JP5261702B2 - 流れ指数が低い射出−延伸−ブロー成形用樹脂 - Google Patents
流れ指数が低い射出−延伸−ブロー成形用樹脂 Download PDFInfo
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- JP5261702B2 JP5261702B2 JP2009515869A JP2009515869A JP5261702B2 JP 5261702 B2 JP5261702 B2 JP 5261702B2 JP 2009515869 A JP2009515869 A JP 2009515869A JP 2009515869 A JP2009515869 A JP 2009515869A JP 5261702 B2 JP5261702 B2 JP 5261702B2
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- injection
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- blow molding
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- 239000011347 resin Substances 0.000 title claims abstract description 21
- 229920005989 resin Polymers 0.000 title claims abstract description 21
- 238000010103 injection stretch blow moulding Methods 0.000 title claims abstract description 14
- 238000002347 injection Methods 0.000 claims abstract description 17
- 239000007924 injection Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000000155 melt Substances 0.000 claims abstract description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005977 Ethylene Substances 0.000 claims abstract description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 8
- 229920005604 random copolymer Polymers 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 5
- 238000010998 test method Methods 0.000 claims description 5
- -1 polypropylene Polymers 0.000 description 10
- 239000004743 Polypropylene Substances 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 238000000071 blow moulding Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000002667 nucleating agent Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000012968 metallocene catalyst Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000007634 remodeling Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012669 compression test Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
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- C08F10/04—Monomers containing three or four carbon atoms
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61J—CONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
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- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Description
下記文献ではISBMで二段階法で物品を製造している。
下記文献ではISBMで二段階法で物品を製造している。
下記文献にはメタロセン触媒を使用して作ったプロピレンのホモ−またはコポリマーをISBMで使用することが開示されている。
上記の樹脂では特性が理想的にバランスした物品を作ることはできない。
本発明の他の目的は、2軸延伸後に優れた光学特性を有する医薬用小びんを製造するための、射出−延伸−ブロー成形法用プリフォームでの低溶融流動性ポリプロピレン樹脂の使用方法を提供することにある。
本発明のさらに他の目的は、厚さ分布の良い医薬用小びんを製造することにある。
本発明のさらに他の目的は、積み重ね特性に優れた医薬用小びんを製造することにある。
本発明のさらに他の目的は、特に低温での耐落下試験性に優れた医薬用小びんを製造することにある。
上記目的の少なくとも一つの少なくとも一部は本発明によって達成できる。
本発明はさらに、プリフォームの製造方法と、この方法で得られるプリフォームと、このプリフォームの医薬用小びんの製造での使用と、プリフォームから製造した医薬用小びんとに関するものである。
本発明で使用するポリプロピレン樹脂はチーグラー−ナッタ(ZN)触媒系で製造したものが好ましい。ZN触媒系では本来的に多分散性指数が広いポリマーが作られる。多分散性指数は数平均分子量Mnに対する重量平均分子量Mwの比Mw/Mnで定義される。分子量はゲル浸透クロマトグラフ(Gel Permeation Chromatography、GPC)で測定する。チーグラー−ナッタ触媒系では一般に多分散性指数が少なくとも6のポリマーが得られる。メタロセン触媒およびシングルサイト触媒はZN触媒でないということは明らかである。
メルトインデックスは3dg/分以下である。好ましい最低MI2は1.5dg/分で、好ましい最大MI2は2.5dg/分、好ましくは2dg/分である。
一般に、このタイプの低溶融流動性樹脂は射出−延伸−ブロー成形の用途では使用されない。従って、射出−延伸−ブロー成形条件をこの樹脂で実施するのに合わせる。
樹脂は5000ppm以下の核剤を含むことができる。核剤が存在する場合、その量は200〜2500ppmにするのが好ましい。
さらに、この分野で一般的に使用される他の添加剤、例えば抗酸化剤または静電気防止剤を加えられることもできる。
プリフォームに生じる応力が最終製品の透明性および衝撃特性に大きな影響を与える。
(1)多重キャビティー金型で射出成形してプリフォームを作る。
(2)得られたプリフォームを室温に冷却する。
(3)プリフォームを延伸−ブロー成形機まで移動させる。
(4)延伸−ブロー成形機中でプリフォームを再加熱する。
(5)必要な場合には、加熱されたプリフォームを平衡化帯域を通してプリフォーム壁に熱を均一に分散させる。
(6)必要な場合にはさらに、プリフォームを予備延伸階段で延伸する。
(7)中心ロッドでプリフォームを軸線方向に延伸すると同時にプリフォームを高圧空気によって放射方向に延伸する。
上記方法では延伸階段がクリティカルな階段である。最終製品で最高特性を得るためには最適化されたプロセスでプリフォームを製造する必要がある。
プリフォームは所定加熱プロフィルを有する赤外線オーブンで再加熱する。再加熱階段に必要なエネルギーは、一つのキャビティーで1時間当り約1500個の物品を生産するシステムの場合、一般に28〜40kW、好ましくは30〜36kWである。典型的な再加熱温度は90〜140℃である。
以下、医薬用小びんの特性を示すが、本発明が下記実施例に示すものに限定されるものではない。
メルトフローインデックスを下げ、従って、射出温度を上げたことによって壁厚分布の均一性が改善された。壁厚さはビンの高さに沿って互いに異なる3つの位置で測定し、ビンの円周に沿って互いに90度異なる4つの位置で測定した。
落下試験は最高6mの高さから落下させて行なった。ビンを垂直に対して15度傾けた金属プレート上に落下させた。水を充填したビンを室温中に48時間放置した後に室温(23 ℃)でテストを実行した。破壊しない最高高H(m)を[表3]に示す。また、テストしたサンプルの50%が壊れた高さも記載した。
透明性は約300マイクロメートルの壁厚さを有するビンでASTM D 1003規格のテスト方法を用いて測定したヘイズで定量化した。結果は[表3]に示した。
Claims (5)
- ISO 1133規格のテスト方法に従って2.16kgの荷重下で230℃の温度で測定したメルトフローインデックスが1〜3dg/分で、エチレン含有量が樹脂重量の2〜3.5重量%であるチーグラー‐ナッタ触媒系を用いて製造されたプロピレンとエチレンとのランダム共重合体を用い、プリフォームの射出温度が少なくとも280℃で、ゲート直径に対する金型充填速度を10cc/秒/mm以下にして、二段階の射出−延伸−ブロー成形で小びんを製造する方法。
- メルトフローインデックスが1.5〜2.5dg/分である請求項1に記載の方法。
- プリフォームの射出温度が少なくとも320℃である請求項1または2に記載の方法。
- プリフォームを28〜40kWのエネルギーを有する赤外線オーブン中で、1500ビン/時の生産性で再加熱する請求項1〜3のいずれか一項に記載の方法。
- 医薬用小びんを二段階の射出−延伸−ブロー成形で製造する方法において、
チーグラー‐ナッタ触媒系を用いて製造した、ISO 1133規格のテスト方法に従って2.16kgの荷重下で230℃の温度で測定したメルトフローインデックスが2〜3dg/分で、エチレン含有量が樹脂重量の2〜3.5重量%であるプロピレンとエチレンのランダム共重合体を使用することを特徴とする方法。
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EP06115765.7 | 2006-06-21 | ||
EP06115765A EP1870223A1 (en) | 2006-06-21 | 2006-06-21 | Low melt flow index resins for injection-stretch-blow-moulding |
PCT/EP2007/056129 WO2007147845A1 (en) | 2006-06-21 | 2007-06-20 | Low melt flow index resins for injections-stretch-blow-moulding |
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JP5261702B2 true JP5261702B2 (ja) | 2013-08-14 |
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US (1) | US8894911B2 (ja) |
EP (2) | EP1870223A1 (ja) |
JP (1) | JP5261702B2 (ja) |
KR (1) | KR101414935B1 (ja) |
CN (1) | CN101472726B (ja) |
AT (1) | ATE486707T1 (ja) |
DE (1) | DE602007010292D1 (ja) |
DK (1) | DK2032333T3 (ja) |
ES (1) | ES2353343T3 (ja) |
PL (1) | PL2032333T3 (ja) |
PT (1) | PT2032333E (ja) |
WO (1) | WO2007147845A1 (ja) |
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EP2168752B1 (en) | 2008-09-30 | 2015-01-14 | The Procter & Gamble Company | Stretch blow molding process and container |
US11292909B2 (en) | 2014-12-19 | 2022-04-05 | Earth Renewable Technologies | Extrudable polymer composition and method of making molded articles utilizing the same |
JP6555915B2 (ja) * | 2015-03-31 | 2019-08-07 | 株式会社吉野工業所 | 液体ブロー成形装置 |
EP3909742A1 (en) * | 2020-05-15 | 2021-11-17 | Borealis AG | Injection stretch blow moulded article |
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KR101414935B1 (ko) | 2014-07-04 |
ATE486707T1 (en) | 2010-11-15 |
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PL2032333T3 (pl) | 2011-04-29 |
EP1870223A1 (en) | 2007-12-26 |
EP2032333B1 (en) | 2010-11-03 |
ES2353343T3 (es) | 2011-03-01 |
US8894911B2 (en) | 2014-11-25 |
WO2007147845A1 (en) | 2007-12-27 |
KR20090018943A (ko) | 2009-02-24 |
DK2032333T3 (da) | 2011-01-03 |
DE602007010292D1 (en) | 2010-12-16 |
CN101472726A (zh) | 2009-07-01 |
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