９２５〜９３５ｋｇ／ｍ３の範囲にあることが、滅菌処理後の医療容器の耐熱性と透明性のバランスが特に優れるため、より好ましい。 The polyethylene resin composition of the present invention preferably has a density in the range of 925 to 935 kg/m 3 because the heat resistance and transparency of the medical container after sterilization are particularly excellent.
本発明のポリエチレン樹脂組成物には、本発明の効果を著しく損なわない範囲において、通常用いられる公知の添加剤、例えば酸化防止剤、帯電防止剤、滑剤、アンチブロッキング剤、防曇剤、有機系あるいは無機系の顔料、紫外線吸収剤、分散剤等を適宜必要に応じて配合することができる。本発明に関わる樹脂材料に前記の添加剤を配合する方法は特に制限されるものではないが、例えば、重合後のペレット造粒工程で直接添加する方法、また、予め高濃度のマスターバッチを作製し、これを成形時にドライブレンドする方法等が挙げられる。 In the polyethylene resin composition of the present invention, as long as the effect of the present invention is not significantly impaired, known additives commonly used, for example, antioxidants, antistatic agents, lubricants, antiblocking agents, antifog agents, organic systems are used. Alternatively, an inorganic pigment, an ultraviolet absorber, a dispersant, etc. can be appropriately added as needed. The method of blending the above-mentioned additive to the resin material according to the present invention is not particularly limited, but for example, a method of directly adding it in a pellet granulation step after polymerization, or preparing a high-concentration master batch in advance Then, a method of dry blending this during molding may be used.
また、本発明のポリエチレン樹脂組成物には、本発明の効果を損なわない程度の範囲内で、直鎖状低密度ポリエチレン、エチレン−プロピレン共重合体ゴム、ポリ−１−ブテン等の他の熱可塑性樹脂を配合して用いることもできる。
［４］医療容器
本発明のポリエチレン製医療容器は、薬液を収容する収容部を備えた医療容器であって、少なくとも収容部が前記［３］のポリエチレン樹脂組成物からなるものである。
In addition, the polyethylene resin composition of the present invention contains other heat-resistant materials such as linear low-density polyethylene, ethylene-propylene copolymer rubber, and poly-1-butene within a range that does not impair the effects of the present invention. It is also possible to mix and use a plastic resin.
[4] Medical Container The polyethylene medical container of the present invention is a medical container having a container for containing a drug solution, and at least the container is made of the polyethylene resin composition described in [3].
前記樹脂組成物を、ブロー成形等によりアンプル状またはボトル状に成形して、収容部を形成させることができる。ブロー成形では、前記エチレン−α−オレフィン共重合体（Ａ）と高圧法低密度ポリエチレン（Ｂ）の樹脂組成物からなるパリソンを押出し、金型でパリソンを挟み込んだ後、パリソン中に清浄エアーを吹き込むこと収容部を形成させることができる。また、ポート部の形成は、収容部との一体成形用金型を使用する方法、ポート部を収容部にヒートシールする方法、インサートブロー成形により収容部の成形と同時に一体化する方法等が挙げられる。 The accommodating portion can be formed by molding the resin composition into an ampoule shape or a bottle shape by blow molding or the like. In blow molding, a parison composed of the resin composition of the ethylene-α-olefin copolymer (A) and the high-pressure low-density polyethylene (B) is extruded, the parison is sandwiched by a mold, and then clean air is introduced into the parison. Blowing can form a housing. Further, the formation of the port portion includes a method of using a mold for integral molding with the housing portion, a method of heat sealing the port portion to the housing portion, a method of integrating the housing portion simultaneously with molding of the housing portion by insert blow molding, and the like. Be done.
本発明のポリエチレン樹脂組成物を使用して製造される医療容器の肉厚は特に限定されず、必要に応じて適宜決定することができるが、好ましくは０．０１〜１ｍｍ、より好ましくは０．１〜０．８ｍｍ、更に好ましくは０．３〜０．７ｍｍである。 The thickness of the medical container produced using the polyethylene resin composition of the present invention is not particularly limited and can be appropriately determined as necessary, but is preferably 0.01 to 1 mm, more preferably 0. It is 1 to 0.8 mm, more preferably 0.3 to 0.7 mm.
本発明の樹脂組成物を使用して製造される医療容器は、１１０℃での滅菌処理後において、純水中で波長４５０ｎｍで測定した光線透過率が５５％以上であるものが好ましい。光線透過率が５５％以上であると、異物の混入がないことや、薬剤配合による変化を目視で容易に確認できる。 A medical container produced using the resin composition of the present invention preferably has a light transmittance of 55% or more measured in pure water at a wavelength of 450 nm after sterilization treatment at 110°C. When the light transmittance is 55% or more, it is possible to easily confirm visually that a foreign substance is not mixed in and a change due to the drug formulation.
本発明の樹脂組成物を使用して製造される医療容器は、１１０℃での滅菌処理後においても変形が抑制される耐熱性を有しているものが好ましい。１１０℃の滅菌処理後においても変形が小さい場合は、１１０℃滅菌処理を行うことが可能であり、無菌状態を担保できる。 The medical container manufactured using the resin composition of the present invention preferably has heat resistance such that deformation is suppressed even after sterilization treatment at 110°C. If the deformation is small even after the sterilization treatment at 110° C., the sterilization treatment at 110° C. can be performed, and the aseptic condition can be secured.
本発明の樹脂組成物を用いて医療容器を製造する方法は特に限定されないが、ブロー成形法、インジェクションブロー成形法等が挙げられる。ブロー成形法やインジェクションブロー成形法を用いた場合、透明性、耐熱性、加工性等の点で多くの利点を有する。ブロー成形の場合は、耐熱性と透明性の観点から、医療容器の肉厚が０．５ｍｍ以上が好ましく、０．５〜０．６ｍｍがより好ましい。 The method for producing a medical container using the resin composition of the present invention is not particularly limited, and examples thereof include a blow molding method and an injection blow molding method. When the blow molding method or the injection blow molding method is used, there are many advantages in terms of transparency, heat resistance, processability, and the like. In the case of blow molding, from the viewpoint of heat resistance and transparency, the wall thickness of the medical container is preferably 0.5 mm or more, more preferably 0.5 to 0.6 mm.
本発明のポリエチレン組成物は、透明性、耐熱性、成形加工性に優れ、さらに滅菌処理後も透明性を維持できるため、高い透明性が求められる医療用のプラアンプルのような医療容器に好適に用いることができる。 The polyethylene composition of the present invention is excellent in transparency, heat resistance, moldability, and can maintain transparency even after sterilization treatment, and thus is suitable for medical containers such as plastic ampoules for which high transparency is required. Can be used.
以下に、実施例を示して本発明を更に詳細に説明するが、本発明はこれら実施例により制限されるものではない。
Ａ．樹脂材料
実施例、比較例に用いた樹脂材料の諸性質は下記の方法により評価した。
Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
A. Resin Material Various properties of the resin materials used in Examples and Comparative Examples were evaluated by the following methods.
＜分子量、分子量分布＞
重量平均分子量（Ｍｗ）、数平均分子量（Ｍｎ）、重量平均分子量と数平均分子量の比（Ｍｗ／Ｍｎ）およびピークトップ分子量（Ｍｐ）は、ＧＰＣによって測定した。ＧＰＣ装置（東ソー（株）製（商品名）ＨＬＣ−８１２１ＧＰＣ／ＨＴ）およびカラム（東ソー（株）製（商品名）ＴＳＫｇｅｌ ＧＭＨｈｒ−Ｈ（２０）ＨＴ）を用い、カラム温度を１４０℃に設定し、溶離液として１，２，４−トリクロロベンゼンを用いて測定した。測定試料は１．０ｍｇ／ｍｌの濃度で調製し、０．３ｍｌ注入して測定した。分子量の検量線は、分子量既知のポリスチレン試料を用いて校正した。なお、ＭｗおよびＭｎは直鎖状ポリエチレン換算の値として求めた。
<Molecular weight, molecular weight distribution>
The weight average molecular weight (Mw), the number average molecular weight (Mn), the ratio of the weight average molecular weight to the number average molecular weight (Mw/Mn), and the peak top molecular weight (Mp) were measured by GPC. A column temperature was set to 140° C. using a GPC device (Tosoh Corp. (trade name) HLC-8121GPC/HT) and a column (Tosoh Corp. (trade name) TSKgel GMHhr-H(20)HT). , 1,2,4-trichlorobenzene was used as an eluent. A measurement sample was prepared at a concentration of 1.0 mg/ml, and 0.3 ml was injected for measurement. The calibration curve of the molecular weight was calibrated using a polystyrene sample of known molecular weight. In addition, Mw and Mn were calculated as linear polyethylene conversion values.
＜分子量分別＞
分子量分別は、カラムとしてガラスビーズ充填カラム（直径：２１ｍｍ、長さ：６０ｃｍ）を用い、カラム温度を１３０℃に設定して、サンプル１ｇをキシレン３０ｍＬに溶解させたものを注入する。次に、キシレン／２−エトキシエタノールの比率が５／５のものを展開溶媒として用い、留出物を除去する。その後、キシレンを展開溶媒として用い、カラム中に残った成分を留出させ、ポリマー溶液を得る。得られたポリマー溶液に５倍量のメタノールを添加しポリマー分を沈殿させ、ろ過および乾燥することにより、Ｍｎが１０万以上である成分を回収した。
<Molecular weight fractionation>
For the molecular weight fractionation, a glass bead-packed column (diameter: 21 mm, length: 60 cm) is used as a column, the column temperature is set to 130° C., and 1 g of a sample dissolved in 30 mL of xylene is injected. Next, a distillate is removed by using a xylene/2-ethoxyethanol ratio of 5/5 as a developing solvent. Then, xylene is used as a developing solvent to distill off the components remaining in the column to obtain a polymer solution. A 5-fold amount of methanol was added to the obtained polymer solution to precipitate a polymer component, which was filtered and dried to recover a component having Mn of 100,000 or more.
＜長鎖分岐＞
長鎖分岐数は、日本電子（株）製ＪＮＭ−ＧＳＸ４００型核磁気共鳴装置を用いて、１３Ｃ−ＮＭＲによってヘキシル基以上の分岐数を測定した。溶媒はベンゼン−ｄ６／オルトジクロロベンゼン（体積比３０／７０）である。主鎖メチレン炭素（化学シフト：３０ｐｐｍ）１，０００個当たりの個数として、α−炭素（３４．６ｐｐｍ）およびβ−炭素（２７．３ｐｐｍ）のピークの平均値から求めた。
<Long-chain branch>
For the number of long chain branches, the number of branches of hexyl groups or more was measured by 13 C-NMR using a JNM-GSX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. The solvent is benzene-d6/orthodichlorobenzene (volume ratio 30/70). The number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).
＜密度＞
密度は、ＪＩＳ Ｋ６７６０（１９９５）に準拠して密度勾配管法で測定した。
<Density>
The density was measured by the density gradient tube method according to JIS K6760 (1995).
＜ＭＦＲ＞
ＭＦＲ（メルトフローレート）は、ＡＳＴＭ Ｄ１２３８条件Ｅに準ずる方法にて測定を行った。
<MFR>
The MFR (melt flow rate) was measured by a method according to ASTM D1238 condition E.
＜溶融張力＞
溶融張力の測定用試料は、サンプルに耐熱安定剤（チバスペシャリティケミカルズ社製、イルガノックス１０１０ＴＭ；１，５００ｐｐｍ、イルガフォス１６８ＴＭ；１，５００ｐｐｍ）を添加したものを、インターナルミキサー（東洋精機製作所製、商品名ラボプラストミル）を用いて、窒素気流下、１９０℃、回転数３０ｒｐｍで３０分間混練したものを用いた。
<Melt tension>
The sample for measuring the melt tension was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals Co., Irganox 1010TM; 1,500 ppm, Irgafos 168TM; 1,500 ppm) to an internal mixer (manufactured by Toyo Seiki Seisakusho, A product obtained by kneading for 30 minutes at 190° C. and a rotation speed of 30 rpm under a nitrogen stream was used.
溶融張力の測定は、バレル直径９．５５ｍｍの毛管粘度計（東洋精機製作所、商品名キャピログラフ）に、長さが８ｍｍ，直径が２．０９５ｍｍのダイスを流入角が９０°になるように装着し測定した。温度を１６０℃に設定し、ピストン降下速度を１０ｍｍ／分、延伸比を４７に設定し、引き取りに必要な荷重（ｍＮ）を溶融張力とした。最大延伸比が４７未満の場合、破断しない最高の延伸比での引き取りに必要な荷重（ｍＮ）を溶融張力とした。 To measure the melt tension, a capillary viscometer with a barrel diameter of 9.55 mm (Toyo Seiki Seisakusho, trade name Capillograph) was attached to a die with a length of 8 mm and a diameter of 2.095 mm at an inflow angle of 90°. It was measured. The temperature was set to 160° C., the piston descending speed was set to 10 mm/min, the stretching ratio was set to 47, and the load (mN) required for take-up was the melt tension. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.
＜融点＞
示差走査型熱量計、パーキンエルマー製「ＤＳＣ−７」を用いて測定した。装置内で試料を２２０℃で５分間融解させた後に、４０℃／分の冷却速度で４０℃まで冷却し、再度１０℃／分の昇温速度で２２０℃まで昇温させたときに得られる融解吸熱曲線のピーク温度を融点とした。
<Melting point>
The measurement was performed using a differential scanning calorimeter, "DSC-7" manufactured by Perkin Elmer. Obtained when the sample is melted at 220° C. for 5 minutes in the apparatus, then cooled to 40° C. at a cooling rate of 40° C./min, and again heated to 220° C. at a heating rate of 10° C./min. The peak temperature of the melting endothermic curve was taken as the melting point.
実施例、比較例では、下記の方法により製造した樹脂材料および市販品を用いた。
（１）エチレン−α−オレフィン共重合体（Ａ）
Ａ−１：
［変性粘土の調製］
１Ｌのフラスコに工業用アルコール（日本アルコール販売社製（商品名）エキネンＦ−３）３００ｍＬ及び蒸留水３００ｍＬを入れ、濃塩酸１７．５ｇ及びジメチルベヘニルアミン（ライオン株式会社製（商品名）アーミンＤＭ２２Ｄ）４９．４ｇ（１４０ｍｍｏｌ）を添加し、４５℃に加熱して合成ヘクトライト（Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ社製（商品名）ラポナイトＲＤＳ）を１００ｇ分散させた後、６０℃に昇温させてその温度を保持したまま１時間攪拌した。このスラリーを濾別後、６０℃の水６００ｍＬで２回洗浄し、８５℃の乾燥機内で１２時間乾燥させることにより１３２ｇの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を１５μｍとした。
［重合触媒の調製］
温度計と還流管が装着された３００ｍＬのフラスコを窒素置換した後に（１）で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍＬ入れ、次いでジメチルシリレン（シクロペンタジエニル）（２，４，７−トリメチルインデニル）ジルコニウムジクロリドを０．４４０６ｇ、及び２０％トリイソブチルアルミニウム１４２ｍＬを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍＬのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た（固形重量分：１２．４ｗｔ％）。
［重合］
２Ｌのオートクレーブにヘキサンを１．２Ｌ、２０％トリイソブチルアルミニウムを１．０ｍＬ、（２）で得られた触媒懸濁液を５２ｍｇ（固形分６．４ｍｇ相当）加え、７０℃に昇温後、１−ブテンを１７．６ｇ加え、分圧が０．８０ＭＰａになるようにエチレン／水素混合ガスを連続的に供給した（エチレン／水素混合ガス中の水素の濃度：５９０ｐｐｍ）。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで６１．８ｇのエチレン−α−オレフィン共重合体（イ）を得た（活性：９，７００ｇ／ｇ触媒）。このエチレン−α−オレフィン共重合体（イ）のＭＦＲは１．６ｇ／１０分、密度は９３０ｋｇ／ｍ３であり、融点は１１８．３℃であった。また、数平均分子量は１７，６００、重量平均分子量は８６，７００であり、分子量３０，５００および１５５，３００の位置にピークが観測された。また、ポリマー中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．１４個であり、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．２７個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの２０．１ｗｔ％であった。また、溶融張力は７５ｍＮであった。
Ａ−２：
［変性粘土の調製］
１Ｌのフラスコに工業用アルコール（日本アルコール販売社製（商品名）エキネンＦ−３）３００ｍＬ及び蒸留水３００ｍＬを入れ、濃塩酸１８．８ｇ及びジメチルヘキサコシルアミン（Ｍｅ２Ｎ（Ｃ２６Ｈ５３）、常法によって合成）４９．１ｇ（１２０ｍｍｏｌ）を添加し、４５℃に加熱して合成ヘクトライト（Ｒｏｃｋｗｏｏｄ Ａｄｄｉｔｉｖｅｓ社製（商品名）ラポナイトＲＤＳ）を１００ｇ分散させた後、６０℃に昇温させてその温度を保持したまま１時間攪拌した。このスラリーを濾別後、６０℃の水６００ｍＬで２回洗浄し、８５℃の乾燥機内で１２時間乾燥させることにより１４０ｇの有機変性粘土を得た。この有機変性粘土はジェットミル粉砕して、メジアン径を１４μｍとした。
［重合触媒の調製］
温度計と還流管が装着された３００ｍＬのフラスコを窒素置換した後に（１）で得られた有機変性粘土２５．０ｇとヘキサンを１０８ｍＬ入れ、次いでジメチルシリレン（シクロペンタジエニル）（２、４，７−トリメチル−１−インデニル）ジルコニウムジクロリドを０．４４０６ｇ、及び２０％トリイソブチルアルミニウム１４２ｍＬを添加して６０℃で３時間攪拌した。４５℃まで冷却した後に上澄み液を抜き取り、２００ｍＬのヘキサンにて５回洗浄後、ヘキサンを２００ｍｌ加えて触媒懸濁液を得た（固形重量分：１２．０ｗｔ％）
［重合］
２Ｌのオートクレーブにヘキサンを１．２Ｌ、２０％トリイソブチルアルミニウムを１．０ｍＬ、（２）で得られた触媒懸濁液を７５ｍｇ（固形分９．０ｍｇ相当）加え、８０℃に昇温後、１−ブテンを８．３ｇ加え、分圧が０．８５ＭＰａになるようにエチレン／水素混合ガスを連続的に供給した（エチレン／水素混合ガス中の水素の濃度：８５０ｐｐｍ）。９０分経過後に脱圧し、スラリーを濾別後、乾燥することで５８．５ｇのエチレン−α−オレフィン共重合体（イ）を得た（活性：６，５００ｇ／ｇ触媒）。このエチレン−α−オレフィン共重合体（イ）のＭＦＲは４．０ｇ／１０分、密度は９４１ｋｇ／ｍ３であり、融点は１２４．９℃であった。また、数平均分子量は２１，２００、重量平均分子量は７４，０００であり、分子量４１，５００および２１７，１００の位置にピークが観測された。また、ポリマー中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．０７個であり、分子量分別した際のＭｎ１０万以上のフラクション中に含まれる長鎖分岐数は、主鎖１０００炭素数あたり０．１８個であった。また、分子量分別した際のＭｎ１０万以上のフラクションの割合は、全ポリマーの１４．１ｗｔ％であった。また、溶融張力は４９ｍＮであった。
（２）高圧法低密度ポリエチレン（Ｂ）
ＬＤ−１：
東ソー（株）製、（商品名）ペトロセン １７３Ｋ（ＭＦＲ＝０．３ｇ／１０分、密度＝９２４ｋｇ／ｍ３）
ＬＤ−２：
東ソー（株）製、（商品名）ペトロセン ２２０Ｋ（ＭＦＲ＝１．０ｇ／１０分、密度＝９３１ｋｇｍ３）
（３）高密度ポリエチレン（Ｃ）
ＨＤ−１：
［変性粘土の調製］
脱イオン水４．８Ｌ、エタノール３．２Ｌの混合溶媒に、ジメチルベヘニルアミン；（Ｃ２２Ｈ４５）（ＣＨ３）２Ｎ ３５４ｇと３７％塩酸８３．３ｍＬを加え、ジメチルベヘニルアミン塩酸塩溶液を調製した。この溶液に合成ヘクトライト１，０００ｇを加え終夜撹拌し、得られた反応液をろ過した後、固体分を水で十分洗浄した。固体分を乾燥させたところ、１，１８０ｇの有機変性粘土化合物を得た。赤外線水分計で測定した含液量は０．８％であった。次に、この有機変性粘土化合物を粉砕し、平均粒径を６．０μｍに調製した。
［重合触媒の調製］
５Ｌのフラスコに、［変性粘土の調製］の項で得た有機変性粘土化合物４５０ｇ、ヘキサン１．４ｋｇを加え、その後トリイソブチルアルミニウムのヘキサン２０重量％溶液１．７８ｋｇ（１．８モル）、ビス（ｎ−ブチル−シクロペンタジエニル）ジルコニウムジクロライド７．３２ｇ（１８ミリモル）を加え、６０℃に加熱して１時間撹拌した。反応溶液を４５℃に冷却し、２時間静置した後に傾斜法で上澄液を除去した。次に、トリイソブチルアルミニウムのヘキサン１重量％溶液１．７８ｋｇ（０．０９モル）を添加し、４５℃で３０分間反応させた。反応溶液を４５℃で２時間静置した後に傾斜法で上澄液を除去し、トリイソブチルアルミニウムのヘキサン２０重量％溶液０．４５ｋｇ（０．４５モル）を加え、ヘキサンで再希釈して全量を４．５Ｌとし重合触媒を調製した。
［重合］
内容量３００Ｌの重合器に、ヘキサンを１３５ｋｇ／時、エチレンを２０．０ｋｇ／時、ブテン−１を０．３ｋｇ／時、水素５ＮＬ／時および［重合触媒の調製］の項で得られた重合触媒を連続的に供給した。また、助触媒として液中のトリイソブチルアルミニウムの濃度を０．９３ミリモル／ｋｇヘキサンとなるように、それぞれ連続的に供給した。重合温度は８５℃に制御した。得られた高密度ポリエチレン（Ｃ−１）はＭＦＲ＝１．０ｇ／１０分、密度９５２ｋｇ／ｍ３であった。
（４）直鎖状低密度ポリエチレン（Ｄ）
ＬＬ−１：
東ソー（株）製、（商品名）ニポロン−Ｚ ＨＦ２５０Ｋ（ＭＦＲ＝２．０ｇ／１０分、密度＝９３０ｋｇ／ｍ３、メタロセン触媒系）
Ｂ．医療容器
実施例、比較例に用いた医療容器は下記の方法により製造し、滅菌処理を行ない評価した。
＜樹脂ペレットの製造＞
上記のエチレン−α−オレフィン共重合体（Ａ）、高圧法低密度ポリエチレン（Ｂ）、高密度ポリエチレン（Ｃ）および直鎖状低密度ポリエチレン（Ｄ）を実施例、比較例に記載の比率でドライブレンドを行い、これをプラコー社製５０ｍｍ径単軸押出機にて溶融混合し、評価樹脂ペレットを作製した。バレルの温度はＣ１：１８０℃、Ｃ２：１９０℃、Ｃ３：２００℃、Ｃ４：２００℃、ダイヘッド：２００℃とした。
＜医療容器の製造＞
評価樹脂を１８０℃に設定した５０ｍｍφの押出スクリューを有するダイレクトブロー成型機（タハラ社製）に投入し、スクリュー回転数８ｒｐｍでパリソンを押し出して、内容積５００ｍＬのプラスチックボトルを作製した。ダイは長径１６．８ｍｍ、短径１６．５ｍｍの扁平ダイを用い、コアは１６．０ｍｍ径のものを用いた。このプラスチックボトルは、胴部の肉厚が０．５ｍｍであった。
In Examples and Comparative Examples, resin materials and commercially available products manufactured by the following methods were used.
(1) Ethylene-α-olefin copolymer (A)
A-1:
[Preparation of modified clay]
300 mL of industrial alcohol (Nippon Alcohol Sales Company (trade name) Ekinen F-3) and 300 mL of distilled water were put into a 1 L flask, concentrated hydrochloric acid 17.5 g and dimethylbehenylamine (Lion Co., Ltd. (trade name) Armin DM22D). ) 49.4 g (140 mmol) was added and heated to 45° C. to disperse 100 g of synthetic hectorite (Rackwood Additives (trade name) Laponite RDS), and then the temperature was raised to 60° C. to maintain the temperature. It was stirred for 1 hour. This slurry was separated by filtration, washed twice with 600 mL of water at 60° C., and dried in a dryer at 85° C. for 12 hours to obtain 132 g of organically modified clay. This organically modified clay was pulverized by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
After replacing a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2, 4, 0.4406 g of 7-trimethylindenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, and the mixture was stirred at 60° C. for 3 hours. After cooling to 45° C., the supernatant was taken out, washed with 200 mL of hexane 5 times, and 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt %).
[polymerization]
To a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 52 mg (corresponding to a solid content of 6.4 mg) of the catalyst suspension obtained in (2) were added, and the temperature was raised to 70°C. 17.6 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied so that the partial pressure became 0.80 MPa (hydrogen concentration in the ethylene/hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was released, the slurry was filtered off, and dried to obtain 61.8 g of ethylene-α-olefin copolymer (a) (activity: 9,700 g/g catalyst). The ethylene-α-olefin copolymer (a) had an MFR of 1.6 g/10 minutes, a density of 930 kg/m 3 and a melting point of 118.3°C. The number average molecular weight was 17,600, the weight average molecular weight was 86,700, and peaks were observed at the positions of molecular weights 30,500 and 155,300. The number of long-chain branches contained in the polymer is 0.14 per 1000 carbons of the main chain, and the number of long-chain branches contained in the fraction of Mn of 100,000 or more when the molecular weight is separated is 1000 carbons of the main chain. It was 0.27 per number. Further, the fraction of Mn of 100,000 or more when the molecular weight was fractionated was 20.1 wt% of the total polymer. The melt tension was 75 mN.
A-2:
[Preparation of modified clay]
300 mL of industrial alcohol (Nippon Alcohol Sales Company (trade name) Ekinen F-3) and 300 mL of distilled water were placed in a 1 L flask, concentrated hydrochloric acid 18.8 g and dimethylhexacosylamine (Me2N (C26H53), synthesized by a conventional method. ) 49.1 g (120 mmol) was added and heated to 45° C. to disperse 100 g of synthetic hectorite (Rackwood Additives (trade name) Laponite RDS), and then the temperature was raised to 60° C. to maintain the temperature. It was stirred for 1 hour. This slurry was separated by filtration, washed twice with 600 mL of water at 60° C., and dried in a dryer at 85° C. for 12 hours to obtain 140 g of organically modified clay. This organically modified clay was pulverized by a jet mill to have a median diameter of 14 μm.
[Preparation of polymerization catalyst]
After replacing a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2, 4, 0.4406 g of 7-trimethyl-1-indenyl)zirconium dichloride and 142 mL of 20% triisobutylaluminum were added, and the mixture was stirred at 60° C. for 3 hours. After cooling to 45° C., the supernatant was drawn off, washed 5 times with 200 mL of hexane, and 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt %).
[polymerization]
To a 2 L autoclave, 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 75 mg (corresponding to a solid content of 9.0 mg) of the catalyst suspension obtained in (2) were added, and the temperature was raised to 80°C. 8.3 g of 1-butene was added, and an ethylene/hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (hydrogen concentration in the ethylene/hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, the slurry was filtered off, and then dried to obtain 58.5 g of an ethylene-α-olefin copolymer (a) (activity: 6,500 g/g catalyst). The ethylene-α-olefin copolymer (a) had an MFR of 4.0 g/10 minutes, a density of 941 kg/m 3 , and a melting point of 124.9°C. The number average molecular weight was 21,200, the weight average molecular weight was 74,000, and peaks were observed at the positions of the molecular weights of 41,500 and 217,100. Further, the number of long chain branches contained in the polymer is 0.07 per 1000 carbon atoms of the main chain, and the number of long chain branches contained in the fraction having Mn of 100,000 or more when the molecular weight is fractionated is 1000 carbons of the main chain. The number was 0.18 per number. Further, the fraction of Mn of 100,000 or more when the molecular weight was fractionated was 14.1 wt% of the total polymer. The melt tension was 49 mN.
(2) High-pressure method low-density polyethylene (B)
LD-1:
Tosoh Corporation, (trade name) Petrosen 173K (MFR=0.3 g/10 minutes, density=924 kg/m 3 ).
LD-2:
Tosoh Corporation, (trade name) Petrosen 220K (MFR=1.0 g/10 minutes, density=931 kgm 3 ).
(3) High density polyethylene (C)
HD-1:
[Preparation of modified clay]
Deionized water 4.8 L, in a mixed solvent of ethanol 3.2 L, dimethyl behenyl amine; (C 22 H 45) ( CH 3) a 2 N 354 g 37% hydrochloric acid 83.3mL added dimethyl behenyl amine hydrochloride solution Prepared. To this solution, 1,000 g of synthetic hectorite was added, and the mixture was stirred overnight, the obtained reaction solution was filtered, and then the solid content was sufficiently washed with water. When the solid content was dried, 1,180 g of an organically modified clay compound was obtained. The liquid content measured by an infrared moisture meter was 0.8%. Next, the organically modified clay compound was pulverized to have an average particle size of 6.0 μm.
[Preparation of polymerization catalyst]
To a 5 L flask, 450 g of the organically modified clay compound obtained in the section of [Preparation of modified clay] and 1.4 kg of hexane were added, and then 1.78 kg (1.8 mol) of a 20% by weight hexane solution of triisobutylaluminum, bis. (32-Butyl-cyclopentadienyl)zirconium dichloride (7.32 g, 18 mmol) was added, and the mixture was heated to 60° C. and stirred for 1 hour. The reaction solution was cooled to 45° C., allowed to stand for 2 hours, and then the supernatant was removed by a gradient method. Next, 1.78 kg (0.09 mol) of a 1 wt% hexane solution of triisobutylaluminum was added, and the mixture was reacted at 45° C. for 30 minutes. After leaving the reaction solution at 45°C for 2 hours, the supernatant was removed by a gradient method, 0.45 kg (0.45 mol) of a 20% by weight hexane solution of triisobutylaluminum was added, and the solution was diluted with hexane to obtain the total amount. To 4.5 L to prepare a polymerization catalyst.
[polymerization]
In a polymerization vessel having an internal capacity of 300 L, hexane was 135 kg/hr, ethylene was 20.0 kg/hr, butene-1 was 0.3 kg/hr, hydrogen was 5 NL/hr, and the polymerization obtained in the section of [Preparation of polymerization catalyst] The catalyst was fed continuously. Further, triisobutylaluminum in the liquid as a co-catalyst was continuously supplied so that the concentration of the liquid was 0.93 mmol/kg hexane. The polymerization temperature was controlled at 85°C. The obtained high-density polyethylene (C-1) had an MFR of 1.0 g/10 minutes and a density of 952 kg/m 3 .
(4) Linear low density polyethylene (D)
LL-1:
Tosoh Corp. (trade name) Nipolon-Z HF250K (MFR=2.0 g/10 min, density=930 kg/m 3 , metallocene catalyst system)
B. Medical containers The medical containers used in Examples and Comparative Examples were manufactured by the following method, and sterilized for evaluation.
<Manufacture of resin pellets>
The above ethylene-α-olefin copolymer (A), high-pressure low-density polyethylene (B), high-density polyethylene (C) and linear low-density polyethylene (D) were used at the ratios described in Examples and Comparative Examples. Dry blending was performed, and this was melt-mixed with a 50 mm diameter single-screw extruder manufactured by Placo Co. to prepare resin pellets for evaluation. The barrel temperature was C1:180° C., C2:190° C., C3:200° C., C4:200° C., and die head: 200° C.
<Manufacture of medical containers>
The evaluation resin was put into a direct blow molding machine (manufactured by Tahara) having a 50 mmφ extrusion screw set to 180° C., and the parison was extruded at a screw rotation speed of 8 rpm to produce a plastic bottle having an internal volume of 500 mL. A flat die having a long diameter of 16.8 mm and a short diameter of 16.5 mm was used as a die, and a core having a diameter of 16.0 mm was used. The thickness of the body of this plastic bottle was 0.5 mm.
＜滅菌処理＞
前記医療容器を、蒸気滅菌装置（（株）日阪製作所製）を用いて、温度１１０℃で３０分間滅菌処理を行なった。
実施例、比較例に用いた医療容器の諸性質は下記の方法により評価した。
<Sterilization>
The medical container was sterilized at a temperature of 110° C. for 30 minutes using a steam sterilizer (manufactured by HISAKA CORPORATION).
The properties of the medical containers used in Examples and Comparative Examples were evaluated by the following methods.
＜加工性＞
ブロー成形機による、成型時の加工性を厚み計により評価した。
<Workability>
The workability at the time of molding by a blow molding machine was evaluated by a thickness meter.
○：パリソンコントロールの調整により、厚みが均一なボトルが得られた。 ◯: A bottle having a uniform thickness was obtained by adjusting the parison control.
×：パリソンコントロールを調整しても、厚みが不均一または０．５ｍｍでの成形できなかった。 X: Even if the parison control was adjusted, the thickness was not uniform or molding at 0.5 mm could not be performed.
＜肌＞
前記成型ボトルの表面状態を目視により観察、評価した。
<Skin>
The surface condition of the molded bottle was visually observed and evaluated.
○：表面平滑性良好
×：表面荒れ大
＜耐熱性＞
前記成形ボトルの形状を目視により観察、評価した。
○: Good surface smoothness ×: Large surface roughness <Heat resistance>
The shape of the molded bottle was visually observed and evaluated.
○：変形なしまたは変形小
×：変形大
また、示差走査型熱量計、パーキンエルマー製「ＤＳＣ−７」を用いて１１０℃残存結晶化度を測定した。前記成型ボトルからサンプルピースを切り出し、装置内で１０℃／分の昇温速度で２２０℃まで昇温して融解させたときに得られる融解吸熱曲線から、１１０℃以上の温度での吸熱量を求めた。吸熱量を２８８．７ｍＪ／ｍｇで除した値を１１０℃残存結晶化度として求めた。
◯: No deformation or small deformation x: Large deformation Further, the residual crystallinity was measured at 110° C. using a differential scanning calorimeter “DSC-7” manufactured by Perkin Elmer. From the melting endothermic curve obtained when a sample piece was cut out from the molding bottle and heated to 220° C. in the apparatus at a heating rate of 10° C./min to melt, the endothermic amount at a temperature of 110° C. or higher was determined. I asked. The value obtained by dividing the endotherm by 288.7 mJ/mg was determined as the 110° C. residual crystallinity.
目視評価が○で、かつ１１０℃残存結晶化度が２１．０％以上である場合に耐熱性良好とした。 When the visual evaluation was ◯ and the residual crystallinity at 110° C. was 21.0% or more, the heat resistance was good.
＜透明性＞
滅菌処理前後の前記成型ボトルから、幅１０ｍｍ×長さ５０ｍｍの試験片を切り出し、紫外可視分光光度計（型式２２０Ａ、日立製作所製）を用いて、純水中で波長４５０ｎｍにおける光線透過率を測定した。滅菌処理前、滅菌処理後それぞれで５５％以上の光線透過率が維持される場合を透明性が良好な医療容器の目安とした。
<Transparency>
A test piece with a width of 10 mm and a length of 50 mm was cut out from the molded bottle before and after the sterilization treatment, and the light transmittance at a wavelength of 450 nm was measured in pure water using an ultraviolet-visible spectrophotometer (model 220A, manufactured by Hitachi, Ltd.). did. The case where the light transmittance of 55% or more was maintained before and after the sterilization treatment was used as a standard for a medical container having good transparency.
実施例１
表１に示す樹脂材料を用いて、ブロー成型機により胴部の肉厚が０．５ｍｍ、内容積５００ｍＬの角型ボトルを成型し、加工性および肌、耐熱性（１１０℃残存結晶化度）、透明性（滅菌前光線透過率）を評価した。次いで、得られた成型ボトルに超純水を充填して密封した医療容器を作製して、１１０℃で３０分間高圧蒸気滅菌を行い、耐熱性（目視）、透明性（滅菌後光線透過率）を評価した。結果を表１に示す。
Example 1
Using the resin materials shown in Table 1, a blow molding machine was used to mold a rectangular bottle with a wall thickness of 0.5 mm and an internal volume of 500 mL, and the workability, skin, and heat resistance (110°C residual crystallinity) , And the transparency (light transmittance before sterilization) was evaluated. Then, the obtained molded bottle was filled with ultrapure water and sealed to prepare a medical container, which was subjected to high-pressure steam sterilization at 110°C for 30 minutes to obtain heat resistance (visual inspection) and transparency (light transmittance after sterilization). Was evaluated. The results are shown in Table 1.
実施例２〜４、参考例１
樹脂材料を表１に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表１に示す。
Examples 2 to 4, Reference Example 1
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 1. The results are shown in Table 1.
比較例１
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative Example 1
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
作製した成型ボトルは、１１０℃残存結晶化度が１１．８％と耐熱性に劣り、滅菌処理後に大きく変形してしまった。 The produced molded bottle had a residual crystallinity of 110° C. of 11.8%, which was inferior in heat resistance, and was greatly deformed after the sterilization treatment.
比較例２
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative example 2
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
作製した成型ボトルは、滅菌処理後に光線透過率が４８．２％まで低下してしまい、透明性に劣った。 The molded bottle produced had a light transmittance of 48.2% after sterilization, and thus was inferior in transparency.
比較例３
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative Example 3
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
作製した成型ボトルは、１１０℃残存結晶化度が２０．５％と耐熱性に劣り、滅菌処理後に大きく変形してしまった。 The produced molded bottle had a residual crystallinity of 110.degree. C. of 20.5%, which was inferior in heat resistance, and was greatly deformed after the sterilization treatment.
比較例４
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative Example 4
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
作製した成型ボトルは、滅菌処理前後に関わらず光線透過率が５５％未満であり、透明性に劣った。 The prepared molded bottle had a light transmittance of less than 55% before and after the sterilization treatment, and was inferior in transparency.
比較例５
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、結果を表２に示す。
Comparative Example 5
A plastic bottle was prepared in the same manner as in Example 1 except that the resin material was changed as shown in Table 2, and the results are shown in Table 2.
成型時のドローダウンが大きく、パリソンコントロールを調整しても、肉厚０．５ｍｍのボトルを成型することができなかった。 The drawdown during molding was large, and even if the parison control was adjusted, it was not possible to mold a bottle having a wall thickness of 0.5 mm.
比較例６
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative Example 6
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
作製した成型ボトルは、肌荒れが生じて、表面が平滑なボトルを作製することができなかった。 The molded bottle produced had rough skin, and it was not possible to produce a bottle having a smooth surface.
比較例７
樹脂材料を表２に示すように変更した以外は、実施例１と同様にしてプラスチックボトルを作製し、評価を行った。結果を表２に示す。
Comparative Example 7
A plastic bottle was prepared and evaluated in the same manner as in Example 1 except that the resin material was changed as shown in Table 2. The results are shown in Table 2.
成型時のドローダウンが大きく、パリソンコントロールを調整しても、肉厚０．５ｍｍのボトルを成型することができなかった。また、成型したボトルには肌荒れが生じていた。 The drawdown during molding was large, and even if the parison control was adjusted, it was not possible to mold a bottle having a wall thickness of 0.5 mm. Also, the molded bottle had rough skin.
Claims (8)
（ａ）密度が９２０〜９５０ｋｇ／ｍ３である。
（ｂ）ＭＦＲが０．１〜１５ｇ／１０分である。
（ｃ）ゲル・パーミエーション・クロマトグラフィーによる分子量測定において２つのピークを示し、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）の比（Ｍｗ／Ｍｎ）が２．０〜７．０の範囲である。
（ｄ）分子量分別した際のＭｎが１０万以上のフラクション中に長鎖分岐を主鎖１０００炭素数あたり０．１５個以上有する。
（ｅ）密度が９１５〜９４０ｋｇ／ｍ３である。
（ｆ）ＭＦＲが０．１〜１５ｇ／１０分である。
（ｉ）密度が９１５ｋｇ／ｍ ３ 以上で９２５ｋｇ／ｍ ３ 未満である。
（ｊ）密度が９２５ｋｇ／ｍ ３ 以上で９４０ｋｇ／ｍ ３ 以下である。 Ethylene-α-olefin copolymer (A) satisfying the following properties (a) to (d) 5% by weight or more and less than 30% by weight, and high-pressure low density polyethylene ((a) satisfying the following properties (e) to (f) ( B) Ri Do from 70 wt% 95 wt% greater than the following, the high-pressure low-density polyethylene (B) is high-pressure low-density polyethylene (B-1 satisfying the following (i)), and the following (j) A polyethylene resin composition comprising a mixture of two high-pressure low-density polyethylenes (B-2) which satisfy the requirements.
(A) The density is 920 to 950 kg/m 3 .
(B) MFR is 0.1 to 15 g/10 minutes.
(C) Two peaks are shown in the molecular weight measurement by gel permeation chromatography, and the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is in the range of 2.0 to 7.0. Is.
(D) 0.15 or more long chain branches per 1000 carbon atoms of the main chain are contained in the fraction having Mn of 100,000 or more when the molecular weight is fractionated.
(E) The density is 915 to 940 kg/m 3 .
(F) MFR is 0.1 to 15 g/10 minutes.
(I) a density of less than 925 kg / m 3 at 915 kg / m 3 or more.
(J) The density is 925 kg/m 3 or more and 940 kg/m 3 or less.
（ｇ）密度が９２５〜９３５ｋｇ／ｍ３である。 The polyethylene resin composition according to claim 1, wherein the ethylene-α-olefin copolymer (A) satisfies the following (g).
(G) The density is 925 to 935 kg/m 3 .
（ｈ）密度が９２０〜９３５ｋｇ／ｍ３である。 The polyethylene resin composition according to claim 1 or 2, wherein the high-pressure low-density polyethylene (B) satisfies the following (h).
(H) The density is 920 to 935 kg/m 3 .
（ｋ）（Ｂ−１）／（（Ｂ−１）＋（Ｂ−２））が０．１〜０．６である。 Polyethylene resin composition according to any one of claims 1 to 3, the ratio of the high-pressure low-density polyethylene (B-1) and high-pressure low-density polyethylene (B-2) satisfies the following (k).
(K)(B-1)/((B-1)+(B-2)) is 0.1 to 0.6.
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