JPH0112770B2 - - Google Patents
Info
- Publication number
- JPH0112770B2 JPH0112770B2 JP54030890A JP3089079A JPH0112770B2 JP H0112770 B2 JPH0112770 B2 JP H0112770B2 JP 54030890 A JP54030890 A JP 54030890A JP 3089079 A JP3089079 A JP 3089079A JP H0112770 B2 JPH0112770 B2 JP H0112770B2
- Authority
- JP
- Japan
- Prior art keywords
- sheet
- polymer
- polypropylene
- intrinsic viscosity
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 229920001155 polypropylene Polymers 0.000 claims description 32
- 239000004743 Polypropylene Substances 0.000 claims description 22
- -1 polypropylene Polymers 0.000 claims description 22
- 229920000642 polymer Polymers 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 description 10
- 238000003856 thermoforming Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 238000007666 vacuum forming Methods 0.000 description 3
- 230000037303 wrinkles Effects 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical class Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】
本発明は溶融弾性の高いポリプロピレンシート
に関するものである。更に詳しくは、押出加工性
が良く、しかも溶融弾性が高い特殊ポリプロピレ
ンの使用により得られる、肌荒れの無い、透明性
の優れた、しかも熱加工性に富んだポリプロピレ
ンシートに関するものである。
ポリプロピレンシートも他の熱加塑性樹脂シー
トと同様真空成形、圧空成形等の熱成形法により
二次加工され、食品包装トレー類、雑貨類、自動
車材料、コンテナー類等の種々の用途に使用され
ている。
しかるにポリプロピレン本来の特性として溶融
時の弾性にとぼしいという性質があり、シート材
料を熱成形する際に加熱によりシート材料が溶融
垂下し、しわ、や偏肉となつて成形品に現われ、
二次成形が困難である。ポリプロピレンの溶融弾
性を向上させる方法として、高分子量ポリプロピ
レンを使用する方法、溶融弾性の高い他ポリマー
を添加する方法等が一般に取られているが、これ
らの方法はそれぞれ以下に記す欠点をもつてい
る。
すなわち、高分子量ポリプロピレンを使用した
押出シートは押出加工時の肌荒れの為にシートの
透明性、光沢が失なわれる。
また溶融弾性の高い他ポリマーの添加による方
法として低密度ポリエチレン等のブレンドが掲げ
られるが、ポリプロピレンシートの剛性を低下さ
せる、あるいは屈折率の異なる物の混入によりポ
リプロピレンシートの透明性が低下する等の欠点
がある。
このようにポリプロピレン本来の剛性、透明
性、光沢を生かした、しかも熱成形の際の加熱に
より溶融垂下しない程度の溶融弾性を持つポリプ
ロピレンシートは現在まで望まれなかつた。
本発明者らはこのポリプロピレン本来の欠点を
克服するため鋭意研究の結果、他樹脂を添加しな
くともプロピレン系高分子量重合体を添加する事
により押出シート加工時の肌荒れもなく、しかも
加熱時の溶融弾性に優れた理想的なポリプロピレ
ンシートが得られる事を見出し、本発明に到達し
たものである。
本発明は、特願昭52−105470、52−105471、52
−105472等に記載されている方法により得られる
プロピレン重合体、すなわち、チーグラーナツタ
触媒を用いたプロピレンの単独重合において同一
系内で重合条件を変えて二段階以上で重合を行な
わせる事により得られる、平均分子量の異なる二
成分を含むプロピピレン系重合体を溶融押出加工
して製造されるポリプロピレンシートで、該プロ
ピレン系重合体が4.0dl／ｇ以下の極限粘度を持
つ重合体成分(A)60〜99.5重量％および重合体成分
(A)の２倍以上の極限粘度をもつ重合成分(B)0.5〜
40重量％とから成り、かつプロピレン系重合体全
体の極限粘度〔η〕が〔η〕＞2.0dl／ｇである事
を特徴とする溶融弾性の高いポリプロピレンシー
トを提供するものである。
極限粘度の値は135℃のテトラリン溶液で測定
したものである。
本発明に用いるプロピレン系重合体は基本的に
は多量の低分子量部分と少量の高分子量部分とか
らなる。
重合体全体としての極限粘度が2.0dl／ｇ以下
となるとシート加工時にエアーギヤツプでのドロ
ーダウンが大きくシートの偏肉が大きくなつて不
都合を生じる。重合体成分(A)についてはその極限
粘度が4.0dl／ｇ以上となると、メルトフラクチ
アーを起こす臨界剪断速度値が低くなり一般の押
出加工においても臨界値を越えるようになり押出
シート表面に肌荒れ現象を発生する。
高分子量重合体成分(B)についてはその極限粘度
が低分子量重合体成分(A)の２倍以上が適当であ
り、２倍未満ではポリプロピレンシートの溶融弾
性が不満足となりシートを熱成形する際に加熱に
よる溶融垂下が大きく、成形品にしわ、偏肉を残
す。
また重合体成分(A)、(B)を必須成分とするが、
(A)、(B)の中間の極限粘度を有する重合体を含有し
ても良好な溶融弾性は変わらない。
重合成分(A)、(B)の量比については、シートに肌
荒れが無く、溶融弾性が十分な範囲は低分子量重
合成分(A)60〜99.5重量％（好ましくは75〜99重量
％）、高分子量重合成分(B)0.5〜40重量％（好まし
くは1.0〜25重量％）であり、低分子量重合成分
がこの範囲を越えるとシートの十分な溶融弾性が
得られず高分子量重合成分がこの範囲を越えると
シートに肌荒れを生ずる。
本発明に使用されるプロピレン系重合体は上記
のような各成分を有するものであり、重合時に調
整される事が必要である。
特にチーグラー・ナツタ触媒による重合におい
て分子量調節剤の濃度を二段階に変えて重合して
製造するのが好ましい。
この方法によれば高分子量成分の分散が良好に
なるため押出加工して得られるシートはフイツシ
ユアイが見られず外観のすぐれたものとなる。
他の方法として例えばそれぞれの分子量成分を
溶融混合することが考えられるが、、高分子量成
分の分散が不良でフイツシユアイが生じるばかり
か良好なシート表面が得られず不適当である。
本発明に使用されるプロピレン系重合体として
は実質的に結晶性を有するプロピピレン単独重合
体、またはプロピレンと他のα−オレフインとの
共重合体であり、α−オレフインとしてはエチレ
ン、ブテン−１などが好ましい。酸化防止剤、そ
の他一般に知られている造核剤、充墳剤、顔料等
の本発明の効果を妨げるものではない。
またシート成形方法としては通常の押出加工法
で十分であり、一般にはＬ／D22〜30、スクリユ
ー圧縮比3.0〜3.5といつた装置が用いられる。
以上述べて来たように、本発明のポリプロピレ
ンシートは表面肌荒れによる透明性、光沢の低下
がなく、熱成形時にその大きな溶融弾性により加
熱しても溶融垂下が小さく、しわ、偏肉のない良
好な成形品を与え、しかも異樹脂を含有しないの
で剛性の低下、透明性の低下等などのない理想的
なポリプロピレンシートである。
以下に実施例によりさらに本発明を具体的に説
明するが本発明はこれらの実施例により限定され
るものではない。
実施例および比較例
液状プロピレンを30Kg／cm2Ｇ、70℃の条件下で
ジエチルアルミニウムクロライドおよび四塩化チ
タンをエチルアルミニウムセスキクロライドにて
還元し、さらに活性化した三塩化チタンを触媒と
して水素の存在下で重合させ比較例１に使用し
た。
さらに抜き出した重合体スラリーを61〜64℃に
保持して再び液状プロピレンと前段より低分圧の
水素存在下で接触させ、更に重合を続行させ、得
られた重合体を実施例１〜４および比較例２〜４
に使用した。
これらの方法により得られたプロピレン重合体
に通常の安定剤を添加して押出機によりペレツト
化したのち、シリンダー径65mm（Ｌ／Ｄ＝24、
CR＝4.0）のシート押出装置を用いて樹脂温度
260℃にて350μ厚みのシートを加工した。
ついで該ポリプロピレンシートを浅野製作所製
真空成形機にてクランプ面積500mm×500mm、シー
ト温度170〜190℃にて絞り比0.3の箱状成形品を
二次成形した。
重合体物性およびシート物性の測定について
は、MIは230℃、2.16Kg／cm2荷重下で測定した。
溶融垂下の程度については真空成形機にて500
mm×500mmのクランンプ面積にて加熱し、シート
中央部が300mm垂下する迄の時間（sec）で表示し
た。
結果は第１表より明らかなように実施例１〜４
について溶融弾性の高い、しかも表面肌荒れのな
いポリプロピレンシートを得た。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polypropylene sheet with high melt elasticity. More specifically, the present invention relates to a polypropylene sheet that is free from roughness, has excellent transparency, and has excellent heat processability, which is obtained by using a special polypropylene that has good extrusion processability and high melt elasticity. Like other thermoplastic resin sheets, polypropylene sheets are subjected to secondary processing using thermoforming methods such as vacuum forming and pressure forming, and are used in a variety of applications such as food packaging trays, miscellaneous goods, automobile materials, and containers. There is. However, the inherent property of polypropylene is that it has poor elasticity when melted, and when thermoforming sheet materials, the sheet material melts and sag due to heating, causing wrinkles and uneven thickness to appear in the molded product.
Secondary molding is difficult. Common methods for improving the melt elasticity of polypropylene include using high molecular weight polypropylene and adding other polymers with high melt elasticity, but each of these methods has the following drawbacks. . That is, extruded sheets using high molecular weight polypropylene lose their transparency and gloss due to roughening during extrusion processing. Blends such as low-density polyethylene are proposed as a method of adding other polymers with high melt elasticity, but this may reduce the rigidity of the polypropylene sheet or reduce the transparency of the polypropylene sheet due to the inclusion of substances with different refractive indexes. There are drawbacks. As described above, there has been no desire to date for a polypropylene sheet that takes advantage of the inherent rigidity, transparency, and gloss of polypropylene, and that also has melt elasticity to the extent that it does not melt and sag when heated during thermoforming. The inventors of the present invention have conducted intensive research to overcome the inherent drawbacks of polypropylene, and have found that by adding a propylene-based high molecular weight polymer without adding any other resin, there is no roughening of the surface during extrusion sheet processing, and moreover, even when heated. It was discovered that an ideal polypropylene sheet with excellent melt elasticity can be obtained, and the present invention was achieved. The present invention is based on Japanese Patent Application No. 52-105470, 52-105471, 52
A propylene polymer obtained by the method described in -105472, etc., i.e., by carrying out the polymerization in two or more stages by changing the polymerization conditions in the same system in the homopolymerization of propylene using a Ziegler-Natsuta catalyst. , a polypropylene sheet produced by melt extrusion processing of a propypylene polymer containing two components with different average molecular weights, wherein the propylene polymer has an intrinsic viscosity of 4.0 dl/g or less as a polymer component (A) 60 to 99.5% by weight and polymer components
Polymer component (B) with an intrinsic viscosity more than twice that of (A) 0.5~
40% by weight, and the intrinsic viscosity [η] of the entire propylene polymer is [η] > 2.0 dl/g. Intrinsic viscosity values were measured in a tetralin solution at 135°C. The propylene polymer used in the present invention basically consists of a large amount of low molecular weight portion and a small amount of high molecular weight portion. If the intrinsic viscosity of the polymer as a whole is less than 2.0 dl/g, the drawdown at the air gap during sheet processing will be large, resulting in a large uneven thickness of the sheet, causing problems. When the intrinsic viscosity of the polymer component (A) is 4.0 dl/g or more, the critical shear rate value that causes melt fracture becomes low and exceeds the critical value even in general extrusion processing, causing roughness on the surface of the extruded sheet. A phenomenon occurs. It is appropriate that the intrinsic viscosity of the high molecular weight polymer component (B) is at least twice that of the low molecular weight polymer component (A); if the intrinsic viscosity is less than twice that of the low molecular weight polymer component (A), the melt elasticity of the polypropylene sheet will be unsatisfactory, which may cause problems when thermoforming the sheet. The melt sag due to heating is large, leaving wrinkles and uneven thickness on the molded product. In addition, polymer components (A) and (B) are essential components,
Even if a polymer having an intrinsic viscosity between (A) and (B) is contained, good melt elasticity remains. Regarding the ratio of the polymeric components (A) and (B), the range in which the sheet does not have rough skin and has sufficient melt elasticity is 60 to 99.5% by weight (preferably 75 to 99% by weight) of the low molecular weight polymeric component (A), The high molecular weight polymeric component (B) is 0.5 to 40% by weight (preferably 1.0 to 25% by weight); if the low molecular weight polymeric component exceeds this range, sufficient melt elasticity of the sheet cannot be obtained, and the high molecular weight polymeric component is Exceeding this range will cause rough skin on the sheet. The propylene polymer used in the present invention has the above-mentioned components, which need to be adjusted during polymerization. In particular, it is preferable to produce the polymer by changing the concentration of the molecular weight regulator in two stages in polymerization using a Ziegler-Natsuta catalyst. According to this method, the high molecular weight components are well dispersed, so that the sheet obtained by extrusion processing has no visible fish eyes and has an excellent appearance. Another method that can be considered is to melt and mix the respective molecular weight components, but this method is unsuitable because not only the high molecular weight components are poorly dispersed, causing stickiness, but also a good sheet surface cannot be obtained. The propylene polymer used in the present invention is a substantially crystalline propylene homopolymer or a copolymer of propylene and other α-olefins, and examples of the α-olefins include ethylene and butene-1. etc. are preferable. It does not interfere with the effects of the present invention of antioxidants and other commonly known nucleating agents, fillers, pigments, and the like. Further, as a sheet forming method, a normal extrusion processing method is sufficient, and generally an apparatus having an L/D of 22 to 30 and a screw compression ratio of 3.0 to 3.5 is used. As described above, the polypropylene sheet of the present invention does not reduce transparency and gloss due to surface roughness, has small melt sag even when heated due to its high melt elasticity during thermoforming, and has good properties with no wrinkles or uneven thickness. It is an ideal polypropylene sheet that provides a molded product with excellent properties, and since it does not contain any foreign resin, there is no decrease in rigidity or transparency. EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Examples and Comparative Examples Diethyl aluminum chloride and titanium tetrachloride are reduced with ethyl aluminum sesquichloride under the conditions of liquid propylene at 30 Kg/cm 2 G and 70°C, and further activated titanium trichloride is used as a catalyst to reduce the presence of hydrogen. It was polymerized below and used in Comparative Example 1. Furthermore, the extracted polymer slurry was maintained at 61 to 64°C and brought into contact with liquid propylene again in the presence of hydrogen at a lower partial pressure than in the previous stage, and the polymerization was further continued. Comparative examples 2 to 4
used for. After adding a normal stabilizer to the propylene polymer obtained by these methods and pelletizing it with an extruder,
The resin temperature was measured using a sheet extrusion device with CR=4.0).
A 350μ thick sheet was processed at 260℃. The polypropylene sheet was then second-formed into a box-shaped product using a vacuum forming machine manufactured by Asano Seisakusho with a clamp area of 500 mm x 500 mm and a drawing ratio of 0.3 at a sheet temperature of 170 to 190°C. Regarding the measurement of polymer physical properties and sheet physical properties, MI was measured at 230° C. and under a load of 2.16 Kg/cm 2 . Regarding the degree of melt droop, use a vacuum forming machine to
Heating was performed using a clamp area of mm x 500 mm, and the time (sec) until the center of the sheet drooped by 300 mm was expressed. As is clear from Table 1, the results are for Examples 1 to 4.
A polypropylene sheet with high melt elasticity and no surface roughening was obtained. 【table】
Claims (1)
で重合条件を変えて二段階以上で重合を行なわせ
る事により得られる、平均分子量の異なる二成分
を含むプロピレン系重合体を溶融押出加工して製
造されるポリプロピレンシートで、該プロピレン
系重合体が4.0dl／ｇ以下の極限粘度を持つ重合
体成分(A)60〜99.5重量％および重合体成分(A)の２
倍以上の極限粘度を持つ重合体成分(B)0.5〜40重
量％とから成り、かつ、プロピレン系重合体全体
の極限粘度〔η〕が〔η〕＞2.0dl／ｇである事を
特徴とするポリプロピレンシート。[Claims] 1. In propylene homopolymerization, melt extrusion of a propylene polymer containing two components with different average molecular weights is obtained by polymerizing in two or more stages by changing polymerization conditions within the same polymerization system. A polypropylene sheet produced by processing, in which the propylene polymer has an intrinsic viscosity of 4.0 dl/g or less, 60 to 99.5% by weight of the polymer component (A), and 2 of the polymer component (A).
It is characterized by comprising 0.5 to 40% by weight of a polymer component (B) having an intrinsic viscosity more than double that, and the intrinsic viscosity [η] of the entire propylene polymer is [η] > 2.0 dl/g. polypropylene sheet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089079A JPS55123637A (en) | 1979-03-15 | 1979-03-15 | Extruded sheet of polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3089079A JPS55123637A (en) | 1979-03-15 | 1979-03-15 | Extruded sheet of polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS55123637A JPS55123637A (en) | 1980-09-24 |
| JPH0112770B2 true JPH0112770B2 (en) | 1989-03-02 |
Family
ID=12316311
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3089079A Granted JPS55123637A (en) | 1979-03-15 | 1979-03-15 | Extruded sheet of polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS55123637A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006057254A1 (en) * | 2004-11-25 | 2006-06-01 | Asahi Kasei Chemicals Corporation | Resin composition suitable for forming sheet |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5638309A (en) * | 1979-09-07 | 1981-04-13 | Mitsui Toatsu Chem Inc | Propylene copolymer for forming film |
| JPS57185304A (en) * | 1981-05-11 | 1982-11-15 | Mitsubishi Chem Ind Ltd | Preparation of propylene polymer |
| JPS57185336A (en) * | 1981-05-11 | 1982-11-15 | Mitsubishi Chem Ind Ltd | Polypropylene composition |
| JPS57187337A (en) * | 1981-05-13 | 1982-11-18 | Mitsubishi Chem Ind Ltd | Polypropylene composition |
| JPS587439A (en) * | 1981-07-06 | 1983-01-17 | Mitsubishi Chem Ind Ltd | Polypropylene composition |
| JPS5827731A (en) * | 1981-08-12 | 1983-02-18 | Mitsubishi Chem Ind Ltd | Polyolefin composition and its preparation |
| JPH075668B2 (en) * | 1987-02-04 | 1995-01-25 | チッソ株式会社 | Highly crystalline polypropylene |
| US4970280A (en) * | 1987-04-01 | 1990-11-13 | Chisso Corporation | Continuous process for producing high molten viscoelastic polypropylene or ethylene-propylene copolymer |
| US5140062A (en) * | 1987-04-01 | 1992-08-18 | Chisso Corporation | Continuous process for producing high molten viscoelastic polypropylene of ethylene-propylene copolymer |
| US4950720A (en) * | 1988-04-29 | 1990-08-21 | Exxon Chemical Patents Inc. | Modified polypropylene, process for making and article made from the same |
| KR100254936B1 (en) | 1995-10-18 | 2000-05-01 | 고토 기치 | Olefin(co-)polymer compositions and method for producing the same and catalyst for olefin(co-)polymerization and method for producing the same |
| EP0864589A4 (en) | 1995-12-01 | 2003-04-02 | Chisso Corp | Molded resin articles |
| KR19980017267A (en) * | 1996-08-30 | 1998-06-05 | 백영배 | Method for producing polypropylene elastomer |
| TW425414B (en) * | 1997-02-18 | 2001-03-11 | Chisso Corp | Preactivated catalyst for olefin (co)polymerization, catalyst for olefin (co)polymerization and olefin (co)polymer composition and their manufacturing method |
| EP0972800A4 (en) | 1997-04-02 | 2004-06-16 | Chisso Corp | Modified olefin (co)polymer composition, process for preparing the same, and modified olefin (co)polymer composition molding |
| US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
| TW504515B (en) | 1997-08-07 | 2002-10-01 | Chisso Corp | Olefin (co)polymer composition |
| SG71878A1 (en) * | 1997-12-11 | 2000-04-18 | Sumitomo Chemical Co | Propylene-based polymer composition and foamed article thereof |
| WO2006010414A1 (en) * | 2004-07-30 | 2006-02-02 | Saudi Basic Industries Corporation | Propylene copolymer compositions with high transparency |
| JP2008274031A (en) * | 2007-04-26 | 2008-11-13 | Sumitomo Chemical Co Ltd | Antistatic resin composition and thermoplastic resin multilayered sheet |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219788A (en) * | 1975-08-05 | 1977-02-15 | Stamicarbon | Method and apparatus for polymerizing alphaaalkene |
| JPS5391954A (en) * | 1977-01-24 | 1978-08-12 | Tokuyama Soda Co Ltd | Method of extrusion molding of polypropylene |
| JPS5439487A (en) * | 1977-09-05 | 1979-03-26 | Showa Denko Kk | Preparation of propylene copolymer |
-
1979
- 1979-03-15 JP JP3089079A patent/JPS55123637A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5219788A (en) * | 1975-08-05 | 1977-02-15 | Stamicarbon | Method and apparatus for polymerizing alphaaalkene |
| JPS5391954A (en) * | 1977-01-24 | 1978-08-12 | Tokuyama Soda Co Ltd | Method of extrusion molding of polypropylene |
| JPS5439487A (en) * | 1977-09-05 | 1979-03-26 | Showa Denko Kk | Preparation of propylene copolymer |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006057254A1 (en) * | 2004-11-25 | 2006-06-01 | Asahi Kasei Chemicals Corporation | Resin composition suitable for forming sheet |
| JPWO2006057254A1 (en) * | 2004-11-25 | 2008-06-05 | 旭化成ケミカルズ株式会社 | Resin composition suitable for sheet molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS55123637A (en) | 1980-09-24 |
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