JP2000093490A5 - Soft molded product - Google Patents
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- JP2000093490A5 JP2000093490A5 JP1998267058A JP26705898A JP2000093490A5 JP 2000093490 A5 JP2000093490 A5 JP 2000093490A5 JP 1998267058 A JP1998267058 A JP 1998267058A JP 26705898 A JP26705898 A JP 26705898A JP 2000093490 A5 JP2000093490 A5 JP 2000093490A5
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- conjugated diene
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- -1 polypropylene Polymers 0.000 claims description 46
- 229920000642 polymer Polymers 0.000 claims description 36
- 150000001993 dienes Chemical class 0.000 claims description 20
- 239000004743 Polypropylene Substances 0.000 claims description 15
- 229920001155 polypropylene Polymers 0.000 claims description 15
- 239000005977 Ethylene Substances 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000005062 Polybutadiene Substances 0.000 claims description 8
- 229920002857 polybutadiene Polymers 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 229920001400 block copolymer Polymers 0.000 claims description 7
- 229920001519 homopolymer Polymers 0.000 claims description 6
- 210000004369 Blood Anatomy 0.000 claims description 5
- 239000008280 blood Substances 0.000 claims description 5
- 229920005604 random copolymer Polymers 0.000 claims description 5
- 238000001802 infusion Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 210000001772 Blood Platelets Anatomy 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 18
- 238000005984 hydrogenation reaction Methods 0.000 description 6
- 239000004711 α-olefin Substances 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-Hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-Octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 125000002897 diene group Chemical group 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 230000001954 sterilising Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- WWUVJRULCWHUSA-UHFFFAOYSA-N 2-methylpent-1-ene Chemical compound CCCC(C)=C WWUVJRULCWHUSA-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5E)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- XCGKRTHKVBCXLN-UHFFFAOYSA-N 3a,4,4a,5,8,8a,9,9a-Octahydro-4,9:5,8-dimethano-1H-benz(f)indene Chemical compound C1C2C3C(C=C4)CC4C3C1C1C2C=CC1 XCGKRTHKVBCXLN-UHFFFAOYSA-N 0.000 description 1
- KLCNJIQZXOQYTE-UHFFFAOYSA-N 4,4-dimethylpent-1-ene Chemical compound CC(C)(C)CC=C KLCNJIQZXOQYTE-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-Methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- YHESWXAODSYVCO-UHFFFAOYSA-N 5-but-1-enylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=CCC)CC1C=C2 YHESWXAODSYVCO-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- DMGCMUYMJFRQSK-UHFFFAOYSA-N 5-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C(=C)C)CC1C=C2 DMGCMUYMJFRQSK-UHFFFAOYSA-N 0.000 description 1
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N Decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Ethylene tetrachloride Chemical compound ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-UHFFFAOYSA-N Norbornene Chemical compound C1C2CCC1C=C2 JFNLZVQOOSMTJK-UHFFFAOYSA-N 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N Pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920002725 Thermoplastic elastomer Polymers 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000903 blocking Effects 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atoms Chemical group C* 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- RRKODOZNUZCUBN-UHFFFAOYSA-N cycloocta-1,3-diene Chemical compound C1CCC=CC=CC1 RRKODOZNUZCUBN-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening Effects 0.000 description 1
Description
【０００１】
【発明の属する技術分野】
本発明は、特に透明性、柔軟性、耐熱性に優れ、かつ耐衝撃性が良好で安全性に優れる軟質成形品に関し、より詳しくは、ポリプロピレン、水添ジエン系重合体、および必要に応じて配合されるエチレンを主体とするオレフィン系重合体からなる、医療用途に好適な特性を有するフィルム、シート、チューブ、容器等の軟質成形品に関する。
[0001]
[Technical field to which the invention belongs]
The present invention particularly relates to a flexible molded article having excellent transparency, flexibility, heat resistance, impact resistance and excellent safety. More specifically, the present invention relates to polypropylene, a hydrogenated diene polymer, and, if necessary, a hydrogenated diene polymer. The present invention relates to a soft molded product such as a film, a sheet, a tube, a container, etc., which is made of an olefin polymer mainly composed of ethylene and has properties suitable for medical use.
【０００２】
【従来の技術】
採血、輸血、輸液等の医療で用いられる容器は、従来のガラス性ボトルやポリプロピレン等の硬質タイプのプラスチック製ボトルから、軟質タイプのプラスチック製バッグへと変わりつつある。
軟質タイプのプラスチックバッグの素材としては、安全性の他、種々の性能が要求され、なかでも、柔軟性、強度、透明性および耐熱性が重要である。従来、軟質素材としては、軟質ポリ塩化ビニル、エチレン−酢酸ビニルコポリマーや低密度ポリエチレン等のエチレン系ポリマーが主として使用されているが、軟質ポリ塩化ビニルでは可塑剤の溶出の問題があり、耐寒性に乏しく、熱滅菌時に着色しやすいという欠点がある。更に、廃棄時に有害ガス発生の問題もある。低密度ポリエチレンの場合は、安全性に優れるが融点が低いため、高温・短時間でのスチーム滅菌をすることができない。また、９０℃程度のスチーム滅菌温度ではブロッキングや熱水による白化が発生しやすい。更に柔軟性の面でも回復性に乏しい等の問題がある。エチレン−酢酸ビニルコポリマー等のポリエチレン系ポリマーの場合には、柔軟性が向上するが耐熱性が更に低下し、両者のバランスに欠けている。耐熱性と柔軟性のバランスの改良手段として、放射線照射による架橋が有効であることが知られているが、製造工程が複雑化し、経済性も低下するなどの問題がある。
これらの問題を解決するために、様々な改良が試みられており、特に、耐熱性に優れたポリプロピレンとスチレン系エラストマーの組み合わせが有効であるとされ、例えば、特開平２−１２７９号公報には、ポリプロピレンとスチレン−エチレン・ブチレン−スチレンブロック共重合体とエチレンアクリル酸エステルポリマーの組み合わせによる血液バッグ、特開平４−２２１５７２号公報には、ポリプロピレンとスチレン−エチレン・ブチレン−スチレンあるいはスチレン−エチレン・プロピレン−スチレンブロック共重合体とエチレン−α−オレフィン共重合体の組み合わせによる医療バッグ、特開平８−２４３３０号公報には、ポリプロピレンとスチレン−エチレン・ブチレン−スチレンあるいはスチレン−エチレン・プロピレン−スチレンブロック共重合体の組み合わせによる医療バッグが提案されているが、自己排液性を満たすほどの柔軟性は持ち合わせておらず、これらの組成物においても、医療容器に要求される透明性、柔軟性、耐熱性のバランスが十分な領域に達していないという問題を有する。
0002.
[Conventional technology]
Containers used in medical treatment such as blood collection, blood transfusion, and infusion are changing from conventional glass bottles and hard type plastic bottles such as polypropylene to soft type plastic bags.
As a material for a soft type plastic bag, various performances are required in addition to safety, and among them, flexibility, strength, transparency and heat resistance are important. Conventionally, as a soft material, ethylene-based polymers such as soft polyvinyl chloride, ethylene-vinyl acetate copolymer and low-density polyethylene are mainly used, but soft polyvinyl chloride has a problem of elution of a plasticizer and has cold resistance. It has the disadvantage that it is poorly colored and easily colored during heat sterilization. Furthermore, there is also the problem of generating harmful gas at the time of disposal. Low-density polyethylene is excellent in safety but has a low melting point, so steam sterilization at high temperature and in a short time cannot be performed. Further, at a steam sterilization temperature of about 90 ° C., blocking and whitening due to hot water are likely to occur. Furthermore, in terms of flexibility, there are problems such as poor recoverability. In the case of a polyethylene-based polymer such as an ethylene-vinyl acetate copolymer, the flexibility is improved, but the heat resistance is further lowered, and the balance between the two is lacking. It is known that cross-linking by irradiation is effective as a means for improving the balance between heat resistance and flexibility, but there are problems such as complicated manufacturing process and reduced economic efficiency.
To solve these problems, has been attempted various improvements, in particular, is the combination of excellent polypropylene and styrene elastomer in heat resistance is effective, for example, JP-A-2-1279 , polypropylene and styrene - ethylene butylene - styrene block copolymer and ethylene acrylic acid ester polymer combinations by blood bags, JP-a-4-221572, polypropylene and styrene - ethylene butylene - styrene or styrene - ethylene propylene - styrene block copolymer and ethylene -α- olefin copolymer combined by medical bags, JP-a-8-24330, polypropylene and styrene - ethylene butylene - styrene or styrene - ethylene-propylene - styrene block Medical bags made of a combination of copolymers have been proposed, but they do not have the flexibility to satisfy self-drainage, and even in these compositions, the transparency and flexibility required for medical containers, There is a problem that the balance of heat resistance does not reach a sufficient region.
【０００４】
【課題を解決するための手段】
本発明は、以下の［１］〜［６］を提供するものである。
［１］ （イ）ポリプロピレン１〜９９重量％、（ロ）１，４−結合含量が７０重量％以上のポリブタジエンブロックセグメント（Ａ）と、共役ジエン化合物の単独重合体、あるいは共役ジエン化合物を７０重量％以上含有する芳香族ビニル化合物と共役ジエン化合物とのランダム共重合体であって、共役ジエン化合物部分のビニル結合含量が６０重量％以上であるブロックセグメント（Ｂ）からなるブロック共重合体であり、共役ジエン部分の二重結合の少なくとも８０％が飽和された水添ジエン系重合体１〜９９重量％、（ハ）エチレンを主体とするオレフィン系重合体０〜９８重量％〔ただし、（イ）＋（ロ）＋（ハ）＝１００重量％〕を主成分とすることを特徴とする軟質成形品。
［２］ 上記（ロ）水添ジエン系重合体は、上記（Ａ）ポリブタジエンブロックセグメント１〜９９重量％と、上記（Ｂ）ブロックセグメント１〜９９重量％〔ただし、（Ａ）＋（Ｂ）＝１００重量％〕からなる上記［１］に記載の軟質成形品。
［３］ 上記（ロ）水添ジエン系重合体のポリスチレン換算の重量平均分子量は、５万〜７０万である上記［１］又は［２］に記載の軟質成形品。
［４］ 上記（イ）ポリプロピレンは、密度が０．８８５〜０．９１５ｇ／ｃｍ 3 であり、かつメルトフローレートが０．１〜５０ｇ／１０分である上記［１］〜［３］のいずれかに記載の軟質成形品。
［５］ 上記軟質成形品は、フィルム、シート、チューブ、及び容器のいずれかの形態を有する医療用成形品である上記［１］〜［４］のいずれかに記載の軟質成形品。
［６］ 上記軟質成形品は、輸液バッグ、ＣＡＰＤバッグ、血液バッグ、及び血小板保存バッグのいずれかである上記［１］〜［４］のいずれかに記載の軟質成形品。
以下、本発明を詳細に説明する。
0004
[Means for solving problems]
The present invention provides the following [1] to [6].
[1] (a) Polybutadiene block segment (A) having 1 to 99% by weight of polypropylene and (b) 1,4- bond content of 70% by weight or more, and a homopolymer of a conjugated diene compound or 70 of a conjugated diene compound. A block copolymer composed of a block segment (B) having a vinyl bond content of 60% by weight or more in the conjugated diene compound portion, which is a random copolymer of an aromatic vinyl compound and a conjugated diene compound containing by weight% or more. Yes, at least 80% of the double bond of the conjugated diene moiety is saturated from 1 to 99% by weight of the hydrogenated diene polymer, and (c) 0 to 98% by weight of the olefin polymer mainly composed of ethylene [however, ( B) + (b) + (c) = 100% by weight] is the main component of the soft molded product .
[2] The hydrogenated diene-based polymer (b) is composed of the (A) polybutadiene block segment 1 to 99% by weight and the (B) block segment 1 to 99% by weight [however, (A) + (B). = 100% by weight] The soft molded product according to the above [1] .
[3] The soft molded product according to the above [1] or [2], wherein the (b) hydrogenated diene polymer has a polystyrene-equivalent weight average molecular weight of 50,000 to 700,000 .
[4] The polypropylene having a density of 0.885 to 0.915 g / cm 3 and a melt flow rate of 0.1 to 50 g / 10 minutes is any one of the above [1] to [3]. The soft molded product described in Crab .
[5] The soft molded product according to any one of the above [1] to [4], which is a medical molded product having any form of a film, a sheet, a tube, and a container .
[6] The soft molded product according to any one of the above [1] to [4], which is any of an infusion bag, a CAPD bag, a blood bag, and a platelet storage bag .
Hereinafter, the present invention will be described in detail.
【０００５】
【発明の実施の形態】
本発明に使用される（イ）ポリプロピレンは、結晶性ポリプロピレンであり、プロピレンの単独重合体あるいはエチレン、１−ブテン、１−ヘキセンなどのα−オレフィンを２０モル％以下、好ましくは０．１〜１５モル％、より好ましくは０．５〜１０モル％含んだ共重合体である。この共重合体としては、ランダム共重合体、あるいは多段重合で得られる共重合体と単独重合体とのブレンド物、あるいは共重合体と単独重合体との通常のブレンド物であってもよい。
また、ポリプロピレンの密度は０．８８５〜０．９１５ｇ／ｃｍ3であり、メルトフローレート（ＭＦＲ）は０．１〜５０ｇ／１０分、好ましくは０．２〜４０ｇ／１０分である。
0005
BEST MODE FOR CARRYING OUT THE INVENTION
The polypropylene (a) used in the present invention is a crystalline polypropylene, and contains 20 mol% or less, preferably 0.1 to 1% of a copolymer of propylene or an α-olefin such as ethylene, 1-butene, and 1-hexene. It is a copolymer containing 15 mol%, more preferably 0.5 to 10 mol%. The copolymer may be a random copolymer, a blend of a copolymer obtained by multistage polymerization and a homopolymer, or a normal blend of a copolymer and a homopolymer.
The density of polypropylene is 0.885 to 0.915 g / cm 3 , and the melt flow rate (MFR) is 0.1 to 50 g / 10 minutes, preferably 0.2 to 40 g / 10 minutes.
本発明の（ロ）水添ジエン系重合体は、１，４−結合含量が７０重量％以上のポリブタジエンブロックセグメント（Ａ）と、共役ジエン化合物の単独重合体、あるいは共役ジエン化合物を７０重量％以上含有する芳香族ビニル化合物と共役ジエン化合物とのランダム共重合体であって、共役ジエン化合物部分のビニル結合含量が６０重量％以上であるブロックセグメント（Ｂ）からなるブロック共重合体を主体とする重合体（以下、「水添前重合体」ともいう）を水素添加したものである。該重合体は、共役ジエン部分の二重結合残基が好ましくは８０％以上、より好ましくは９０％以上水素添加されており、数平均分子量が４万〜７０万であるものが好ましい。二重結合残基の水素添加率が８０％未満であると透明性、機械的強度、耐熱性、耐候性が十分でないものとなる。数平均分子量が４万未満では得られる水添ジエン系共重合体をペレット化した場合ブロッキングしやすくなるほか、他の樹脂とブレンドした場合、十分な機械的強度、成形外観が得にくく、７０万を超えると良好な成形加工性が得難い。 The (b) hydrogenated diene-based polymer of the present invention contains a polybutadiene block segment (A) having a 1,4- bond content of 70 % by weight or more, a homopolymer of a conjugated diene compound, or 70% by weight of a conjugated diene compound. A random copolymer of the aromatic vinyl compound and the conjugated diene compound contained above, mainly composed of a block copolymer composed of a block segment (B) having a vinyl bond content of 60% by weight or more in the conjugated diene compound portion. This is a hydrogenated polymer (hereinafter, also referred to as “pre-hydrogenated polymer”). The polymer preferably has a double bond residue of a conjugated diene moiety hydrogenated at an amount of preferably 80% or more, more preferably 90% or more, and has a number average molecular weight of 40,000 to 700,000. If the hydrogenation rate of the double bond residue is less than 80%, the transparency, mechanical strength, heat resistance, and weather resistance become insufficient. When the hydrogenated diene-based copolymer obtained when the number average molecular weight is less than 40,000 is pelletized, it becomes easy to block, and when it is blended with other resins, it is difficult to obtain sufficient mechanical strength and molded appearance, and 700,000. If it exceeds , it is difficult to obtain good molding processability.
前記水添前重合体を構成するブロックセグメント（Ａ）に含まれるポリブタジエン部分の好ましい１，４−結合含量は７０重量％以上、より好ましくは８０重量％以上である。１，４−結合含量が７０重量％未満では、水素添加された後に樹脂的性質が低下し、またブロック共重合体としての熱可塑性エラストマーの性質が十分でないものとなる。 The preferable 1,4-bond content of the polybutadiene moiety contained in the block segment (A) constituting the pre-hydrogenation polymer is 70% by weight or more, more preferably 80% by weight or more. If the 1,4-bond content is less than 70% by weight, the resinous properties will deteriorate after hydrogenation, and the properties of the thermoplastic elastomer as a block copolymer will be insufficient.
また、前記水添前重合体を構成するブロックセグメント（Ｂ）の共役ジエン化合物部分の好ましいビニル結合（１，２−結合および３，４−結合）を有する共役ジエンの含量は６０重量％以上、より好ましくは７０重量％以上である。ビニル結合含量が６０重量％未満では、例えば共役ジエンがブタジエンの場合、水素添加されるとポリエチレン連鎖が多く生成し、ゴム的性質が失われて好ましくない。
ブロックセグメント（Ｂ）の好ましい含量は、１〜９９重量％、より好ましくは３０〜９０重量％、さらに好ましくは３５〜９０重量％である。ブロックセグメント（Ｂ）の含量が１重量％未満では、柔軟性が低下し、一方９９重量％を超えると機械的強度、成形加工性が低下する。
Further, the content of the conjugated diene having a preferable vinyl bond (1,2- bond and 3,4 -bond) of the conjugated diene compound portion of the block segment (B) constituting the pre-hydrogenated polymer is 60% by weight or more. More preferably, it is 70% by weight or more. If the vinyl bond content is less than 60% by weight, for example, when the conjugated diene is butadiene, a large amount of polyethylene chains are formed when hydrogenated, and the rubbery property is lost, which is not preferable.
The preferred content of the block segment (B) is 1 to 99% by weight, more preferably 30 to 90% by weight, still more preferably 35 to 90% by weight. If the content of the block segment (B) is less than 1% by weight, the flexibility is lowered, while if it exceeds 99% by weight, the mechanical strength and moldability are lowered.
本発明の（ロ）水添ジエン系共重合体は、上述の１，４−結合含量が７０重量％以上のポリブタジエンブロックセグメント（Ａ）と、共役ジエン化合物の単独重合体、あるいは共役ジエン化合物を７０重量％以上含有する芳香族ビニル化合物と共役ジエン化合物とのランダム共重合体であって、共役ジエン化合物部分のビニル結合含量が６０重量％以上であるブロックセグメント（Ｂ）からなるブロック共重合体を主体とする重合体を水素添加することによって得られるが、（ロ）水添ジエン系共重合体中に、ブロック（Ａ）、（Ｂ）はそれぞれの少なくとも一つずつあれば良く、複数存在していても良い。 The (b) hydrogenated diene-based copolymer of the present invention comprises the above-mentioned polybutadiene block segment (A) having a 1,4- bond content of 70 % by weight or more, a homopolymer of a conjugated diene compound, or a conjugated diene compound. A random copolymer of an aromatic vinyl compound and a conjugated diene compound containing 70% by weight or more, and a block copolymer composed of a block segment (B) having a vinyl bond content of 60% by weight or more in the conjugated diene compound portion. It can be obtained by hydrogenating a polymer mainly composed of (b) , and at least one block (A) and (B) may be present in each of the (b) hydrogenated diene-based copolymers. You may do it.
なお本発明の（ロ）成分としては、２種またはそれ以上の水添前重合体のブレンド物を水添したものも好適に用いられる。さらに、２種またはそれ以上の水添ジエン系重合体同士のブレンド物も、本発明の（ロ）成分として好適である。本発明の（ロ）水添ジエン系重合体において、分子鎖中の共役ジエン部分の二重結合の水素添加率は、好ましくは８０％、より好ましくは８５％以上、さらに好ましくは９０％以上である。８０％未満では、得られるフィルム・シートの透明性、ヒートシール性が不十分なものとなり好ましくない。さらに、本発明の（ロ）水添ジエン系重合体はポリスチレン換算の重量平均分子量が好ましくは５万〜７０万、より好ましくは５万〜６０万であり、５万未満では得られるフィルム・シートの耐衝撃性が劣り、一方７０万を超えると加工性が不十分なものとなる。なお、本発明に使用される（ロ）水添ジエン系共重合体は、例えば特開平３−１２８９５７号公報に開示されている方法によって得ることができる。 As the component (b) of the present invention, a product obtained by hydrogenating a blend of two or more pre-hydrogenated polymers is also preferably used. Further, a blend of two or more hydrogenated diene-based polymers is also suitable as the component (b) of the present invention. In the (b) hydrogenated diene polymer of the present invention, the hydrogenation rate of the double bond of the conjugated diene moiety in the molecular chain is preferably 80%, more preferably 85% or more, still more preferably 90% or more. is there. If it is less than 80%, the transparency and heat sealability of the obtained film / sheet will be insufficient, which is not preferable. Further, the hydrogenated diene polymer of the present invention preferably has a polystyrene-equivalent weight average molecular weight of 50,000 to 700,000, more preferably 50,000 to 600,000, and a film sheet obtained when the weight average is less than 50,000. The impact resistance of the above is inferior, while when it exceeds 700,000, the workability becomes insufficient. The (b) hydrogenated diene-based copolymer used in the present invention can be obtained , for example, by the method disclosed in JP-A-3-128957.
本発明に使用される（ハ）エチレンを主体とするオレフィン系重合体は、２０モル％を超えるエチレンを有する重合体であり、直鎖状あるいは分岐状のオレフィン系重合体である。この直鎖状あるいは分岐状のオレフィン系重合体の代表的な例としては、エチレン−α−オレフィン系共重合体や高圧法低密度ポリエチレンなどが挙げられる。
ここでエチレン−α−オレフィン系共重合体におけるα−オレフィンとしては、炭素数３〜１２のものが一般的であり、具体的にはプロピレン、１−ブテン、２−ブテン、２−メチル−１−プロペン、１−ペンテン、２−メチル−１−ブテン、１−ヘキセン、４−メチル−１−ペンテン、２−メチル−１−ペンテン、３−メチル−１−ペンテン、１−ヘプテン、５−メチル−１−ヘキセン、４−メチル−１−ヘキセン、４，４−ジメチル−１−ペンテン、１−オクテン、１−デセン、およびこれらの混合物が挙げられる。
これらのα−オレフィンの中では、プロピレン、１−ブテン、１−ヘキセン、１−オクテンが好ましいが、中でも１−ブテンが最も好ましく、次いでプロピレンおよび１−オクテンが好ましく、次いで１−ヘキセンが好ましい。すなわち、（ハ）成分としては、エチレン−１−ブテン共重合体が最も好ましく、次いでエチレン−プロピレン共重合体およびエチレン−１−オクテン共重合体が好ましく、次いでエチレン−１−ヘキセン共重合体が好ましい。
(C) The ethylene-based olefin polymer used in the present invention is a polymer having more than 20 mol% of ethylene, and is a linear or branched olefin polymer. Typical examples of this linear or branched olefin-based polymer include ethylene-α-olefin-based copolymers and high-pressure low-density polyethylene.
Here, the α-olefin in the ethylene-α-olefin-based copolymer is generally one having 3 to 12 carbon atoms, and specifically, propylene, 1-butene, 2-butene, 2-methyl-1. -Propene, 1-pentene, 2-methyl-1-pentene, 1-hexene, 4-methyl-1-pentene, 2-methyl-1-pentene, 3-methyl-1-pentene, 1-hexene, 5-methyl Included are -1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 1-octene, 1-decene, and mixtures thereof.
Among these α-olefins, propylene, 1-butene, 1-hexene and 1-octene are preferable, but 1-butene is most preferable, then propylene and 1-octene are preferable, and 1-hexene is preferable. That is, as the component (c), an ethylene-1-butene copolymer is most preferable, followed by an ethylene-propylene copolymer and an ethylene-1-octene copolymer, followed by an ethylene-1-hexene copolymer. preferable.
また、（ハ）成分には、必要に応じて非共役ジエン化合物が共重合されても良い。（ハ）成分に用いられることのある非共役ジエン化合物としては、ジシクロペンタジエン、トリシクロペンタジエン、５−メチル−２，５−ノルボナジエン、５−メチレン−２−ノルボルネン、５−エチリデン−２−ノルボルネン、５−イソプロペニル−２−ノルボルネン、５−イソプロピリデン−２−ノルボルネン、５−（１−ブテニル）−２−ノルボルネン、シクロオクタジエン、ビニルシクロヘキセン、１，５，９−シクロドデカトリエン、１，４−ヘキサジエン、１，６−オクタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン、３，６−ジメチル−１，７−オクタジエンなどが挙げられ、好ましくは５−エチリデン−２−ノルボルネン、ジシクロペンタジエンである。これらは、１種単独であるいは２種以上併用して使用することができる。
上記各種のエチレンを主体とするオレフィン系重合体は、各々単独でも（ハ）成分として好適に用いられるが、２種またはそれ以上の重合体のブレンド物であってもよい。このブレンド物としては、例えば２種の重合体のブレンド物の場合、直鎖状重合体同士のブレンド物、分岐状重合体同士のブレンド物、さらに直鎖状重合体と分岐状重合体とのブレンド物のいずれの組み合わせも、（ハ）成分として好適である。
Further, a non-conjugated diene compound may be copolymerized with the component (c), if necessary. Examples of the non-conjugated diene compound that may be used as the component (c) include dicyclopentadiene, tricyclopentadiene, 5-methyl-2,5-norbornene, 5-methylene-2-norbornene, and 5-ethylidene-2-norbornene. , 5-Isopropenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5- (1-butenyl) -2-norbornene, cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatrine, 1, Examples thereof include 4-hexadiene, 1,6-octadene, 1,7-octadene, 1,8-norbornene, 1,9-decadene, 3,6-dimethyl-1,7-octadene, and the like, preferably 5-ethylidene-. 2-Norbornene, dicyclopentadiene. These can be used alone or in combination of two or more.
The above-mentioned various ethylene-based olefin-based polymers are preferably used alone or as the component (c), but may be a blend of two or more polymers. As this blend, for example, in the case of a blend of two kinds of polymers, a blend of linear polymers, a blend of branched polymers, and a blend of linear polymer and branched polymer. Any combination of blends is suitable as the component (c).
本発明の成形品において、（イ）成分は１〜９９重量％、好ましくは１０〜９９重量％、より好ましくは３０〜９９重量％、さらに好ましくは５０〜９９重量％、（ロ）成分は１〜９９重量％、好ましくは１〜９０重量％、より好ましくは１〜７０重量％、さらに好ましくは１〜５０重量％、（ハ）成分は０〜９８重量％、好ましくは０〜９０重量％、より好ましくは０〜７０重量％、さらに好ましくは０〜５０重量％〔ただし（イ）＋（ロ）＋（ハ）＝１００重量％〕である。（イ）成分が１重量％未満および／または（ロ）成分が９９重量％を超える場合、ヒートシール性が低下し、また成形性も劣る。また（ロ）成分が１重量％未満および／または（イ）成分が９９重量％を超える場合、透明性、耐衝撃性が劣るものとなる。（ハ）成分は必要に応じて用いられるが、これが９８重量％を超える場合、柔軟性および成形性が劣るものとなり、好ましくない。 In the molded product of the present invention, the component (a) is 1 to 99% by weight, preferably 10 to 99% by weight, more preferably 30 to 99% by weight, further preferably 50 to 99% by weight, and the component (b) is 1. ~ 99% by weight, preferably 1 to 90% by weight, more preferably 1 to 70% by weight, further preferably 1 to 50% by weight, and the component (c) is 0 to 98% by weight, preferably 0 to 90% by weight. It is more preferably 0 to 70% by weight, still more preferably 0 to 50% by weight [however, (a) + (b) + (c) = 100% by weight]. When the component (a) is less than 1% by weight and / or the component (b) exceeds 99% by weight, the heat sealability is lowered and the moldability is also poor. Further, when the component (b) is less than 1% by weight and / or the component (a) exceeds 99% by weight, the transparency and impact resistance are inferior. The component (c) is used as needed, but if it exceeds 98% by weight, the flexibility and moldability will be inferior, which is not preferable.
共役ジエンのビニル結合含量およびポリブタジエンの１，４−結合含量
赤外分析法を用い、ハンプトン法により算出した。
水添率
四塩化エチレンを溶媒に用い、１００ＭＨｚ、1Ｈ−ＮＭＲスペクトルから算出した。
水添ジエン系共重合体の重量平均分子量
トリクロロベンゼンを溶媒に用い、１３５℃におけるゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用いてポリスチレン換算で求めた。
透明性
ＪＩＳ Ｋ６７８２に準拠して全ヘイズを測定し、透明性の指標とした。
○；Ｈａｚｅ≦３０％
×；Ｈａｚｅ＞３０％
耐熱性
１２１℃にセットした蒸気圧力容器内に、フィルムを吊り下げ、１時間投入後の形状保持性を観察し、評価した。
○；変形せずフィルム形状が保持されている。
×；変形した（大きな収縮を示した）。
柔軟性
ＪＩＳ Ｋ７１２７に準拠してヤング率を測定し、柔軟性の指標とした。
○；ヤング率≦５０００ｋｇｆ／ｃｍ2
×；ヤング率＞５０００ｋｇｆ／ｃｍ2
The vinyl bond content of the conjugated diene and the 1,4-bond content of polybutadiene were calculated by the Hampton method using infrared analysis.
Hydrogenation rate Ethylene tetrachloride was used as a solvent, and it was calculated from a 100 MHz, 1 H-NMR spectrum.
With weight average molecular weight tri-chloro benzene hydrogenated diene copolymer in the solvent was determined in terms of polystyrene by gel permeation chromatography (GPC) at 135 ° C..
Transparency All haze was measured according to JIS K6782 and used as an index of transparency.
◯; Haze ≦ 30%
×; Haze> 30%
The film was suspended in a steam pressure vessel set at a heat resistance of 121 ° C., and the shape retention after being charged for 1 hour was observed and evaluated.
◯; The film shape is maintained without deformation.
X; deformed (showed large contraction).
Flexibility The Young's modulus was measured in accordance with JIS K7127 and used as an index of flexibility.
○; Young's modulus ≦ 5000 k gf / cm 2
×; Young's modulus> 5000 k gf / cm 2
参考例
実施例および比較例に示す配合に用いられる各種の成分は、以下の通りである。
ポリプロピレン
ＰＰ−１〔チッソ石油化学（株）製ＸＦ１８００〕密度０．９ｇ／ｃｍ3、ＭＦＲ１．８ｇ／１０分
ＰＰ−２〔三菱化学（株）製ＦＸ−４〕密度０．９ｇ／ｃｍ3、ＭＦＲ７ｇ／１０分
水添ジエン系共重合体
表１に示すミクロ構造、重量平均分子量、水添率の水添ジエン系共重合体（ＤＲ−１〜ＤＲ−２）。
Reference Examples Various components used in the formulations shown in Examples and Comparative Examples are as follows.
Polypropylene PP-1 [XF1800 manufactured by Chisso Petrochemical Corporation] Density 0.9 g / cm 3 , MFR 1.8 g / 10 minutes PP-2 [FX-4 manufactured by Mitsubishi Chemical Corporation] Density 0.9 g / cm 3 , MFR 7g / 10 minutes
Microstructure shown in hydrogenated diene copolymer Table 1, the weight average molecular weight, hydrogenated diene copolymer hydrogenation ratio (DR-1~DR-2).
実施例１〜５および比較例１〜３
表２に示す配合の組成物を口径５０ｍｍ、Ｌ／Ｄ３６の押出機を用いて１８０〜２３０℃で混練し、Ｔダイに供給して、ダイ温度２１０〜２３０℃、厚み２００μｍのポリプロピレン系フィルムを作製した。得られたフィルムの物性の評価結果を併せて表２に示す。実施例１〜５の結果から明らかなように、本発明のフィルムは、透明性と耐熱性に優れ、かつ柔軟性に優れていることが分かる。これに対して、比較例１は（イ）成分のみを使用した例であるが、本発明のフィルムと比較して、透明性と柔軟性が劣ることがわかる。また比較例２〜３は（ロ）成分のみを使用した例であるが、いずれも耐熱性が劣ることがわかる。
Examples 1-5 and Comparative Examples 1-3
The compositions of the formulations shown in Table 2 are kneaded at 180 to 230 ° C. using an extruder having a diameter of 50 mm and L / D36, and supplied to a T die to obtain a polypropylene film having a die temperature of 210 to 230 ° C. and a thickness of 200 μm. Made. Table 2 also shows the evaluation results of the physical characteristics of the obtained film. As is clear from the results of Examples 1 to 5, the film of the present invention is excellent in transparency, heat resistance, and flexibility. On the other hand, Comparative Example 1 is an example in which only the component (a) is used, but it can be seen that the transparency and flexibility are inferior to those of the film of the present invention. Further, Comparative Examples 2 and 3 are examples in which only the component (b) is used, but it can be seen that all of them are inferior in heat resistance.
Claims (6)
Priority Applications (1)
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| JP10267058A JP2000093490A (en) | 1998-09-21 | 1998-09-21 | Molded goods for medical treatment |
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| JP10267058A JP2000093490A (en) | 1998-09-21 | 1998-09-21 | Molded goods for medical treatment |
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| JP2000093490A JP2000093490A (en) | 2000-04-04 |
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| BR0111655A (en) * | 2000-05-31 | 2003-05-20 | Dow Global Technologies Inc | Olefin polymer compositions |
| JP5973118B2 (en) * | 2005-11-10 | 2016-08-23 | 田辺三菱製薬株式会社 | Plastic container filled with aqueous solution containing pyrazolone compound |
| JP4676382B2 (en) * | 2006-05-25 | 2011-04-27 | リケンテクノス株式会社 | Thermoplastic elastomer composition for tube or hose |
| JP5706678B2 (en) * | 2010-12-20 | 2015-04-22 | テルモ株式会社 | Method for manufacturing medical bag and medical bag |
| EP3348396B1 (en) | 2015-09-09 | 2019-08-14 | Asahi Kasei Kabushiki Kaisha | Film |
| JP6648145B2 (en) | 2015-09-09 | 2020-02-14 | 旭化成株式会社 | Hydrogenated block copolymer, polypropylene resin composition and molded article |
| SG11201801743QA (en) | 2015-09-09 | 2018-04-27 | Asahi Chemical Ind | Tube using hydrogenated block copolymer |
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