JPH0788430B2 - Film or tape - Google Patents
Film or tapeInfo
- Publication number
- JPH0788430B2 JPH0788430B2 JP61222092A JP22209286A JPH0788430B2 JP H0788430 B2 JPH0788430 B2 JP H0788430B2 JP 61222092 A JP61222092 A JP 61222092A JP 22209286 A JP22209286 A JP 22209286A JP H0788430 B2 JPH0788430 B2 JP H0788430B2
- Authority
- JP
- Japan
- Prior art keywords
- styrene
- based polymer
- polymer
- film
- stretching
- 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 - Fee Related
Links
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 143
- 229920000642 polymer Polymers 0.000 claims description 77
- 238000004458 analytical method Methods 0.000 claims description 7
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 16
- 239000004793 Polystyrene Substances 0.000 description 13
- 229920002223 polystyrene Polymers 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000000944 Soxhlet extraction Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- -1 poly (alkyl styrene Chemical compound 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-UHFFFAOYSA-N 0.000 description 1
- CEBRPXLXYCFYGU-UHFFFAOYSA-N 3-methylbut-1-enylbenzene Chemical compound CC(C)C=CC1=CC=CC=C1 CEBRPXLXYCFYGU-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QROGIFZRVHSFLM-UHFFFAOYSA-N prop-1-enylbenzene Chemical compound CC=CC1=CC=CC=C1 QROGIFZRVHSFLM-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は主としてシンジオタクチック構造を有するスチ
レン系重合体を延伸してなる、機械的強度や耐熱性に優
れたフィルム又はテープに関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a film or tape mainly obtained by stretching a styrene polymer having a syndiotactic structure and having excellent mechanical strength and heat resistance.
スチレン系重合体、特にポリスチレンは、その立体規則
性がアタクチック構造を有するものが一般に用いられて
いるが、このようなアタクチックポリスチレンは結晶化
しないため、機械的強度や耐熱性に劣り、また延伸して
もその物性の改善は期待できない。Styrene-based polymers, particularly polystyrene, are generally used in which their stereoregularity has an atactic structure, but such atactic polystyrene does not crystallize, and thus is poor in mechanical strength and heat resistance, and also stretched. Even so, improvement of the physical properties cannot be expected.
さらに、立体規則性がアイソタクチック構造のポリスチ
レンも知られており、またこれを延伸した成形品も提案
〔高分子化学21,206（1964）〕されているが、このアイ
ソタクチックポリスチレンは結晶化速度が遅く、しかも
結晶構造が螺旋状であるため、延伸してもその効果の発
現が充分なものではない。Furthermore, polystyrene having an isotactic structure in stereoregularity is also known, and a molded product obtained by stretching this is also proposed [Polymer Chemistry 21,206 (1964)]. This isotactic polystyrene has a crystallization rate. However, since the crystal structure is slow and the crystal structure is spiral, the effect is not sufficiently exhibited even when the film is stretched.
本発明者らは、先般、シンジオタクティシティーの高い
スチレン系重合体を開発することに成功した（特開昭62
−104818号公報）。The present inventors have recently succeeded in developing a styrene-based polymer having high syndiotacticity (Japanese Patent Laid-Open No. Sho 62-62).
-104818 publication).
本発明者らは、この新たなシンジオタクチック構造のス
チレン系重合体の物性等についてさらに研究を進めたと
ころ、このスチレン系重合体を延伸処理すると、得られ
る繊維の機械的強度、特に弾性率が飛躍的に向上するこ
とを見出した。本発明は、かかる知見に基づいて完成し
たものである。The present inventors further studied the physical properties of the new styrene-based polymer having a syndiotactic structure. When the styrene-based polymer was subjected to a stretching treatment, the mechanical strength of the obtained fiber, particularly the elastic modulus, was obtained. Has been found to improve dramatically. The present invention has been completed based on such findings.
すなわち本発明は、主としてシンジオタクチック構造を
有するスチレン系重合体を延伸してなるフィルム又はテ
ープを提供するものである。That is, the present invention mainly provides a film or tape obtained by stretching a styrene polymer having a syndiotactic structure.
本発明のフィルム又はテープの材料は、主としてシンジ
オタクチック構造を有するスチレン系重合体である。The material of the film or tape of the present invention is mainly a styrene polymer having a syndiotactic structure.
このスチレン系重合体は、主としてシンジオタクチック
構造、すなわち炭素−炭素結合から形成される主鎖に対
して側鎖であるフェニル基や置換フェニル基が交互に反
対方向に位置する立体構造を有するものであり、そのタ
クティシティーは同位体元素による核磁気共鳴法（13C
−NMR法）により定量される。13 C−NMR法により測定されるタクティシティーは、連続
する複数個の構成単位の存在割合、例えば２個の場合は
ダイアッド、３個の場合はトリアッド、５個の場合はペ
ンタッドによって示すことができるが、本発明に言う主
としてシンジオタクチック構造を有するスチレン系重合
体とは、通常はペンタッド（ラセミペンタッド）で85％
以上、好ましくは95％以上のシンジオタクティシティー
を有するポリスチレン，ポリ（アルキルスチレン），ポ
リ（ハロゲン化スチレン），ポリ（アルコキシスチレ
ン），ポリ（安息香酸エステルスチレン）及びこれらの
混合物、或いはこれらを主成分とする共重合体を指称す
る。This styrene polymer mainly has a syndiotactic structure, that is, one having a three-dimensional structure in which a phenyl group or a substituted phenyl group, which is a side chain, is alternately located in opposite directions with respect to a main chain formed from carbon-carbon bonds. And its tacticity is the nuclear magnetic resonance method ( 13 C
-NMR method). The tacticity measured by the 13 C-NMR method can be indicated by the abundance ratio of a plurality of continuous constitutional units, for example, diad in the case of 2 units, triad in the case of 3 units, and pentad in the case of 5 units. However, the styrene-based polymer mainly having a syndiotactic structure referred to in the present invention is usually pentad (racemic pentad) at 85%.
Above, preferably polystyrene having a syndiotacticity of 95% or more, poly (alkyl styrene), poly (halogenated styrene), poly (alkoxy styrene), poly (benzoic acid ester styrene) and mixtures thereof, or these The copolymer containing the main component is referred to.
なお、ここでポリ（アルキルスチレン）としては、ポリ
（メチル）スチレン，ポリ（エチルスチレン），ポリ
（イソプロピルスチレン），ポリ（ターシャリーブチル
スチレン）などがある。また、ポリ（ハロゲン化スチレ
ン）としては、ポリ（クロロスチレン），ポリ（ブロモ
スチレン）などがある。さらに、ポリ（アルコキシスチ
レン）としては、ポリ（メトキシスチレン），ポリ（エ
トキシスチレン）などがある。Here, examples of poly (alkylstyrene) include poly (methyl) styrene, poly (ethylstyrene), poly (isopropylstyrene), and poly (tertiarybutylstyrene). Examples of poly (halogenated styrene) include poly (chlorostyrene) and poly (bromostyrene). Furthermore, examples of the poly (alkoxystyrene) include poly (methoxystyrene) and poly (ethoxystyrene).
上述の如く、本発明に用いるスチレン系重合体のラセミ
ペンタッドでのシンジオタクティシティーは、通常85％
以上であるが、多少低い値であっても、延伸処理の条件
を選定すれば、充分な引張弾性率を発現することができ
る。しかし、シンジオタクティシティーがあまり低いス
チレン系重合体では、延伸処理しても充分な引張弾性率
の向上は期待できない。As described above, the syndiotacticity of the styrene polymer used in the present invention in the racemic pentad is usually 85%.
As described above, even if the value is somewhat low, a sufficient tensile elastic modulus can be exhibited by selecting the conditions of the stretching treatment. However, with a styrene-based polymer having a very low syndiotacticity, a sufficient improvement in the tensile elastic modulus cannot be expected even if the stretching treatment is performed.
また、本発明に用いるスチレン系重合体は、重量平均分
子量が300,000以上のものであることが望ましく、特に
1,000,000以上のものが好適である。ここで重量平均分
子量が300,000未満のものでは、充分な強度や弾性率を
得ることができない。また、分子量分布については、広
くても狭くても制約を受けることなく用いることができ
る。The styrene polymer used in the present invention preferably has a weight average molecular weight of 300,000 or more,
Those of 1,000,000 or more are preferable. Here, if the weight average molecular weight is less than 300,000, sufficient strength and elastic modulus cannot be obtained. The molecular weight distribution can be used without restriction regardless of whether it is wide or narrow.
本発明によれば、上述のスチレン系重合体を延伸するこ
とにより、優れた物性のフィルム又はテープが得られる
が、ここで延伸は一軸延伸，二軸延伸のいずれで行なっ
てもよく、また延伸倍率は特に制約はないが、３倍以上
が好ましく、５〜10倍が最適である。According to the present invention, by stretching the above-mentioned styrene-based polymer, a film or tape having excellent physical properties can be obtained. Here, the stretching may be uniaxial stretching or biaxial stretching, or stretching The magnification is not particularly limited, but is preferably 3 times or more, and optimally 5 to 10 times.
さらに、延伸方法としても、溶融延伸，湿潤延伸，ゲル
延伸などを挙げることができる。ここで湿潤延伸又はゲ
ル延伸を行なう場合には、溶媒としてベンゼン，トルエ
ン，キシレン，エチルベンゼン，シクロヘキサン，デカ
リン,N−メチルピロリドン，テトラヒドロフラン，四塩
化炭素，クロロホルム，ジクロロメタン，モノクロロベ
ンゼン，ジクロロベンゼン，トリクロロベンゼン，トリ
クレンなどを用いればよい。Further, as the stretching method, melt stretching, wet stretching, gel stretching and the like can be mentioned. When wet stretching or gel stretching is performed here, benzene, toluene, xylene, ethylbenzene, cyclohexane, decalin, N-methylpyrrolidone, tetrahydrofuran, carbon tetrachloride, chloroform, dichloromethane, monochlorobenzene, dichlorobenzene, trichlorobenzene are used as solvents. , Trichlene, etc. may be used.
また、このシンジオタクチック構造のスチレン系重合体
に、アタクチック構造のスチレン系重合体、アイソタク
チック構造のスチレン系重合体、或いは低分子量のシン
ジオタクチック構造のスチレン系重合体を配合したもの
を用いて延伸処理を行なうこともできる。In addition, this styrene-based polymer of syndiotactic structure, styrene-based polymer of atactic structure, styrene-based polymer of isotactic structure, or a mixture of styrene-based polymer of low molecular weight syndiotactic structure It can also be used for stretching treatment.
次に、本発明を実施例及び比較例によりさらに詳しく説
明する。Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１ （１）スチレン系重合体の製造 反応容器に、溶媒としてトルエン20mlと、触媒成分とし
てテトラエトキシチタニウム0.05ミリモル及びメチルア
ルミノキサンをアルミニウム原子として５ミリモル加
え、40℃においてこれにスチレン150mlを加え、４時間
重合反応を行なった。反応終了後、生成物を塩酸−メタ
ノール混合液で洗浄し、接触成分を分解除去した。次い
で乾燥し、スチレン系重合体（ポリスチレン）25gを得
た。Example 1 (1) Production of Styrene Polymer To a reaction vessel, 20 ml of toluene as a solvent, 0.05 mmol of tetraethoxytitanium as a catalyst component and 5 mmol of methylaluminoxane as an aluminum atom were added, and 150 ml of styrene was added thereto at 40 ° C. The polymerization reaction was carried out for 4 hours. After completion of the reaction, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove contact components. Then, it was dried to obtain 25 g of a styrene polymer (polystyrene).
次に、この重合体を、メチルエチルケトンを溶媒として
ソックスレー抽出し、抽出残分（以下、MIPという。）9
5wt％を得た。このものの重量平均分子量は1,350,000で
あり、数平均分子量は480,000であって、融点は270℃で
あった。また、13C−NMRによる分析から、シンジオタク
チック構造に基因する145.35ppmに吸収が認められ、そ
のピーク面積から算出したラセミペンタッドでのシンジ
オタクティシティーは96％であった。Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent, and the extraction residue (hereinafter referred to as MIP) 9
5 wt% was obtained. This product had a weight average molecular weight of 1,350,000, a number average molecular weight of 480,000 and a melting point of 270 ° C. Also, from the analysis by 13 C-NMR, absorption was observed at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in the racemic pentad calculated from the peak area was 96%.
（２）延伸フィルム（テープ）の製造 上記（１）で得られたシンジオタクチック構造のスチレ
ン系重合体を、溶媒のエチルベンゼン中に入れて加熱溶
解し、２重量％の濃度のスチレン系重合体溶液を得た。
この溶液を充分に冷却したアルミニウム製の箱に流し込
み、寒天状のゲルを得た。このゲルをヌッチェ上でプレ
スしつつ、吸引乾燥し、室温において減圧下、24時間乾
燥してゲル板を得た。次に、このゲル板を短冊状に切断
し、この短冊を空気中、130℃において延伸倍率８倍に
延伸した。得られた延伸物につき、機械的強度を測定し
た。結果を第１表に示す。(2) Production of Stretched Film (Tape) The styrene-based polymer having the syndiotactic structure obtained in (1) above was put into ethylbenzene as a solvent and dissolved by heating to give a styrene-based polymer having a concentration of 2% by weight. A solution was obtained.
The solution was poured into a sufficiently cooled aluminum box to obtain an agar-like gel. The gel was pressed and dried on a Nutsche with suction, and dried at room temperature under reduced pressure for 24 hours to obtain a gel plate. Next, the gel plate was cut into strips, and the strips were stretched in air at 130 ° C. at a stretch ratio of 8 times. The mechanical strength of the obtained stretched product was measured. The results are shown in Table 1.
実施例２ （１）スチレン系重合体の製造 重合温度を30℃としたほかは、実施例１の（１）と同様
の操作を行ない、スチレン系重合体（ポリスチレン）9.
0gを得た。このもののMIPは、99wt％であった。また、
得られたスチレン系重合体（MIP）は、重量平均分子量
1,800,000であり、数平均分子量650,000であって、シン
ジオタクティシティー98％であった。Example 2 (1) Manufacture of styrene-based polymer A styrene-based polymer (polystyrene) was prepared in the same manner as in (1) of Example 1 except that the polymerization temperature was 30 ° C.
I got 0g. The MIP of this product was 99 wt%. Also,
The obtained styrene polymer (MIP) has a weight average molecular weight.
It was 1,800,000, the number average molecular weight was 650,000, and the syndiotacticity was 98%.
（２）延伸フィルム（テープ）の製造 上記（１）で得たスチレン系重合体を用い、延伸倍率を
７倍としたほかは、実施例１の（２）と同様の操作を行
なった。結果を第１表に示す。(2) Production of Stretched Film (Tape) The same operation as in (2) of Example 1 was performed except that the styrene-based polymer obtained in (1) above was used and the stretching ratio was set to 7 times. The results are shown in Table 1.
実施例３ （１）スチレン系重合体の製造 重合温度を20℃としたほかは、実施例１の（１）と同様
の操作を行ない、スチレン系重合体（ポリスチレン）4.
0gを得た。このもののMIPは、92wt％であった。また、
得られたスチレン系重合体（MIP）は、重量平均分子量
2,400,000であり、数平均分子量860,000であって、シン
ジオタクティシティー100％であった。Example 3 (1) Production of styrene-based polymer A styrene-based polymer (polystyrene) was prepared in the same manner as in (1) of Example 1 except that the polymerization temperature was 20 ° C.
I got 0g. The MIP of this product was 92 wt%. Also,
The obtained styrene polymer (MIP) has a weight average molecular weight.
It was 2,400,000, the number average molecular weight was 860,000, and the syndiotacticity was 100%.
（２）延伸フィルム（テープ）の製造 上記（１）で得たスチレン系重合体を用い、延伸倍率を
６倍としたほかは、実施例１の（２）と同様の操作を行
なった。結果を第１表に示す。(2) Production of Stretched Film (Tape) The same operation as in (2) of Example 1 was performed, except that the styrene-based polymer obtained in (1) above was used and the stretch ratio was 6 times. The results are shown in Table 1.
実施例４ （１）スチレン系重合体の製造 重合温度を０℃とし、かつ重合時間を８時間としたほか
は、実施例１の（１）と同様の操作を行ない、スチレン
系重合体（ポリスチレン）1.5gを得た。このもののMIP
は、70wt％であった。また、得られたスチレン系重合体
（MIP）は、重量平均分子量4,500,000であり、数平均分
子量1,600,000であって、シンジオタクティシティー100
％であった。Example 4 (1) Production of styrene-based polymer A styrene-based polymer (polystyrene) was prepared in the same manner as in (1) of Example 1 except that the polymerization temperature was 0 ° C. and the polymerization time was 8 hours. ) Obtained 1.5 g. MIP of this thing
Was 70 wt%. The obtained styrene-based polymer (MIP) has a weight average molecular weight of 4,500,000, a number average molecular weight of 1,600,000, and a syndiotacticity of 100.
%Met.
（２）延伸フィルム（テープ）の製造 上記（１）で得たスチレン系重合体を用い、延伸倍率を
５倍としたほかは、実施例１の（２）と同様の操作を行
なった。結果を第１表に示す。(2) Production of Stretched Film (Tape) The same operation as in (2) of Example 1 was performed except that the styrene-based polymer obtained in (1) above was used and the stretch ratio was set to 5 times. The results are shown in Table 1.
比較例１ 延伸処理をしなかったほかは、実施例１の（２）と同様
の操作を行なった。結果を第１表に示す。Comparative Example 1 The same operation as in (2) of Example 1 was performed except that the stretching treatment was not performed. The results are shown in Table 1.
比較例２ 触媒として、マグネシウムジエトキシド10.0gに四塩化
チタン50mlを反応させ、チタン化合物を担持したチタン
触媒成分1.0ミリモルと、トリエチルアルミニウム10ミ
リモルを組み合わせたものを用い、ヘプタン溶媒中、70
℃において、スチレン100mlの重合反応を２時間行な
い、重量平均分子量1,000,000であり、数平均分子量26
0,000のアイソタクチック構造のスチレン系重合体（ポ
リスチレン）48.7gを得た。このスチレン系重合体は、
実施例１と同様にメチルエチルケトンで抽出した残分は
96wt％であった。このアイソタクチック構造のスチレン
系重合体について、実施例１の（２）と同様に延伸した
（但し、延伸倍率６倍）。得られた延伸物について機械
的強度を測定した。結果を第１表に示す。Comparative Example 2 As a catalyst, 10.0 g of magnesium diethoxide was reacted with 50 ml of titanium tetrachloride, and a combination of 1.0 mmol of a titanium catalyst component carrying a titanium compound and 10 mmol of triethylaluminum was used.
Polymerization reaction of styrene 100 ml at ℃ for 2 hours, the weight average molecular weight is 1,000,000 and the number average molecular weight is 26.
48.7 g of a styrene-based polymer (polystyrene) having an isotactic structure of 0,000 was obtained. This styrene polymer is
The residue extracted with methyl ethyl ketone as in Example 1 was
It was 96 wt%. This isotactic styrene-based polymer was stretched in the same manner as in (2) of Example 1 (however, the stretching ratio was 6 times). The mechanical strength of the obtained stretched product was measured. The results are shown in Table 1.
比較例３ 延伸処理をしなかったほかは、比較例２と同様の操作を
行なった。結果を第１表に示す。Comparative Example 3 The same operation as in Comparative Example 2 was performed except that the stretching treatment was not performed. The results are shown in Table 1.
実施例５ （１）スチレン系重合体の製造 反応容器に、溶媒としてトルエン20mlと、触媒成分とし
てテトラエトキシチタニウム0.0445ミリモル及びメチル
アルミノキサンをアルミニウム原子として4.45ミリモル
加え、20℃においてこれにスチレン110mlを加え、７時
間重合反応を行なった。反応終了後、生成物を塩酸−メ
タノール混合液で洗浄し、触媒成分を分解除去した。次
いで乾燥し、スチレン系重合体（ポリスチレン）1.7gを
得た。Example 5 (1) Production of styrene-based polymer To a reaction vessel, 20 ml of toluene as a solvent, 0.0445 mmol of tetraethoxytitanium as a catalyst component and 4.45 mmol of methylaluminoxane as an aluminum atom were added, and 110 ml of styrene was added thereto at 20 ° C. The polymerization reaction was carried out for 7 hours. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain 1.7 g of a styrene polymer (polystyrene).
次に、この重合体を、メチルエチルケトンを溶媒として
ソックスレー抽出し、MIP98wt％を得た。このものの重
量平均分子量は3,040,000であり、数平均分子量は1,22
0,000であって、融点は270℃であった。また、13C−NMR
による分析から、シンジオタクチック構造に基因する14
5.35ppmに吸収が認められ、そのピーク面積から算出し
たラセミペンタッドでのシンジオタクティシティーは99
％であった。Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain MIP of 98 wt%. The weight average molecular weight of this product was 3,040,000, and the number average molecular weight was 1,22.
The melting point was 000 ° C. In addition, 13 C-NMR
Analysis suggests that it is due to the syndiotactic structure 14
Absorption was observed at 5.35 ppm, and the syndiotacticity in racemic pentad calculated from the peak area was 99.
%Met.
（２）延伸フィルム（テープ）の製造 上記（１）で得られたシンジオタクチック構造のスチレ
ン系重合体を、溶媒のｐ−キシレン中に入れて加熱溶解
し、１重量％の濃度のスチレン系重合体溶液を得た。こ
の溶液をフラットシャーレに流し込み、寒天状の固いゲ
ルを得た。このゲルをアセトンで洗浄し、圧縮し、ゲル
マットを得た。このゲルマットを短冊状に切断し、室温
において減圧下、10時間乾燥した。この短冊を空気中、
150℃において延伸倍率７倍に延伸した。得られた延伸
物につき、機械的強度を測定した。結果を第１表に示
す。(2) Production of Stretched Film (Tape) The styrene-based polymer having the syndiotactic structure obtained in (1) above was put into p-xylene as a solvent and dissolved by heating to form a styrene-based polymer having a concentration of 1% by weight. A polymer solution was obtained. This solution was poured into a flat petri dish to obtain an agar-like hard gel. The gel was washed with acetone and compressed to obtain a gel mat. This gel mat was cut into strips and dried at room temperature under reduced pressure for 10 hours. In the air,
It was stretched at a draw ratio of 7 times at 150 ° C. The mechanical strength of the obtained stretched product was measured. The results are shown in Table 1.
実施例６ （１）スチレン系重合体の製造 実施例５の（１）の全く同様にしてスチレン系重合体を
得た。Example 6 (1) Production of styrene-based polymer A styrene-based polymer was obtained in exactly the same manner as in (1) of Example 5.
（２）延伸フィルム（テープ）の製造 上記（１）で得たスチレン系重合体を、溶媒のクロロホ
ルム中に入れて加熱溶解し、0.1重量％の濃度のスチレ
ン系重合体溶液を得た。この溶液を充分に冷却した銅製
の箱に流し込み、寒天状の柔らかいゲルを得た。このゲ
ルをヌッチェ上でプレスしつつ吸引乾燥し、室温におい
て減圧下、10時間乾燥してゲル板を得た。次に、このゲ
ル板を短冊状に切断し、この短冊を空気中、150℃にお
いてポリ（４−メチルペンテン１）と共に固相共押出し
することにより、延伸倍率７倍に延伸した。得られた延
伸物の機械的強度を第１表に示す。(2) Production of Stretched Film (Tape) The styrene polymer obtained in (1) above was put into chloroform as a solvent and dissolved by heating to obtain a styrene polymer solution having a concentration of 0.1% by weight. This solution was poured into a sufficiently cooled copper box to obtain an agar-like soft gel. This gel was sucked and dried while pressing it on a Nutsche, and dried at room temperature under reduced pressure for 10 hours to obtain a gel plate. Next, the gel plate was cut into strips, and the strips were coextruded in the air at 150 ° C. with poly (4-methylpentene 1) in a solid phase to stretch the strip at a draw ratio of 7 times. The mechanical strength of the obtained stretched product is shown in Table 1.
実施例７ （１）スチレン系重合体の製造 重合温度を50℃とし、かつ重合時間を１時間20分とした
ほかは、実施例５の（１）と同様の操作を行ない、スチ
レン系重合体2.2gを得た。このもののMIPは、97wt％で
あった。また、得られたスチレン系重合体（MIP）は、
重量平均分子量940,000であり、数平均分子量380,000で
あって、シンジオタクティシティー97％であった。Example 7 (1) Production of styrene-based polymer A styrene-based polymer was prepared in the same manner as in (1) of Example 5 except that the polymerization temperature was 50 ° C. and the polymerization time was 1 hour and 20 minutes. Obtained 2.2 g. The MIP of this product was 97 wt%. Further, the obtained styrenic polymer (MIP) is
The weight average molecular weight was 940,000, the number average molecular weight was 380,000, and the syndiotacticity was 97%.
（２）フィルムの製造 上記（１）で得たスチレン系重合体を用いてクロロホル
ムを溶媒としてキャストフィルムを作成した。このキャ
ストフィルムを短冊状に切断し、実施例５の（２）と同
様に延伸し、延伸倍率７倍の延伸物を得た。得られた延
伸物の機械的強度を第１表に示す。(2) Production of Film Using the styrene-based polymer obtained in (1) above, a cast film was prepared using chloroform as a solvent. This cast film was cut into strips and stretched in the same manner as in (5) of Example 5 to obtain a stretched product having a stretch ratio of 7 times. The mechanical strength of the obtained stretched product is shown in Table 1.
実施例８ （１）スチレン系重合体の製造 反応容器に、溶媒としてトルエン180mlと触媒成分とし
てテトラエトキシチタニウム0.15ミリモル及びメチルア
ルミノキサンをアルミニウム原子として15ミリモル加
え、30℃においてこれにスチレン145ミリモルとｐ−メ
チルスチレン15ミリモルの混合物を加え、２時間重合反
応を行なった。反応終了後、生成物を塩酸−メタノール
混合液で洗浄し、触媒成分を分解除去した。次いで乾燥
し、スチレン系重合体22gを得た。Example 8 (1) Production of styrene-based polymer To a reaction vessel, 180 ml of toluene as a solvent, 0.15 mmol of tetraethoxytitanium as a catalyst component and 15 mmol of methylaluminoxane as an aluminum atom were added, and at 30 ° C., 145 mmol of styrene and p were added thereto. A mixture of 15 mmol of methylstyrene was added, and a polymerization reaction was carried out for 2 hours. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain 22 g of a styrene polymer.
次に、この重合体を、メチルエチルケトンを溶媒として
ソックスレー抽出し、MIP9.9wt％を得た。このものの重
量平均分子量は960,000であり、数平均分子量は460,000
であって、融点は225℃であった。また、ｐ−メチルス
チレン含量は23モル％で、13C−NMRによる分析から、特
願昭62−017973に示した共重合体と同様に、145.11ppm,
145.22ppm,142.09ppmに吸収がみられ、共シンジオタク
チック構造であることがわかった。Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain MIP 9.9 wt%. This product has a weight average molecular weight of 960,000 and a number average molecular weight of 460,000.
And the melting point was 225 ° C. Further, the p-methylstyrene content was 23 mol%, and as a result of 13 C-NMR analysis, it was found to be 145.11 ppm, similar to the copolymer shown in Japanese Patent Application No. 62-017973.
Absorption was observed at 145.22ppm and 142.09ppm, which revealed that it had a co-syndiotactic structure.
（２）延伸フィルム（テープ）の製造 上記（１）で得られたスチレン系重合体を用い、溶媒と
してｐ−キシレンを用いたこと以外は、実施例６の
（２）と同様にゲル板を作製し、延伸し、延伸倍率７倍
の延伸物を得た。得られた延伸物の機械的強度を第１表
に示す。(2) Production of Stretched Film (Tape) A gel plate was prepared in the same manner as (2) in Example 6 except that the styrene-based polymer obtained in (1) above was used and p-xylene was used as the solvent. It was produced and stretched to obtain a stretched product having a stretch ratio of 7 times. The mechanical strength of the obtained stretched product is shown in Table 1.
実施例９ 実施例１（１）で得られたスチレン系重合体を、抽出機
により押出し、冷却してシートを得た。このシートを12
0℃で、縦，横それぞれ３倍に二軸延伸し、緊張下に室
温まで冷却した。このようにして得られた延伸フィルム
の機械的強度を実施例１と同様にして測定した。結果を
第１表に示す。Example 9 The styrene polymer obtained in Example 1 (1) was extruded by an extractor and cooled to obtain a sheet. This sheet 12
At 0 ° C., the film was biaxially stretched 3 times in the length and width and cooled to room temperature under tension. The mechanical strength of the stretched film thus obtained was measured in the same manner as in Example 1. The results are shown in Table 1.
比較例４ 実施例９で得られた、未延伸の状態のシートの機械的強
度を実施例１と同様にして測定した。結果を第１表に示
す。Comparative Example 4 The mechanical strength of the unstretched sheet obtained in Example 9 was measured in the same manner as in Example 1. The results are shown in Table 1.
実施例10 （１）スチレン系重合体の製造 反応容器に、溶媒としてトルエン２リットルと、触媒成
分としてシクロペンタジエニルトリクロリド１ミリモル
及びメチルアルミノキサンをアルミニウム原子として0.
6モル加え、20℃においてこれにスチレン3.6リットルを
加え、１時間重合反応を行なった。反応終了後、生成物
を塩酸−メタノール混合液で洗浄し、触媒成分を分解除
去した。次いで乾燥し、スチレン重合体（ポリスチレ
ン）330gを得た。Example 10 (1) Production of styrene-based polymer In a reaction vessel, 2 liters of toluene as a solvent, 1 mmol of cyclopentadienyl trichloride as a catalyst component and methylaluminoxane as an aluminum atom were used.
After adding 6 mol, 3.6 liter of styrene was added to this at 20 ° C., and a polymerization reaction was carried out for 1 hour. After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain 330 g of a styrene polymer (polystyrene).
次に、この重合体を、メチルエチルケトンを溶媒として
ソックスレー抽出し、抽出残分（MIP）95wt％を得た。
この抽出残分の重量平均分子量は290,000であり、数平
均分子量は158,000であって、融点は270℃であった。ま
た、この重合体は、13C−NMRによる分析から、シンジオ
タクチック構造に基因する145.35ppmに吸収が認めら
れ、そのピーク面積から算出したラセミペンタッグでの
シンジオタクティシティーは96％であった。Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue (MIP) of 95 wt%.
This extraction residue had a weight average molecular weight of 290,000, a number average molecular weight of 158,000 and a melting point of 270 ° C. Further, this polymer was found by absorption analysis at 13 C-NMR to have an absorption at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in racemic pentag calculated from the peak area was 96%. It was
（２）フィルムの製造 上記（１）で得られたスチレン系重合体より、実施例９
と同様にして、未延伸シートを得た。この未延伸シート
を、120℃で縦，横それぞれ４倍に二軸延伸し、緊張下
に230℃で５分間熱処理した。このようにして得られた
延伸フィルムの機械的強度を実施例１と同様にして測定
した。結果を第１表に示す。(2) Production of film Example 9 was prepared from the styrene-based polymer obtained in (1) above.
An unstretched sheet was obtained in the same manner as in. This unstretched sheet was biaxially stretched at 120 ° C. by a factor of 4 in both length and width, and heat-treated under tension at 230 ° C. for 5 minutes. The mechanical strength of the stretched film thus obtained was measured in the same manner as in Example 1. The results are shown in Table 1.
実施例11 反応容器に、溶媒としてトルエン４リットルと、触媒成
分として四塩化チタン40ミリモル及びメチルアルミノキ
サンをアルミニウム原子として1600モル加え、50℃にお
いてこれにスチレン４リットルを加え、８時間重合反応
を行なった。反応終了後、生成物を塩酸−メタノール混
合液で洗浄し、触媒成分を分解除去した。次いで乾燥
し、スチレン重合体（ポリスチレン）を得た。Example 11 To a reaction vessel, 4 liters of toluene as a solvent, 40 mmol of titanium tetrachloride as a catalyst component and 1600 moles of methylaluminoxane as an aluminum atom were added, and 4 liters of styrene was added thereto at 50 ° C. to carry out a polymerization reaction for 8 hours. It was After the reaction was completed, the product was washed with a hydrochloric acid-methanol mixed solution to decompose and remove the catalyst component. Then, it was dried to obtain a styrene polymer (polystyrene).
次に、この重合体を、メチルエチルケトンを溶媒として
ソックスレー抽出し、抽出残分（MIP）21wt％を得た。
この抽出残分の重量平均分子量は678,000であり、数平
均分子量は272,000であった。また、この重合体は、13C
−NMRによる分析から、シンジオタクチック構造に基因
する145.35ppmに吸収が認められ、そのピーク面積から
算出したラセミペンタッドでのシンジオタクティシティ
ーは86％であった。Next, this polymer was subjected to Soxhlet extraction using methyl ethyl ketone as a solvent to obtain an extraction residue (MIP) of 21 wt%.
The weight average molecular weight of this extraction residue was 678,000, and the number average molecular weight was 272,000. In addition, this polymer is 13 C
-By NMR analysis, absorption was observed at 145.35 ppm due to the syndiotactic structure, and the syndiotacticity in the racemic pentad calculated from the peak area was 86%.
（２）フィルム製造 上記（１）で得られたスチレン系重合体より、実施例９
と同様にして、未延伸シートを得た。この未延伸シート
を、110℃で縦，横それぞれ４倍に二軸延伸し、緊張下
に室温まで冷却した。このようにして得られた延伸フィ
ルム機械的強度を実施例１と同様にして測定した。結果
を第１表に示す。(2) Film production From the styrene-based polymer obtained in (1) above, Example 9 was used.
An unstretched sheet was obtained in the same manner as in. This unstretched sheet was biaxially stretched at 110 ° C. by a factor of 4 in the length and width, and cooled to room temperature under tension. The mechanical strength of the thus obtained stretched film was measured in the same manner as in Example 1. The results are shown in Table 1.
比較例５ 比較例２で得られたスチレン系重合体より、実施例９と
同様にして、未延伸シートを得た。この未延伸シート
を、120℃で縦，横それぞれ３倍に二軸延伸し、緊張下
に室温まで冷却した。このようにして得られた延伸フィ
ルムの機械的強度を実施例１と同様にして測定した。結
果を第１表に示す。Comparative Example 5 An unstretched sheet was obtained from the styrene-based polymer obtained in Comparative Example 2 in the same manner as in Example 9. This unstretched sheet was biaxially stretched at 120 ° C. in the longitudinal and transverse directions by 3 times and cooled to room temperature under tension. The mechanical strength of the stretched film thus obtained was measured in the same manner as in Example 1. The results are shown in Table 1.
比較例６ 比較例５で得られた、未延伸の状態のシートの機械的強
度を実施例１と同様にして測定した。結果を第１表に示
す。Comparative Example 6 The mechanical strength of the unstretched sheet obtained in Comparative Example 5 was measured in the same manner as in Example 1. The results are shown in Table 1.
〔発明の効果〕 本発明のフィルム又はテープは、シンジオタクチック構
造のスチレン系重合体の属性である耐熱性を維持しつ
つ、延伸処理によって機械的強度、特に弾性率が著しく
改善されたものである。 [Effect of the Invention] The film or tape of the present invention is one in which the mechanical strength, particularly the elastic modulus, is remarkably improved by the stretching treatment while maintaining the heat resistance which is an attribute of the styrene polymer having a syndiotactic structure. is there.
従って、本発明のフィルム又はテープは、ケーブル，複
合強化材をはじめとして、各種用途に幅広く、かつ有効
に利用される。Therefore, the film or tape of the present invention can be widely and effectively used in various applications including cables and composite reinforcing materials.
Claims (6)
スチレン系重合体を延伸してなるフィルム又はテープ。1. A film or tape mainly obtained by stretching a styrene polymer having a syndiotactic structure.
スチレン系重合体が、同位体元素による核磁気共鳴スペ
クトル分析のラセミペンタッドでのシンジオタクティシ
ティー85％以上の立体規則性を有するスチレン系重合体
である特許請求の範囲第１項記載のフィルム又はテー
プ。2. A styrene-based polymer mainly having a syndiotactic structure, wherein the styrene-based polymer has a stereoregularity of 85% or more of syndiotacticity in racemic pentad in nuclear magnetic resonance spectrum analysis by isotope. The film or tape according to claim 1, wherein
の範囲第１項記載のフィルム又はテープ。3. The film or tape according to claim 1, which is drawn at a draw ratio of 3 times or more.
スチレン系重合体が、同位体元素による核磁気共鳴スペ
クトル分析のラセミペンタッドでのシンジオタクティシ
ティー85％以上の立体規則性を有するスチレン系重合体
であり、かつ、該スチレン系重合体を延伸倍率３倍以上
に延伸してなる特許請求の範囲第１項記載のフィルム又
はテープ。4. A styrenic polymer mainly having a syndiotactic structure, wherein the styrenic polymer has a stereoregularity of 85% or more of syndiotacticity in racemic pentad in nuclear magnetic resonance spectrum analysis by isotope. The film or tape according to claim 1, which is obtained by stretching the styrene-based polymer at a draw ratio of 3 times or more.
000以上のものである特許請求の範囲第１項記載のフィ
ルム又はテープ。5. The styrene polymer has a weight average molecular weight of 300,
The film or tape according to claim 1, which is 000 or more.
スチレン系重合体が、同位体元素による核磁気共鳴スペ
クトル分析のラセミペンタッドでのシンジオタクティシ
ティー85％以上の立体規則性を有するスチレン系重合体
である特許請求の範囲第５項記載のフィルム又はテー
プ。6. A styrene-based polymer mainly having a syndiotactic structure, wherein the styrene-based polymer has a stereoregularity of 85% or more of syndiotacticity in racemic pentad in nuclear magnetic resonance spectrum analysis by isotope. The film or tape according to claim 5, wherein
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222092A JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
| PCT/JP1987/000891 WO1989004846A1 (en) | 1986-09-22 | 1987-11-17 | Styrenic polymer moldings |
| DE3789900T DE3789900T2 (en) | 1986-09-22 | 1987-11-17 | STYRENE POLYMER MOLDED PARTS. |
| EP87907535A EP0342234B1 (en) | 1986-09-22 | 1987-11-17 | Styrenic polymer moldings |
| US07/524,372 US5166238A (en) | 1986-09-22 | 1990-05-15 | Styrene-based resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61222092A JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7078470A Division JP2538845B2 (en) | 1995-03-10 | 1995-03-10 | Fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6377905A JPS6377905A (en) | 1988-04-08 |
| JPH0788430B2 true JPH0788430B2 (en) | 1995-09-27 |
Family
ID=16777002
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61222092A Expired - Fee Related JPH0788430B2 (en) | 1986-09-22 | 1986-09-22 | Film or tape |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0788430B2 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5166238A (en) * | 1986-09-22 | 1992-11-24 | Idemitsu Kosan Co., Ltd. | Styrene-based resin composition |
| JP2748935B2 (en) * | 1987-12-25 | 1998-05-13 | 旭化成工業株式会社 | Syndiotactic polystyrene film |
| JP2597392B2 (en) * | 1988-06-30 | 1997-04-02 | 出光興産株式会社 | Non-woven |
| JP2790636B2 (en) * | 1988-08-31 | 1998-08-27 | 出光興産株式会社 | Stretched film for food packaging |
| US5145950A (en) * | 1988-08-31 | 1992-09-08 | Idemitsu Kosan Co., Ltd. | Method of storing food or plant materials by wrapping with a stretched syndiotactic polystyrene film |
| US5089353A (en) * | 1988-10-14 | 1992-02-18 | Kuraray Co., Ltd. | Multi-layer material having gas barrier properties |
| JP2812971B2 (en) * | 1989-01-24 | 1998-10-22 | 出光興産株式会社 | Extrusion molding material and method for producing molded article |
| IT1228915B (en) * | 1989-02-28 | 1991-07-09 | Himont Inc | MANUFACTURED IN A NEW CRYSTALLINE FORM OF SYNDIOTACTIC POLYSTYRENE. |
| JPH0691750A (en) * | 1992-09-11 | 1994-04-05 | Toyobo Co Ltd | Syndiotactic polystyrene biaxially drawn film |
| JPH0699485A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially stretched film |
| JPH06100711A (en) * | 1992-09-21 | 1994-04-12 | Toyobo Co Ltd | Syndiotactic polystyrenic biaxially oriented film |
| JPH06107812A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06107813A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Biaxially oriented syndiotactic polystyrene film |
| JPH06106616A (en) * | 1992-09-28 | 1994-04-19 | Toyobo Co Ltd | Syndiotactic polystyrenr biaxially oriented film |
| JPH0724911A (en) * | 1993-07-08 | 1995-01-27 | Toyobo Co Ltd | Syndyotactic polystyrene film |
| US5446117A (en) * | 1993-08-19 | 1995-08-29 | Queen's University At Kingston | Process for producing amorphous syndiotactic polystyrene |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61101926A (en) * | 1984-10-25 | 1986-05-20 | 株式会社東芝 | Refiring surge test for gas-insulated switch gear |
-
1986
- 1986-09-22 JP JP61222092A patent/JPH0788430B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6377905A (en) | 1988-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0788430B2 (en) | Film or tape | |
| JP2597375B2 (en) | Vinylcyclohexane-based polymer and method for producing the same | |
| JP2505001B2 (en) | Method for producing syndiotactic polystyrene film | |
| JPH01182346A (en) | Molded body of styrene based resin and production thereof | |
| JPS62257950A (en) | Thermoplastic resin composition | |
| DE3872721T2 (en) | METHOD FOR PRODUCING STYRENE POLYMERS. | |
| KR960006161B1 (en) | Styrene polymer molding material and process for preparing the same | |
| JPH06104337B2 (en) | Stretched styrene resin film and method for producing the same | |
| JPH01242607A (en) | Styrenic polymer production method and its catalyst | |
| JP2888856B2 (en) | Syndiotactic polystyrene transparent film | |
| JP2748935B2 (en) | Syndiotactic polystyrene film | |
| JPH0755994B2 (en) | Polystyrene resin composition | |
| JP2672589B2 (en) | Styrene-based polymer molded article and method for producing the same | |
| EP0342234B1 (en) | Styrenic polymer moldings | |
| JPH03114728A (en) | Manufacturing method for rolled products | |
| JPS62259809A (en) | Manufacturing method for resin molded products | |
| JP2538845B2 (en) | Fiber | |
| US5721327A (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominant syndiotactic structure | |
| JPH04502488A (en) | Method for producing syndiotactic copolymer of propylene and olefin | |
| US6066706A (en) | Process for the preparation of crystalline vinylaromatic polymers with a predominately syndiotactic structure | |
| JP3649257B2 (en) | Styrenic resin sheet / film manufacturing method | |
| JP3734892B2 (en) | Styrene resin stretched sheet | |
| DE69605355T3 (en) | Syndiotactic styrene terpolymers | |
| JPH03109405A (en) | Arylstyrene-based polymer and production thereof | |
| JPS6399202A (en) | Manufacturing method of styrenic polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |