JP6343886B2 - Polyethylene medical container - Google Patents

Polyethylene medical container Download PDF

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JP6343886B2
JP6343886B2 JP2013165145A JP2013165145A JP6343886B2 JP 6343886 B2 JP6343886 B2 JP 6343886B2 JP 2013165145 A JP2013165145 A JP 2013165145A JP 2013165145 A JP2013165145 A JP 2013165145A JP 6343886 B2 JP6343886 B2 JP 6343886B2
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明治 鶴田
明治 鶴田
晋平 濱
晋平 濱
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Tosoh Corp
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Description

本発明は、透明性、柔軟性、バリアー性、クリーン性(低微粒子性)に優れたポリエチレン製医療容器に関する。さらに詳しくは、滅菌処理による透明性の低下が少なく、水蒸気や酸素等の透過に対するバリア性に優れ、かつ、薬液中への微粒子の溶出が少ないため、輸液バッグやプラアンプルのような薬液、血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 medical container excellent in transparency, flexibility, barrier properties, and cleanliness (low particle size). More specifically, there is little loss of transparency due to sterilization, excellent barrier properties against permeation of water vapor, oxygen, etc., and there is little elution of fine particles into the drug solution, so drug solutions such as infusion bags and plastic ampules, blood, etc. It is related with the medical container made from polyethylene suitable for filling of.

薬液、血液等を充填する医療容器には、異物の混入や薬剤配合による変化を確認するための透明性、滅菌処理等に耐えられる耐熱性、薬液の排出を容易にするための柔軟性、容器内への水蒸気や酸素の滲入による薬液等の変質や品質の低下を抑制するためのガスバリア性、さらに容器からの微粒子溶出の低減(低微粒子性)などが要求される。   For medical containers filled with chemicals, blood, etc., transparency for confirming changes due to contamination of foreign substances and chemical composition, heat resistance that can withstand sterilization, flexibility for easy discharge of chemicals, containers Gas barrier properties for suppressing deterioration of quality and deterioration of chemicals due to intrusion of water vapor or oxygen into the inside, and reduction of fine particle elution from the container (low particle property) are required.

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、透明性や柔軟性を満足するために密度を低くすると耐熱性、ガスバリア性等が低下し、さらにクリーン性も悪化するなどの問題がある。   Conventionally, glass containers have been used as medical containers that satisfy such performance, but there are problems such as damage to the containers due to impact and dropping, contamination due to intrusion of outside air into the containers at the time of drug administration, etc. Plastic containers that have excellent impact properties, are flexible, and can be easily discharged are used. As the plastic container, a soft vinyl chloride resin, an ethylene-vinyl acetate copolymer resin, a polypropylene resin, and a polyethylene resin such as a high pressure method low density polyethylene, a linear low density polyethylene, and a high density polyethylene are used. However, soft vinyl chloride resin has problems in terms of hygiene, such as the plasticizer eluting into the chemical solution, ethylene-vinyl acetate copolymer resin is inferior in heat resistance, and polypropylene resin is flexible and clean (low particle size) Has become an issue. Also, in the case of polyethylene resins, there is a problem that if the density is lowered in order to satisfy transparency and flexibility, heat resistance, gas barrier properties and the like are lowered, and further cleanliness is deteriorated.

近年、透明性に優れるシングルサイト系触媒で製造された直鎖状ポリエチレンが開発され、それらを原料としたフィルムを積層させることで前記問題を解決する方法(特許文献1〜3参照)が提案されている。しかしながら、それらの方法においても透明性がなお不十分であり、滅菌処理により透明性が低下する問題は依然解決されていない。   In recent years, linear polyethylene manufactured with a single-site catalyst having excellent transparency has been developed, and a method (see Patent Documents 1 to 3) for solving the above-mentioned problem by laminating films made of these raw materials has been proposed. ing. However, the transparency is still insufficient in these methods, and the problem that transparency is reduced by sterilization has not been solved.

特開平8−309939号公報JP-A-8-309939 特開平7−125738号公報Japanese Patent Laid-Open No. 7-125738 特開平8−244791号公報JP-A-8-244791

本発明の目的は、従来のプラスチック製医療容器の欠点である透明性、柔軟性、バリアー性およびクリーン性(低微粒子性)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。   The object of the present invention is a polyethylene medical that is excellent in transparency, flexibility, barrier properties and cleanliness (low particle size), which are disadvantages of conventional plastic medical containers, and that maintains high transparency even after sterilization. To provide a container.

本発明者らは、鋭意検討を行なった結果、直鎖状低密度ポリエチレンに、特定の物性を有するエチレン系重合体を特定量配合し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 found that the above problem can be solved by blending a specific amount of an ethylene-based polymer having specific physical properties with a linear low density polyethylene into a medical container. The present invention has been completed.

すなわち、本発明は、下記特性(a)〜(b)を満足する直鎖状低密度ポリエチレン(A)95〜20重量%と下記特性(c)〜(f)を満足するエチレン系重合体(B)5〜80重量%((A)と(B)の合計は100重量%)を含む組成物からなることを特徴とするポリエチレン製医療容器に関するものである。
(a)密度が890〜940kg/mである。
(b)MFRが0.1〜15g/10分である。
(c)密度が920〜960kg/mである。
(d)MFRが0.1〜15g/10分である。
(e)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。
(f)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。
That is, the present invention relates to a linear low density polyethylene (A) 95 to 20% by weight satisfying the following characteristics (a) to (b) and an ethylene polymer satisfying the following characteristics (c) to (f) ( B) The present invention relates to a polyethylene medical container comprising a composition containing 5 to 80% by weight (the total of (A) and (B) is 100% by weight).
(A) The density is from 890 to 940 kg / m 3 .
(B) MFR is 0.1 to 15 g / 10 min.
(C) The density is 920 to 960 kg / m 3 .
(D) MFR is 0.1 to 15 g / 10 min.
(E) 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. It is.
(F) The fraction having a Mn of 100,000 or more when molecular weight fractionation has 0.15 or more long-chain branches per 1000 carbons of the main chain.

本発明に用いる直鎖状低密度ポリエチレン(A)とエチレン系重合体(B)の配合割合は、直鎖状低密度ポリエチレン(A)が95〜20重量%、好ましくは90〜30重量%、より好ましくは85〜40重量%、エチレン系重合体(B)が5〜80重量%、好ましくは10〜70重量%、より好ましくは15〜60重量%である。   The blending ratio of the linear low density polyethylene (A) and the ethylene polymer (B) used in the present invention is 95 to 20% by weight of the linear low density polyethylene (A), preferably 90 to 30% by weight, More preferably, it is 85 to 40% by weight, and the ethylene polymer (B) is 5 to 80% by weight, preferably 10 to 70% by weight, and more preferably 15 to 60% by weight.

直鎖状低密度ポリエチレン(A)が20重量%未満の場合(即ち、エチレン系重合体(B)が80重量%を超える場合)は、得られた医療容器の表面平滑性が悪化するため好ましくない。直鎖状低密度ポリエチレン(A)が95重量%を超える場合(即ち、エチレン系重合体(B)が5重量%未満の場合)は、溶融張力が不足し成形安定性が低下するため好ましくない。   When the linear low density polyethylene (A) is less than 20% by weight (that is, when the ethylene polymer (B) exceeds 80% by weight), the surface smoothness of the obtained medical container is deteriorated. Absent. When the linear low density polyethylene (A) exceeds 95% by weight (that is, when the ethylene polymer (B) is less than 5% by weight), the melt tension is insufficient and the molding stability is lowered, which is not preferable. .

さらに、エチレン系重合体(B)を前記範囲内で配合した場合は、該エチレン系重合体(B)を配合しない場合に比べて医療容器の透明性が大幅に向上すると共に、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。   Furthermore, when the ethylene polymer (B) is blended within the above range, the transparency of the medical container is greatly improved as compared with the case where the ethylene polymer (B) is not blended, and also after the sterilization treatment. A high level of transparency can be maintained.

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、該エチレン系重合体(B)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、該エチレン系重合体(B)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。
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。
The reason why such an effect appears is not necessarily clear, but it is confirmed that the size of the spherulites formed during cooling crystallization is remarkably reduced by blending the ethylene polymer (B). Thus, it is considered that the ethylene polymer (B) has an effect of inhibiting spherulite growth in the molding process and the sterilization process.
Thereby, in this invention, the medical container which maintained the high level transparency after the sterilization process can be obtained.

以下に、本発明の医療容器の製造に使用する樹脂材料について説明する。
[1]直鎖状低密度ポリエチレン(A)
本発明に用いる直鎖状低密度ポリエチレン(A)は、エチレンとα−オレフィンの共重合体である。
該直鎖状低密度ポリエチレン(A)は、JIS K6922−1に準拠し、190℃、荷重2.16kgで測定したMFRが0.1〜15.0g/10分、好ましくは0.5〜10.0g/10分、さらに好ましくは1.0〜5.0g/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、成形時に表面荒れが発生するため好ましくない。また、MFRが15.0g/10分を超える場合、成形安定性が低下するため好ましくない。
Below, the resin material used for manufacture of the medical container of this invention is demonstrated.
[1] Linear low density polyethylene (A)
The linear low density polyethylene (A) used in the present invention is a copolymer of ethylene and α-olefin.
The linear low density polyethylene (A) has an MFR of 0.1 to 15.0 g / 10 min, preferably 0.5 to 10 measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1. 0.0 g / 10 min, more preferably 1.0 to 5.0 g / 10 min. An MFR of less than 0.1 g / 10 minutes is not preferable because the extrusion load during molding increases and surface roughness occurs during molding. Moreover, when MFR exceeds 15.0 g / 10min, since molding stability falls, it is unpreferable.

該直鎖状低密度ポリエチレン(A)は、JIS K6922−1に準拠した密度が890〜940kg/m、好ましくは900〜930kg/mである。密度が890kg/m未満だと耐熱性が不足すると共に、容器に充填した薬液中の微粒子が増加し、クリーン性が低下する恐れがある。密度が940kg/mを超える場合は、透明性、柔軟性が低下するため好ましくない。 It said linear low density polyethylene (A) is, JIS density conforming to K6922-1 is 890~940kg / m 3, preferably 900~930kg / m 3. When the density is less than 890 kg / m 3 , the heat resistance is insufficient, and the fine particles in the chemical solution filled in the container increase, which may reduce the cleanliness. When the density exceeds 940 kg / m 3 , the transparency and flexibility are lowered, which is not preferable.

α−オレフィンとしては、一般にα−オレフィンと称されているものでよく、プロピレン、ブテン−1、ヘキセン−1、オクテン−1、4−メチル−1−ペンテン等の炭素数3〜12のα−オレフィンであることが好ましい。エチレンとα−オレフィンの共重合体としては、例えばエチレン・ヘキセン−1共重合体、エチレン・ブテン−1共重合体、エチレン・オクテン−1共重合体等が挙げられる。   The α-olefin may be generally referred to as α-olefin, and α-olefin having 3 to 12 carbon atoms such as propylene, butene-1, hexene-1, octene-1, and 4-methyl-1-pentene. Preferably it is an olefin. Examples of the copolymer of ethylene and α-olefin include an ethylene / hexene-1 copolymer, an ethylene / butene-1 copolymer, and an ethylene / octene-1 copolymer.

該直鎖状低密度ポリエチレン(A)は、例えば高圧法、溶液法、気相法等の製造法により製造することが可能である。該直鎖状低密度ポリエチレンを製造する際には、一般的にマグネシウムとチタンを含有する固体触媒成分及び有機アルミニウム化合物からなるチーグラー触媒、シクロペンタジエニル誘導体を含有する有機遷移金属化合物と、これと反応してイオン性の錯体を形成する化合物及び/又は有機金属化合物からなるメタロセン触媒、バナジウム系触媒等を用いることができ、該触媒によりエチレンとα−オレフィンを共重合することにより製造可能である。   The linear low density polyethylene (A) can be produced by a production method such as a high pressure method, a solution method, or a gas phase method. In producing the linear low-density polyethylene, generally, a solid catalyst component containing magnesium and titanium, a Ziegler catalyst comprising an organoaluminum compound, an organic transition metal compound containing a cyclopentadienyl derivative, and It is possible to use a metallocene catalyst, a vanadium-based catalyst, or the like comprising a compound and / or an organometallic compound that reacts with an ionic complex and can be produced by copolymerizing ethylene and an α-olefin using the catalyst. is there.

前記特性を有する直鎖状低密度ポリエチレン(A)は、後述するエチレン系重合体(B)と配合することで、成形容器の透明性向上効果および滅菌処理後の透明性維持効果が発現するが、直鎖状低密度ポリエチレン(A)が下記(g)〜(h)の特性を有する場合は、本発明の医療容器のクリーン性(低微粒子性)がさらに向上するため特に好ましい。このような(g)〜(h)の特性を有する直鎖状低密度ポリエチレン(A)は前記メタロセン触媒を用いることで製造することができる。
(g)ゲル・パーミエーション・クロマトグラフィーにより求められる重量平均分子量(Mw)と数平均分子量(Mn)の比(Mw/Mn)が3.0以下。
(h)50℃におけるn−ヘプタン抽出量が1.5wt%以下。
The linear low-density polyethylene (A) having the above-mentioned characteristics is blended with an ethylene polymer (B) described later, thereby exhibiting the effect of improving the transparency of the molded container and the effect of maintaining the transparency after sterilization. When the linear low density polyethylene (A) has the following properties (g) to (h), the cleanliness (low particle property) of the medical container of the present invention is further improved, which is particularly preferable. The linear low-density polyethylene (A) having the characteristics (g) to (h) can be produced by using the metallocene catalyst.
(G) The ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) determined by gel permeation chromatography is 3.0 or less.
(H) The amount of n-heptane extracted at 50 ° C. is 1.5 wt% or less.

前記の直鎖状低密度ポリエチレン(A)としては、市販品として入手したものであってもよく、例えば、東ソー(株)製(商品名)ニポロン−Z ZF220、東ソー(株)製(商品名)ニポロン−Z ZF260、東ソー(株)製(商品名)ニポロン−L F14等を挙げることができる。   As said linear low density polyethylene (A), what was obtained as a commercial item may be used, for example, Tosoh Co., Ltd. (brand name) Nipolon-Z ZF220, Tosoh Corporation (brand name) ) Nipolon-Z ZF260, Tosoh Corporation (trade name) Nipolon-LF14, and the like.

また、以下の方法により製造することができる。例えば、特開2013−81494公報等に記載の重合触媒の存在下に、エチレンと炭素数3〜8のα−オレフィンを共重合する方法を用いることができる。
[2]エチレン系重合体(B)
本発明に関わるエチレン系重合体(B)は、JIS K6922−1に準拠し、190℃、荷重2.16kgで測定したMFRが0.1〜15.0g/10分、好ましくは0.5〜10.0g/10分、より好ましくは1.0〜5.0g/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、成形時に表面荒れが発生するため好ましくない。また、MFRが15.0g/10分を超える場合、溶融張力が小さくなり、成形時の加工安定性が低下するため好ましくない。
Moreover, it can manufacture with the following method. For example, a method of copolymerizing ethylene and an α-olefin having 3 to 8 carbon atoms in the presence of a polymerization catalyst described in JP2013-81494A can be used.
[2] Ethylene polymer (B)
The ethylene polymer (B) according to the present invention has an MFR measured at 190 ° C. under a load of 2.16 kg in accordance with JIS K6922-1, 0.1 to 15.0 g / 10 min, preferably 0.5 to 10.0 g / 10 minutes, more preferably 1.0 to 5.0 g / 10 minutes. An MFR of less than 0.1 g / 10 minutes is not preferable because the extrusion load during molding increases and surface roughness occurs during molding. Moreover, when MFR exceeds 15.0 g / 10min, since melt tension becomes small and the processing stability at the time of shaping | molding falls, it is unpreferable.

本発明に関わるエチレン系重合体(B)は、JIS K6922−1に準拠した密度が920〜960kg/mの範囲であり、好ましくは925〜955kg/m、特に好ましくは930〜950kg/mの範囲である。密度が920kg/m未満だと耐熱性が不足し、960kg/mを超える場合は透明性、柔軟性が低下するため好ましくない。 Ethylene polymer according to the present invention (B) is in the range density conforming to JIS K6922-1 of 920~960kg / m 3, preferably 925~955kg / m 3, particularly preferably 930~950kg / m 3 range. When the density is less than 920 kg / m 3 , the heat resistance is insufficient, and when it exceeds 960 kg / m 3 , the transparency and flexibility are undesirably lowered.

本発明に関わるエチレン系重合体(B)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 polymer (B) according to the present invention exhibits two peaks in 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 later, and evaluating the top molecular weight of the high molecular weight side peak and the low molecular weight side peak. The case of 100,000 or more was assumed 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 molecular weight distribution curve was divided 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 molecular weight obtained by GPC measurement, and an arbitrary average value (molecular weight at the peak top position) A composite curve is created by adding together two logarithmic distribution curves having) at an arbitrary ratio. Further, the average value and the ratio are obtained so that the deviation sum of squares of the weight ratio with respect to the same molecular weight (M) value of the actually measured molecular weight distribution curve and the composite curve becomes a minimum value. The minimum value of the deviation sum of squares was set to 0.5% or less with respect to the deviation sum of squares when the ratios of the respective peaks were all zero. When the average value and the ratio giving the minimum value of the deviation sum of squares were obtained, the molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves was defined as Mp.

GPCによる分子量測定においてピークが1つのエチレン系重合体は、本発明に関わる直鎖状低密度ポリエチレン(A)に配合しても、2つのピークを有するエチレン系重合体(B)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。   When the ethylene polymer having one peak in the molecular weight measurement by GPC is blended with the linear low density polyethylene (A) according to the present invention, the ethylene polymer (B) having two peaks is blended. Thus, a medical container having high transparency and maintaining transparency even after sterilization treatment cannot be obtained.

本発明に関わるエチレン系重合体(B)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を越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 polymer (B) according to the present invention has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn) of 2.0 to 7.0, preferably 2.5 to 6. 5, More preferably, it is 3.0-6.0. When Mw / Mn is less than 2.0, not only the extrusion load at the time of molding is large, but also the appearance (surface skin) of the obtained medical container is deteriorated. 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, there is a possibility that the fine particles in the filled chemical solution increase.

本発明に関わるエチレン系重合体(B)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 polymer (B) 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 preferred. When Mn is 15,000 or more, the strength of the obtained medical container is increased.

本発明に関わるエチレン系重合体(B)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、本発明に関わる直鎖状低密度ポリエチレン(A)に特定量配合しても、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-based polymer (B) 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 carbons of the main chain. When the number of long-chain branches in the fraction with Mn of 100,000 or more is less than 0.15 per 1000 carbons of the main chain, even if a specific amount is blended with the linear low-density polyethylene (A) according to the present invention, it is remarkable The effect of improving transparency and maintaining transparency after sterilization cannot be obtained.

また、本発明に関わるエチレン系重合体(B)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、エチレン系重合体(B)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、エチレン系重合体(B)全体の40%未満である場合、成形加工時の押出負荷が小さく、得られた医療容器の外観(表面肌)が良好である。   Moreover, it is preferable that the ratio of the fraction whose Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the whole ethylene polymer (B). When the proportion of the fraction of Mn obtained by molecular weight fractionation is 100,000 or more is less than 40% of the entire ethylene polymer (B), the extrusion load during molding is small, and the appearance of the obtained medical container ( Surface skin) is good.

以上、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として、直鎖状低密度ポリエチレン(A)にエチレン系重合体(B)を配合することにより、耐熱性を低下させることなく、透明性を大幅に高めることが可能となる。さらには、驚くべきことに、該エチレン系重合体(B)を配合して製造した医療容器は、ガスバリア性、クリーン性(低微粒子性)が大幅に改善されることが判明した。   As described above, as a resin material for producing the polyethylene medical container of the present invention, by blending the ethylene-based polymer (B) with the linear low density polyethylene (A), it is transparent without reducing heat resistance. It is possible to greatly improve the performance. Furthermore, surprisingly, it has been found that a medical container manufactured by blending the ethylene polymer (B) has a significantly improved gas barrier property and clean property (low particle size).

本発明のポリエチレン製医療容器に関わるエチレン系重合体(B)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。又、市販品として、(商品名)TOSOH−HMS CK37、CK47(以上、東ソー(株)製)等を用いることができる。
[3]樹脂組成物
本発明のポリエチレン製医療容器の製造に用いる樹脂組成物は、直鎖状低密度ポリエチレン(A)とエチレン系重合体(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。
Examples of the ethylene polymer (B) related to the polyethylene medical container of the present invention include JP2012-126862A, JP2012-126863A, JP2012-158654A, and JP2012-158656A. It can obtain by the method as described in gazette, Unexamined-Japanese-Patent No. 2013-28703, etc. Moreover, (trade name) TOSOH-HMS CK37, CK47 (above, Tosoh Co., Ltd. product) etc. can be used as a commercial item.
[3] Resin composition The resin composition used for the production of the polyethylene medical container of the present invention is a linear low-density polyethylene (A) and an ethylene polymer (B) obtained by a conventionally known method such as a Henschel mixer, A method of mixing with a V-blender, ribbon blender, tumbler blender, or the like, or a mixture obtained by such a method is further melt-kneaded with a single screw extruder, twin screw extruder, kneader, Banbury mixer, etc., and granulated. Can be obtained.

本発明のポリエチレン製医療容器の製造に用いる樹脂組成物は、密度が915〜930kg/mの範囲にあることが、滅菌処理後の医療容器の柔軟性と透明性のバランスが特に優れるため、より好ましい。 Since the resin composition used in the production of the polyethylene medical container of the present invention has a density in the range of 915 to 930 kg / m 3 , the balance between flexibility and transparency of the medical container after sterilization is particularly excellent, More preferred.

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組成物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。
また、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組成物には、本発明の効果を損なわない程度の範囲内で、高密度ポリエチレン、高圧法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直鎖状低密度ポリエチレン(A)とエチレン系重合体(B)を含む組成物からなるものである。
In the resin composition for producing the polyethylene medical container of the present invention, known additives generally used, for example, an antioxidant, an antistatic agent, a lubricant, and an anti-blocking, within a range that does not significantly impair the effects of the present invention. An agent, an antifogging agent, an organic or inorganic pigment, an ultraviolet absorber, a dispersant and the like can be appropriately blended as necessary. The method of blending the above-mentioned additives into the resin composition according to the present invention is not particularly limited. For example, a method of directly adding in the pellet granulation step after polymerization, or a high-concentration master batch in advance. The method of producing and dry blending this at the time of shaping | molding etc. is mentioned.
In addition, the resin composition for producing the polyethylene medical container of the present invention includes a high-density polyethylene, a high-pressure method low-density polyethylene, and an ethylene-propylene copolymer rubber as long as the effects of the present invention are not impaired. Also, other thermoplastic resins such as poly-1-butene can be blended and used.
[4] Medical container The polyethylene medical container of the present invention is a medical container provided with a storage part for storing a chemical solution, and at least the storage part is a linear low density polyethylene (A) and an ethylene-based polymer (B). It consists of a composition containing.

前記組成物を、水冷式インフレーション成形、空冷式インフレーション成形、キャスト成形等によりフィルム状に成形した場合は、得られたフィルムを2枚重ね合わせて、周辺部をヒートシールすることで、袋状の収容部を成形することができる。また、得られたフィルムを真空成形、圧空成形などの熱板成形により、収容部となる凹部を成形した後、凹部同士が対向するように重ね合わせて、周辺部をヒートシールすることで収容部を成形することもできる。この際、薬液の注出入口となるポート部は、前記収容部の成形時に同時にヒートシールして形成させてもよいし、収容部の形成とポート部の形成を別工程で行なうことも可能である。   When the composition is formed into a film by water-cooled inflation molding, air-cooled inflation molding, cast molding, or the like, two sheets of the obtained films are overlapped, and the peripheral part is heat-sealed, so that a bag-like shape is obtained. The accommodating part can be molded. Moreover, after forming the recessed part used as an accommodating part by hot plate shaping | molding, such as vacuum forming and pressure forming, the obtained film is overlap | superposed so that recessed parts may oppose, and an accommodating part is heat-sealed by a peripheral part Can also be molded. At this time, the port portion that serves as the chemical liquid inlet may be formed by heat sealing at the same time as the housing portion is formed, or the housing portion and the port portion may be formed in separate steps. .

前記配合物を、ブロー成形等によりボトル状に成形して、収容部を形成させることも可能である。ブロー成形では、前記直鎖状低密度ポリエチレン(A)とエチレン系重合体(B)の配合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で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。   It is also possible to form the container by forming the compound into a bottle by blow molding or the like. In blow molding, a parison made of a blend of the above-mentioned linear low density polyethylene (A) and ethylene polymer (B) is extruded, the parison is sandwiched between molds, and then clean air is blown into the parison. The part can be formed. In addition, the formation of the port part includes a method of using a mold for integral molding with the accommodating part, a method of heat-sealing the port part to the accommodating part, a method of integrating the accommodating part at the same time by insert blow molding, and the like. It is done.

本発明のポリエチレン製医療容器の厚みは特に限定されず、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0.1〜0.5mmである。   The thickness of the polyethylene medical container 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 0.1 to 0.5 mm.

本発明の医療容器を製造する方法は特に限定されないが、水冷式または空冷式インフレーション成形 法、キャスト成形法、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。これらの中で、水冷式インフレーション成形法を用いるのが、透明性、衛生性等の点で多くの利点を有する。   A method for producing the medical container of the present invention is not particularly limited, and examples thereof include a water-cooled or air-cooled inflation molding method, a cast molding method, a blow molding method, and an injection blow molding method. Among these, the use of the water-cooled inflation molding method has many advantages in terms of transparency and hygiene.

また、ブロー成形により、容器を成形すると同時に容器内に薬液を充填する同時充填ブロー成形法を用いた場合は、衛生性、生産性等の点で多くの利点を有する。   In addition, when a simultaneous filling blow molding method in which a container is filled with a chemical solution at the same time as molding by blow molding, there are many advantages in terms of hygiene, productivity, and the like.

本発明のポリエチレン製医療容器の用途としては、医療関係全般に用いることができ、例えば血液バッグ、血小板保存バッグ、輸液(薬液)バッグ、医療用複室容器、人工透析用バッグ、点眼用アンプル等が挙げられる。   Applications of the polyethylene medical container of the present invention can be used in general medical applications, such as blood bags, platelet storage bags, infusion (medical solution) bags, medical multi-chamber containers, artificial dialysis bags, eye drop ampoules, etc. Is mentioned.

本発明のポリエチレン製医療容器は、透明性、柔軟性、バリアー性およびクリーン性(低微粒子性)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輸液バッグや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 medical container of the present invention is excellent in transparency, flexibility, barrier properties and cleanliness (low particle size), and can maintain transparency even after sterilization treatment, and therefore, a medical infusion solution that requires high transparency. It can be suitably used for medical containers such as bags and plastic ampules.

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
実施例、比較例に用いた樹脂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. Resins Various properties of the resins 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>
Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and peak top molecular weight (Mp) were measured by GPC. The column temperature was set to 140 ° C. using a GPC device (trade name: HLC-8121 GPC / HT, manufactured by Tosoh Corporation) and a column (trade name: TSKgel GMHhr-H (20) HT, manufactured by Tosoh Corporation). The measurement was performed using 1,2,4-trichlorobenzene as an eluent. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

<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 molecular weight fractionation, a glass bead packed column (diameter: 21 mm, length: 60 cm) is used as the column, the column temperature is set to 130 ° C., and 1 g of sample dissolved in 30 mL of xylene is injected. Next, distillate is removed by using a xylene / 2-ethoxyethanol ratio of 5/5 as a developing solvent. Thereafter, using xylene as a developing solvent, the components remaining in the column are distilled off to obtain a polymer solution. A component having Mn of 100,000 or more was recovered by adding 5-fold amount of methanol to the obtained polymer solution to precipitate the polymer, filtering and drying.

<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 branching>
The number of long chain branches was determined by 13 C-NMR using a JNM-GSX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. and the number of branches equal to or greater than the hexyl group. 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).

<n−ヘプタン抽出量>
200メッシュパスの粉砕試料約10gを精秤し、400mlのn−ヘプタンを加えて50℃で2時間抽出を行い、抽出液から溶媒を蒸発させて、乾燥固化させて得た抽出物の重量の初期重量に対する百分率を求めることによって算出した。
<密度>
密度は、JIS K6922−1に準拠して密度勾配管法で測定した。
<Extracted amount of n-heptane>
About 10 g of a 200 mesh pass crushed sample is precisely weighed, 400 ml of n-heptane is added, extraction is performed at 50 ° C. for 2 hours, the solvent is evaporated from the extract, and the weight of the extract obtained by drying and solidifying is measured. It was calculated by determining the percentage with respect to the initial weight.
<Density>
The density was measured by a density gradient tube method in accordance with JIS K6922-1.

<MFR>
MFR(メルトフローレート)は、JIS K6922−1に準拠して測定を行った。
<MFR>
MFR (melt flow rate) was measured according to JIS K6922-1.

<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。
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。
<Melting tension>
The sample for melt tension measurement was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgaphos 168TM; 1,500 ppm) to an internal mixer (Toyo Seiki Seisakusho, The product kneaded for 30 minutes at 190 ° C. and 30 rpm in a nitrogen stream was used.
To measure the melt tension, a capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is attached with a die with a length of 8 mm and a diameter of 2.095 mm so that the inflow angle is 90 °. It was measured. The temperature was set to 160 ° C., the piston lowering speed was set to 10 mm / min, the stretch 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.

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)直鎖状低密度ポリエチレン
LL−1
[変性粘土の調製]
水1,500mlに37%塩酸30mlおよびN,N−ジメチル−ベヘニルアミンを106g加え、N,N−ジメチル−ベヘニルアンモニウム塩酸塩水溶液を調製した。平均粒径7.8μmのモンモリロナイト300g(クニミネ工業製、商品名クニピアFをジェット粉砕機で粉砕することによって調製した)を上記塩酸塩水溶液に加え、6時間反応させた。反応終了後、反応溶液を濾過し、得られたケーキを6時間減圧乾燥し、変性粘土化合物370gを得た。
[重合触媒の調製]
窒素雰囲気下の20Lステンレス容器にヘプタン2.5L、トリエチルアルミニウムのヘプタン溶液(20wt%希釈品)をアルミニウム原子当たり4.5mol(3.6L)および上記で得られた変性粘土化合物300gを加えて1時間撹拌した。そこへジフェニルメチレン(シクロペンタジエニル)(2,7−ジ−t−ブチル−9−フルオレニル)ジルコニウムジクロライドをジルコニウム原子当たり10mmol加えて12時間撹拌した.得られた懸濁系に脂肪族系飽和炭化水素溶媒(出光石油化学製、商品名IPソルベント2835)8.7Lを加えることにより、触媒を調製した。(ジルコニウム濃度0.67mmol/L)。
[LL−1の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1−ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1−ヘキセン濃度を10mol%、水素濃度を5mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン(LL−1)はMFR=3.6g/10分、密度931kg/mであった。LL−1の基本特性評価結果を表1に示す。
In Examples and Comparative Examples, resin materials produced by the following method and commercially available products were used.
(1) Linear low density polyethylene LL-1
[Preparation of modified clay]
To 1,500 ml of water, 30 ml of 37% hydrochloric acid and 106 g of N, N-dimethyl-behenylamine were added to prepare an aqueous solution of N, N-dimethyl-behenylammonium hydrochloride. 300 g of montmorillonite having an average particle size of 7.8 μm (manufactured by Kunimine Kogyo Co., Ltd., prepared by pulverizing trade name Kunipia F with a jet pulverizer) was added to the above hydrochloride aqueous solution and reacted for 6 hours. After completion of the reaction, the reaction solution was filtered, and the resulting cake was dried under reduced pressure for 6 hours to obtain 370 g of a modified clay compound.
[Preparation of polymerization catalyst]
To a 20 L stainless steel container in a nitrogen atmosphere, add 2.5 L of heptane, a heptane solution of triethylaluminum (diluted at 20 wt%), 4.5 mol (3.6 L) per aluminum atom, and 300 g of the modified clay compound obtained above. Stir for hours. Diphenylmethylene (cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride was added thereto in an amount of 10 mmol per zirconium atom, and the mixture was stirred for 12 hours. A catalyst was prepared by adding 8.7 L of an aliphatic saturated hydrocarbon solvent (trade name IP Solvent 2835, manufactured by Idemitsu Petrochemical Co., Ltd.) to the obtained suspension system. (Zirconium concentration 0.67 mmol / L).
[Manufacture of LL-1]
Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 10 mol%, and the hydrogen concentration was 5 mol%. Was set to be. And the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed. The obtained linear low density polyethylene (LL-1) had MFR = 3.6 g / 10 min and a density of 931 kg / m 3 . Table 1 shows the basic characteristic evaluation results of LL-1.

LL−2
[変性粘土の調製]
LL−1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
LL−1と同様の方法により重合触媒を調製した。
[LL−2の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1−ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1−ヘキセン濃度を20mol%、水素濃度を4mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン(LL−2)はMFR=2.5g/10分、密度921kg/mであった。LL−2の基本特性評価結果を表1に示す。
LL-2
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared by the same method as LL-1.
[Manufacture of LL-2]
Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 20 mol%, and the hydrogen concentration was 4 mol%. Was set to be. And the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed. The obtained linear low density polyethylene (LL-2) had MFR = 2.5 g / 10 min and a density of 921 kg / m 3 . The basic characteristic evaluation results of LL-2 are shown in Table 1.

LL−3
[変性粘土の調製]
LL−1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
窒素雰囲気下の20Lステンレス容器にヘプタン3.3L、トリエチルアルミニウムのヘプタン溶液(20wt%希釈品)をアルミニウム原子当たり1.13mol(0.9L)および上記で得られた変性粘土化合物50gを加えて1時間撹拌した。そこへジフェニルメチレン(4−フェニル−インデニル)(2,7−ジ−t−ブチル−9−フルオレニル)ジルコニウムジクロライドをジルコニウム原子当たり1.25mmol加えて12時間撹拌した.得られた懸濁系に脂肪族系飽和炭化水素溶媒(出光石油化学製、商品名IPソルベント2835)5.8Lを加えることにより、触媒を調製した。(ジルコニウム濃度0.125mmol/L)。
[LL−3の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1−ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1−ヘキセン濃度を23mol%、水素濃度を1mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン(LL−3)はMFR=0.8g/10分、密度900kg/mであった。LL−3の基本特性評価結果を表1に示す。
LL-3
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
To a 20 L stainless steel container under a nitrogen atmosphere, add 3.3 L of heptane, a heptane solution of triethylaluminum (diluted 20 wt%) 1.13 mol (0.9 L) per aluminum atom, and 50 g of the modified clay compound obtained above. Stir for hours. Thereto was added 1.25 mmol of diphenylmethylene (4-phenyl-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride per zirconium atom, and the mixture was stirred for 12 hours. A catalyst was prepared by adding 5.8 L of an aliphatic saturated hydrocarbon solvent (trade name IP Solvent 2835, manufactured by Idemitsu Petrochemical Co., Ltd.) to the obtained suspension system. (Zirconium concentration 0.125 mmol / L).
[Manufacture of LL-3]
Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 23 mol%, and the hydrogen concentration was 1 mol%. Was set to be. And the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed. The obtained linear low density polyethylene (LL-3) had MFR = 0.8 g / 10 minutes and a density of 900 kg / m 3 . Table 1 shows the basic characteristic evaluation results of LL-3.

LL−4
[変性粘土の調製]
LL−1と同様の方法により変性粘土化合物を調製した。
[重合触媒の調製]
LL−3と同様の方法により重合触媒を調製した。
[LL−4の製造]
高温高圧重合用に装備された槽型反応器を用い、エチレンおよび1−ヘキセンを連続的に反応器に圧入して、全圧を90MPa、1−ヘキセン濃度を20mol%、水素濃度を15mol%になるように設定した。そして反応器を1,500rpmで撹拌し、上記により得られた重合触媒を反応器の供給口より連続的に供給し、平均温度を200℃に保ち重合反応を行なった。得られた直鎖状低密度ポリエチレン(LL−4)はMFR=12.0g/10分、密度907kg/mであった。LL−4の基本特性評価結果を表1に示す。
LL-4
[Preparation of modified clay]
A modified clay compound was prepared in the same manner as LL-1.
[Preparation of polymerization catalyst]
A polymerization catalyst was prepared in the same manner as in LL-3.
[Manufacture of LL-4]
Using a tank reactor equipped for high-temperature and high-pressure polymerization, ethylene and 1-hexene were continuously injected into the reactor so that the total pressure was 90 MPa, the 1-hexene concentration was 20 mol%, and the hydrogen concentration was 15 mol%. Was set to be. And the reactor was stirred at 1,500 rpm, the polymerization catalyst obtained by the above was continuously supplied from the supply port of the reactor, and average temperature was maintained at 200 degreeC, and the polymerization reaction was performed. The obtained linear low-density polyethylene (LL-4) had MFR = 12.0 g / 10 min and a density of 907 kg / m 3 . The basic characteristic evaluation results of LL-4 are shown in Table 1.

LL−5
東ソー(株)製、(商品名)ニポロン−Z ZF230(MFR=2.0g/10分、密度=920kg/m)LL−5の基本特性評価結果を表1に示す。
(2)高密度ポリエチレン
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;(C2245)(CHN 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、[変性粘土化合物の調製]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。
[HD−1の製造]
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0.45kg/時、水素8NL/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(HD−1)はMFR=4.0g/10分、密度944kg/mであった。HD−1の基本特性評価結果を表1に示す。
LL-5
Table 1 shows the results of evaluation of basic properties of Tosoh Corporation, (trade name) Nipolon-Z ZF230 (MFR = 2.0 g / 10 min, density = 920 kg / m 3 ) LL-5.
(2) High density polyethylene HD-1
[Preparation of modified clay]
To a mixed solvent of 4.8 L of deionized water and 3.2 L of ethanol, 354 g of dimethylbehenylamine; (C 22 H 45 ) (CH 3 ) 2 N and 83.3 mL of 37% hydrochloric acid are added, and the dimethylbehenylamine hydrochloride solution is added. Prepared. To this solution, 1,000 g of synthetic hectorite was added and stirred overnight. The resulting reaction solution was filtered, and the solid 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 with an infrared moisture meter was 0.8%. Next, this organically modified clay compound was pulverized to prepare 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 [Preparation of modified clay compound] and 1.4 kg of hexane were added, and then 1.78 kg (1.8 mol) of a 20 wt% solution of triisobutylaluminum in hexane, Bis (n-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. and 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% by weight hexane solution of triisobutylaluminum was added and reacted at 45 ° C. for 30 minutes. After allowing the reaction solution to stand at 45 ° C. for 2 hours, the supernatant was removed by a gradient method, 0.45 kg (0.45 mol) of a 20 wt% solution of hexane in triisobutylaluminum was added, and the whole amount was re-diluted with hexane. Was 4.5 L to prepare a polymerization catalyst.
[Production of HD-1]
Polymerization obtained in the section "Preparation of polymerization catalyst" in a polymerization vessel having an internal capacity of 300 L, hexane 135 kg / h, ethylene 20.0 kg / h, butene-1 0.45 kg / h, hydrogen 8 NL / h The catalyst was fed continuously. Further, the co-catalyst was continuously fed so that the concentration of triisobutylaluminum in the liquid was 0.93 mmol / kg hexane. The polymerization temperature was controlled at 85 ° C. The obtained high-density polyethylene (HD-1) had MFR = 4.0 g / 10 min and a density of 944 kg / m 3 . Table 1 shows the results of evaluation of basic characteristics of HD-1.

Figure 0006343886
(3)エチレン系重合体
PE−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[変性粘度の調製]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%)。
[PE−1の製造]
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、[重合触媒の調製]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のポリマーを得た。得られたポリマーのMFRは1.56g/10分、密度は923kg/m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、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。PE−1の基本特性評価結果を表2に示す。
Figure 0006343886
(3) Ethylene polymer PE-1
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 17.5 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 49.4 g (140 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 132 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified viscosity] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-Trimethylindenyl) zirconium dichloride was added in an amount of 0.4406 g and 142 mL of 20% triisobutylaluminum, followed by stirring at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt%).
[Production of PE-1]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 52 mg of the catalyst suspension obtained in [Preparation of polymerization catalyst] (corresponding to 6.4 mg solid content), and the temperature is raised to 70 ° C. After warming, 17.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.80 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.8 g of polymer. The obtained polymer had an MFR of 1.56 g / 10 min and a density of 923 kg / m 3 . The number average molecular weight was 17,600, the weight average molecular weight was 86,700, and peaks were observed at the molecular weights of 30,500 and 155,300. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.27 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 20.1 wt% of the total polymer. The melt tension was 75 mN. Table 2 shows the results of evaluation of basic characteristics of PE-1.

PE−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(MeN(C2653)、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[変性粘土の調製]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%)
[PE−2の製造]
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、[重合触媒の調製]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のポリマーを得た。得られたポリマーのMFRは4.0g/10分、密度は941kg/m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、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14.8wt%であった。また、溶融張力は49mNであった。PE−2の基本特性評価結果を表2に示す。
PE-2
[Preparation of modified clay]
Into a 1 L flask, 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water were added. 18.8 g of concentrated hydrochloric acid and dimethylhexacosylamine (Me 2 N (C 26 H 53 ) 49.1 g (120 mmol) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then heated to 60 ° C. The mixture was stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 140 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 14 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
[Production of PE-2]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 75 mg of the catalyst suspension obtained in [Preparation of polymerization catalyst] (corresponding to a solid content of 9.0 mg). After warming, 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 (concentration of hydrogen in the ethylene / hydrogen mixed gas: 850 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 58.5 g of polymer. The obtained polymer had an MFR of 4.0 g / 10 min and a density of 941 kg / m 3 . The number average molecular weight was 21,200, the weight average molecular weight was 74,000, and peaks were observed at the molecular weights 41,500 and 217,100. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.18 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 14.8 wt% of the total polymer. The melt tension was 49 mN. Table 2 shows the results of basic characteristic evaluation of PE-2.

PE−3
[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20.0g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)56.5g(160mmol)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145g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−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:11.2wt%)。
[PE−3の製造]
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、[重合触媒の調製]で得られた触媒懸濁液を74mg(固形分8.3mg相当)加え、65℃に昇温後、1−ブテンを17.5g加え、分圧が0.75MPa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:570ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで51.5gのポリマーを得た。得られたポリマーのMFRは0.8g/10分、密度は928kg/mであった。また、数平均分子量は17,900、重量平均分子量は99,300であり、分子量28,100および229,100の位置にピークが観測された。また、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0.26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25.4wt%であった。また、溶融張力は90mNであった。PE−3の基本特性評価結果を表2に示す。
PE-3
[Preparation of modified clay]
Into a 1 L flask, put 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 20.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 56.5 g (160 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. This slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 145 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
After a 300 mL flask equipped with a thermometer and a reflux tube was purged 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, 4 0.4406 g of 7-trimethyl-1-indenyl) zirconium dichloride and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.2 wt%).
[Production of PE-3]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 74 mg (equivalent to 8.3 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst], and raise the temperature to 65 ° C. After warming, 17.5 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure was 0.75 MPa (hydrogen concentration in the ethylene / hydrogen mixed gas: 570 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 51.5 g of polymer. The obtained polymer had an MFR of 0.8 g / 10 min and a density of 928 kg / m 3 . The number average molecular weight was 17,900, the weight average molecular weight was 99,300, and peaks were observed at molecular weights of 28,100 and 229,100. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.26 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 25.4 wt% of the total polymer. The melt tension was 90 mN. Table 2 shows the results of evaluation of basic characteristics of PE-3.

PE−4
[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15.0g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)42.4g(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122g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[変性粘土の調製]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:11.5wt%)。
[PE−4の製造]
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、[重合触媒の調製]で得られた触媒懸濁液を70mg(固形分8.4mg相当)加え、80℃に昇温後、1−ブテンを2.4g加え、分圧が0.90MPa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:720ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで63.0gのポリマーを得た。得られたポリマーのMFRは11.5g/10分、密度は954kg/mであった。また、数平均分子量は16,200、重量平均分子量は58,400であり、分子量28,200および181,000の位置にピークが観測された。また、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0.16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6.8wt%であった。また、溶融張力は38mNであった。PE−4の基本特性評価結果を表2に示す。
PE-4
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.5 wt%).
[Production of PE-4]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 70 mg (equivalent to 8.4 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst] and raise the temperature to 80 ° C. After warming, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 720 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.0 g of polymer. The obtained polymer had an MFR of 11.5 g / 10 min and a density of 954 kg / m 3 . The number average molecular weight was 16,200, the weight average molecular weight was 58,400, and peaks were observed at molecular weights of 28,200 and 181,000. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.16 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 6.8 wt% of the total polymer. The melt tension was 38 mN. Table 2 shows the results of basic characteristic evaluation of PE-4.

PE−5
[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15.0g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)42.4g(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122g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[変性粘土の調製]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:11.5wt%)。
[PE−5の製造]
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、[重合触媒の調製]で得られた触媒懸濁液を70mg(固形分8.4mg相当)加え、80℃に昇温後、1−ブテンを2.4g加え、分圧が0.90MPa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:750ppm)。90分経過後に脱圧し、スラリーを濾別後、乾燥することで63.0gのポリマーを得た。得られたポリマーのMFRは15.5g/10分、密度は954kg/mであった。また、数平均分子量は15,500、重量平均分子量は52,700であり、分子量27,900および179,000の位置にピークが観測された。また、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0.16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6.5wt%であった。また、溶融張力は35mNであった。PE−5の基本特性評価結果を表2に示す。
PE-5
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
A 300 mL flask equipped with a thermometer and a reflux tube was purged with nitrogen, and 25.0 g of the organically modified clay obtained in [Preparation of modified clay] and 108 mL of hexane were added, and then dimethylsilylene (cyclopentadienyl) (2 , 4,7-trimethyl-1-indenyl) zirconium dichloride and 0.4406 g of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was extracted, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 11.5 wt%).
[Production of PE-5]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 70 mg (equivalent to 8.4 mg of solid content) of the catalyst suspension obtained in [Preparation of polymerization catalyst] and raise the temperature to 80 ° C. After warming, 2.4 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 750 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 63.0 g of polymer. The obtained polymer had an MFR of 15.5 g / 10 min and a density of 954 kg / m 3 . Moreover, the number average molecular weight was 15,500, the weight average molecular weight was 52,700, and peaks were observed at positions of molecular weights 27,900 and 179,000. Further, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.16 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn 100,000 or more when molecular weight fractionation was 6.5 wt% of the total polymer. The melt tension was 35 mN. Table 2 shows the results of evaluation of basic characteristics of PE-5.

PE−6
[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15.0g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)42.4g(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122g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[変性粘土の調製]で得られた有機変性粘土25.0gをヘキサン165mLに懸濁させ、ジメチルシランジイルビス(シクロペンタジエニル)ジルコニウムジクロリド0.3485gおよびトリエチルアルミニウムのヘキサン溶液(1.18M)85mLを添加して60℃で3時間撹拌した。静置して室温まで冷却後に上澄み液を抜き取り、1%トリイソブチルアルミニウムのヘキサン溶液200mLにて2回洗浄した。洗浄後の上澄み液を抜き出し、5%トリイソブチルアルミニウムのヘキサン溶液にて全体を250mLとした。次いで、別途ジフェニルメチレン(1−シクロペンタジエニル)(2,7−ジ−tert−ブチル−9−フルオレニル)ジルコニウムジクロライド0.1165gのヘキサン10mL懸濁液に20%トリイソブチルアルミニウムのヘキサン溶液(0.71M)5mlを加えることにより調製した溶液を添加して、室温で6時間撹拌した。静置して上澄み液を除去、ヘキサン200mLにて2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%)。
[PE−6の製造]
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、[重合触媒の調製]で得られた触媒懸濁液を125mg(固形分15.0mg相当)加え、85℃に昇温後、1−ブテンを2.4g加え、分圧が0.90MPaになるようにエチレンを連続的に供給した。90分経過後に脱圧し、スラリーを濾別後、乾燥することで45.0gのポリマーを得た。得られたポリマーのMFRは4.4g/10分であり、密度は9517kg/mであった。数平均分子量は9,100、重量平均分子量は77,100であり、分子量10,400および168,400の位置にピークが観測された。また、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0.24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15.7wt%であった。また、溶融張力210mNであった。PE−6の基本特性評価結果を表2に示す。
PE-6
[Preparation of modified clay]
Into a 1 L flask is placed 300 mL of industrial alcohol (Japan Alcohol Sales (trade name) Echinen F-3) and 300 mL of distilled water, 15.0 g of concentrated hydrochloric acid and dimethylbehenylamine (Lion Corporation (trade name) Armin DM22D). ) 42.4 g (120 mmol) was added, heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), and then heated to 60 ° C. to maintain the temperature. The mixture was stirred for 1 hour. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm.
[Preparation of polymerization catalyst]
After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in [Preparation of modified clay] was suspended in 165 mL of hexane, and dimethylsilanediylbis (cyclopentadienyl) was suspended. ) 0.3485 g of zirconium dichloride and 85 mL of a hexane solution of triethylaluminum (1.18 M) were added and stirred at 60 ° C. for 3 hours. After allowing to stand and cooling to room temperature, the supernatant was taken out and washed twice with 200 mL of a 1% triisobutylaluminum hexane solution. The supernatant liquid after washing was extracted and the whole was made up to 250 mL with a 5% triisobutylaluminum hexane solution. Subsequently, a 20% triisobutylaluminum hexane solution (0%) was added to a suspension of diphenylmethylene (1-cyclopentadienyl) (2,7-di-tert-butyl-9-fluorenyl) zirconium dichloride 0.1165 g in hexane 10 mL. .71M) The solution prepared by adding 5 ml was added and stirred at room temperature for 6 hours. The supernatant was removed by standing, and after washing twice with 200 mL of hexane, 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.0 wt%).
[Production of PE-6]
To a 2 L autoclave, add 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum, and 125 mg (corresponding to a solid content of 15.0 mg) of the catalyst suspension obtained in [Preparation of polymerization catalyst]. After warming, 2.4 g of 1-butene was added, and ethylene was continuously supplied so that the partial pressure became 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 45.0 g of polymer. The obtained polymer had an MFR of 4.4 g / 10 min and a density of 9517 kg / m 3 . The number average molecular weight was 9,100, the weight average molecular weight was 77,100, and peaks were observed at molecular weights of 10,400 and 168,400. Moreover, the number of long chain branches contained in the fraction of Mn 100,000 or more when molecular weight fractionation was 0.24 per 1000 carbons of the main chain. Moreover, the ratio of the fraction of Mn of 100,000 or more when molecular weight fractionation was 15.7 wt% of the total polymer. The melt tension was 210 mN. Table 2 shows the results of evaluating basic characteristics of PE-6.

Figure 0006343886
B.単層フィルムおよび医療容器
実施例、比較例に用いた単層フィルムおよび医療容器は下記の方法により製造し、滅菌処理を行なった。
<単層フィルムおよび医療容器の製造>
単層水冷インフレーション成形機(プラコー社製)を用いて、シリンダ温度180℃、水槽温度15℃、引取速度4m/分でフィルム幅135mm、フィルム厚み250μmの単層フィルムを成形した。次いで、前記単層フィルムから長さ195mmのサンプルを切出し、一方の端をヒートシールして袋状にした後、超純水を300ml充填し、ヘッドスペースを50ml設けてヒートシールして医療容器を作製した。
Figure 0006343886
B. Single-layer film and medical container The single-layer film and medical container used in Examples and Comparative Examples were produced by the following method and sterilized.
<Manufacture of monolayer film and medical container>
A single-layer film having a film width of 135 mm and a film thickness of 250 μm was formed at a cylinder temperature of 180 ° C., a water bath temperature of 15 ° C., and a take-off speed of 4 m / min using a single-layer water-cooled inflation molding machine (manufactured by Placo). Next, a sample having a length of 195 mm was cut out from the single-layer film, heat sealed at one end, filled with 300 ml of ultrapure water, 50 ml of headspace was provided, and heat sealed to form a medical container. Produced.

<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112℃で30分間滅菌処理を行なった。
実施例、比較例に用いた積層体および医療容器の諸性質は下記の方法により評価した。
<Sterilization treatment>
The medical container was sterilized at a temperature of 112 ° C. for 30 minutes using a steam sterilizer (manufactured by Nisaka Manufacturing Co., Ltd.).
Various properties of the laminates and medical containers used in Examples and Comparative Examples were evaluated by the following methods.

<成形安定性>
単層水冷インフレーション成形機による、成膜時のフィルム(バブル)の安定性を目視により観察、評価した。
○:バブル安定性良好
×:バブル変動大
<フィルムの表面平滑性>
前記成形フィルムの表面状態を目視により観察、評価した。
○:表面平滑性良好
×:表面荒れ大
<フィルム外観>
滅菌処理後のフィルム表面のシワ、変形およびフィルムの融着等を目視により評価し、シワ、変形、が見られない場合を4点、若干のシワ、変形が見られる場合を3点、顕著なシワ、変形が見られる場合を2点、内層同士が融着した場合を1点とした。
<Molding stability>
The stability of the film (bubble) at the time of film formation was visually observed and evaluated by a single-layer water-cooled inflation molding machine.
○: Bubble stability is good ×: Bubble fluctuation is large <Surface smoothness of film>
The surface state of the molded film was visually observed and evaluated.
○: Excellent surface smoothness ×: Large surface roughness <Film appearance>
The film surface after sterilization is visually evaluated for wrinkles, deformation, film fusion, etc., and 4 points when wrinkles and deformation are not observed, 3 points when slight wrinkles and deformation are observed, 3 points. Two points were given when wrinkles and deformation were observed, and one point was given when the inner layers were fused together.

<透明性>
前記単層フィルムおよび滅菌処理後の医療容器から、幅10mm×長さ50mmの試験片を切出し、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。滅菌処理後に70%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 having a width of 10 mm and a length of 50 mm was cut out from the single-layer film and the medical container after sterilization, and light at a wavelength of 450 nm in pure water using an ultraviolet-visible spectrophotometer (model 220A, manufactured by Hitachi, Ltd.). The transmittance was measured. A case where a light transmittance of 70% or more was maintained after sterilization was regarded as a guideline for a medical container having good transparency.

<フィルムの柔軟性>
JIS K 7161に準拠して、前記滅菌処理後の医療容器から試験片を打抜き、引張試験機(型式 オートグラフ DCS−500、島津製作所製)を用いて5%弾性率を測定した。弾性率の値が200MPa以下の場合を柔軟性良好、200MPaを超える場合を柔軟性不良とした。
○:柔軟性良好
×:柔軟性不良
<透湿度>
JIS K 7129 A法(感湿センサー法)に準拠して、水蒸気透過度計(型式 L80−5000、Lyssy社製)により前記滅菌処理後の医療容器から切出した試験片の透湿度を測定した。
<Flexibility of film>
In accordance with JIS K 7161, a test piece was punched out from the sterilized medical container, and a 5% elastic modulus was measured using a tensile tester (model Autograph DCS-500, manufactured by Shimadzu Corporation). When the value of the elastic modulus was 200 MPa or less, the flexibility was good, and when it exceeded 200 MPa, the flexibility was poor.
○: Good flexibility ×: Poor flexibility <Moisture permeability>
In accordance with JIS K 7129 A method (humidity sensitive sensor method), the moisture permeability of a test piece cut out from the sterilized medical container was measured with a water vapor permeability meter (model L80-5000, manufactured by Lyssy).

<クリーン性(微粒子数)>
1μm以上の微粒子数が0個/10mlであることが確認された超純水を、前記「医療容器の製造」の項に記載した方法で製造した医療容器に充填密封した後、112℃で30分間の熱水滅菌処理を実施し、1日放置後、HIAC/ROYCO社製微粒子カウンター「 M−3000・4100・HR−60HA」 を用いて1μm以上の微粒子数を測定した。尚、これらの操作は、すべてクラス1000のクリーンルーム中で行った。
<Cleanness (number of fine particles)>
The ultrapure water whose number of fine particles of 1 μm or more was confirmed to be 0/10 ml was filled and sealed in a medical container manufactured by the method described in the above-mentioned “Manufacture of medical container”, and then 30 ° C. at 112 ° C. After carrying out the hot water sterilization process for 1 minute and leaving it to stand for 1 day, the number of microparticles | fine-particles 1 micrometer or more was measured using the microparticle counter "M-3000 * 4100 * HR-60HA" by HIAC / ROYCO. These operations were all performed in a class 1000 clean room.

実施例1
表1および2に示す樹脂を用いて、水冷インフレーション成形機により単層フィルムを成形し、成形安定性、フィルムの表面平滑性、透明性、柔軟性、透湿度を評価した。尚、フィルムの厚みは250μmとした。次いで、得られたフィルムをヒートシールし、超純水を充填した医療容器を作製して、112℃で高圧蒸気滅菌を行い、滅菌後のフィルム外観、透明性およびクリーン性を評価した。結果を表3に示す。
Example 1
Using the resins shown in Tables 1 and 2, single-layer films were formed by a water-cooled inflation molding machine, and the molding stability, film surface smoothness, transparency, flexibility, and moisture permeability were evaluated. The film thickness was 250 μm. Next, the obtained film was heat-sealed, a medical container filled with ultrapure water was prepared, and high-pressure steam sterilization was performed at 112 ° C., and the film appearance, transparency, and cleanness after sterilization were evaluated. The results are shown in Table 3.

実施例2〜7、比較例1〜5
樹脂を表3および表4に示すように変更した以外は、実施例1と同様にして単層フィルムおよび医療容器を作製し、評価を行った。結果を表3および表4に示す。
Examples 2-7, Comparative Examples 1-5
A single layer film and a medical container were prepared and evaluated in the same manner as in Example 1 except that the resin was changed as shown in Tables 3 and 4. The results are shown in Table 3 and Table 4.

比較例6
エチレン系重合体(B)をPE−1からGPCによる分子量測定においてピークが1つの市販の低密度ポリエチレン[東ソー(株)製、(商品名)ペトロセン 339、(MFR=3.0g/10分、密度=924kg/m)](以下S−1という)に変更した以外は、実施例1と同様にして単層フィルムおよび医療容器を作製し、評価を行った。結果を表4に示す。尚、S−1の特性を表2に示す。
Comparative Example 6
In the molecular weight measurement by PEPC-1 and GPC, the ethylene-based polymer (B) has one peak with a commercially available low density polyethylene [manufactured by Tosoh Corporation, (trade name) Petrocene 339, (MFR = 3.0 g / 10 min. Density = 924 kg / m 3 )] (hereinafter referred to as S-1), a single-layer film and a medical container were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4. The characteristics of S-1 are shown in Table 2.

比較例7
エチレン系重合体(B)をPE−1からGPCによる分子量測定においてピークが1つの市販の高密度ポリエチレン[S−2:日本ポリエチレン(株)製、(商品名)RS1000、(MFR=0.1g/10分、密度=953kg/m)](以下S−2という)に変更した以外は、実施例1と同様にして単層フィルムおよび医療容器を作製し、評価を行った。結果を表4に示す。尚、S−2の特性を表2に示す。
Comparative Example 7
In the molecular weight measurement of PE-based polymer (B) by GPC, commercially available high-density polyethylene [S-2: manufactured by Nippon Polyethylene Co., Ltd., (trade name) RS1000, (MFR = 0.1 g) / 10 min, density = 953 kg / m 3 )] (hereinafter referred to as S-2), a monolayer film and a medical container were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4. The characteristics of S-2 are shown in Table 2.

比較例8
エチレン系重合体(B)をPE−1からGPCによる分子量測定においてピークが1つの市販の高密度ポリエチレン[S−3:日本ポリエチレン(株)製、(商品名)KBX47D、(MFR=0.04g/10分、密度=946kg/m)](以下S−3という)に変更した以外は、実施例1と同様にして単層フィルムおよび医療容器を作製し、評価を行った。結果を表4に示す。尚、S−3の特性を表2に示す。
Comparative Example 8
A commercially available high-density polyethylene [S-3: manufactured by Nippon Polyethylene Co., Ltd., (trade name) KBX47D, (MFR = 0.04 g) in the molecular weight measurement by PEPC-1 to GPC of the ethylene polymer (B). / 10 min, density = 946 kg / m 3 )] (hereinafter referred to as S-3), a monolayer film and a medical container were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 4. The characteristics of S-3 are shown in Table 2.

Figure 0006343886
Figure 0006343886

Figure 0006343886
Figure 0006343886

Claims (6)

下記特性(a)〜(b)を満足する直鎖状低密度ポリエチレン(A)95〜20重量%と下記特性(c)〜(f)を満足するエチレン系重合体(B)5〜80重量%((A)と(B)の合計は100重量%)を含む組成物からなるポリエチレン製医療容器。
(a)密度が890〜940kg/mである。
(b)MFRが0.1〜15g/10分である。
(c)密度が920〜960kg/mである。
(d)MFRが0.1〜15g/10分である。
(e)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。
(f)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。
95 to 20% by weight of a linear low density polyethylene (A) satisfying the following characteristics (a) to (b) and 5 to 80% by weight of an ethylene polymer (B) satisfying the following characteristics (c) to (f) % (A total of (A) and (B) is 100% by weight).
(A) The density is from 890 to 940 kg / m 3 .
(B) MFR is 0.1 to 15 g / 10 min.
(C) The density is 920 to 960 kg / m 3 .
(D) MFR is 0.1 to 15 g / 10 min.
(E) 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. It is.
(F) The fraction having a Mn of 100,000 or more when molecular weight fractionation has 0.15 or more long-chain branches per 1000 carbons of the main chain.
エチレン系重合体(B)のMw/Mnが3.0〜6.0の範囲であり、Mnが15,000以上であることを特徴とする請求項1に記載のポリエチレン製医療容器。 The polyethylene medical container according to claim 1, wherein Mw / Mn of the ethylene-based polymer (B) is in the range of 3.0 to 6.0, and Mn is 15,000 or more. エチレン系重合体(B)の分子量分別した際のMnが10万以上である成分の割合がエチレン系重合体(B)全体の40%未満であることを特徴とする請求項1または請求項2に記載のポリエチレン製医療容器。 The ratio of the component having Mn of 100,000 or more when the molecular weight of the ethylene polymer (B) is fractionated is less than 40% of the entire ethylene polymer (B). The medical container made of polyethylene as described in 1. 薬液を収容する収容部を備えた医療容器であって、少なくとも前記収容部は、下記特性(a)〜(b)を満足する直鎖状低密度ポリエチレン(A)95〜20重量%と下記特性(c)〜(f)を満足するエチレン系重合体(B)5〜80重量%((A)と(B)の合計は100重量%)を含む組成物からなることを特徴とするポリエチレン製医療容器。
(a)密度が890〜940kg/m である。
(b)MFRが0.1〜15g/10分である。
(c)密度が920〜960kg/m である。
(d)MFRが0.1〜15g/10分である。
(e)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。
(f)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。
A medical container including a container for storing a chemical solution, wherein at least the container includes 95 to 20% by weight of linear low density polyethylene (A) satisfying the following characteristics (a) to (b): A polyethylene product characterized by comprising a composition containing 5 to 80% by weight of an ethylene polymer (B) satisfying (c) to (f) (the total of (A) and (B) is 100% by weight) Medical container.
(A) The density is from 890 to 940 kg / m 3 .
(B) MFR is 0.1 to 15 g / 10 min.
(C) The density is 920 to 960 kg / m 3 .
(D) MFR is 0.1 to 15 g / 10 min.
(E) 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. It is.
(F) The fraction having a Mn of 100,000 or more when molecular weight fractionation has 0.15 or more long-chain branches per 1000 carbons of the main chain.
薬液を収容する収容部が、フィルム状成形体をヒートシールにより袋状に成形したものであることを特徴とする請求項4に記載のポリエチレン製医療容器。 The polyethylene medical container according to claim 4, wherein the container for storing the chemical solution is a film-shaped molded body formed into a bag shape by heat sealing. 薬液を収容する収容部が、ブロー成形によりボトル状に成形したものであることを特徴とする請求項4に記載のポリエチレン製医療容器。 The polyethylene medical container according to claim 4, wherein the container for storing the chemical solution is formed into a bottle shape by blow molding.
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