JPS62212125A - Manufacture of uniaxially stretched polypropylene matter - Google Patents
Manufacture of uniaxially stretched polypropylene matterInfo
- Publication number
- JPS62212125A JPS62212125A JP5668186A JP5668186A JPS62212125A JP S62212125 A JPS62212125 A JP S62212125A JP 5668186 A JP5668186 A JP 5668186A JP 5668186 A JP5668186 A JP 5668186A JP S62212125 A JPS62212125 A JP S62212125A
- Authority
- JP
- Japan
- Prior art keywords
- stretched
- polypropylene
- matter
- stretching
- uniaxially
- 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.)
- Granted
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 48
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 43
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
- 229930195734 saturated hydrocarbon Natural products 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229920005629 polypropylene homopolymer Polymers 0.000 claims abstract description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 13
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 28
- 238000005336 cracking Methods 0.000 abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 11
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 10
- 238000002156 mixing Methods 0.000 abstract description 10
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 abstract 1
- 150000001993 dienes Chemical class 0.000 description 13
- 238000005984 hydrogenation reaction Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 8
- 239000011342 resin composition Substances 0.000 description 7
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920013639 polyalphaolefin Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical class C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 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 compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は機械的特性、透明性、延伸性及び割れ特性の改
善されたポリプロピレン一軸延伸物の製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing a uniaxially drawn polypropylene product having improved mechanical properties, transparency, stretchability and cracking properties.
ポリプロピレンの一軸延伸フイルム、延伸テープ、ヤー
ン、バンド及びモノフィラメント等の一軸延伸物は光沢
等の光学的特性、耐熱性、耐薬品性及び電気的特性に優
れ、且つ、引張強度（延伸強度）、クリープ特性、剛性
等の機械的特性も良好であることから、各種の包装用フ
ィルム及び織物等に広く使用されている。しかしながら
、用途によっては、これらの性質が十分に満足されてい
るとは言えない場合があり、そのため具体的用途の拡大
が制限されている。Uniaxially stretched polypropylene films, stretched tapes, yarns, bands, monofilaments, and other uniaxially stretched products have excellent optical properties such as gloss, heat resistance, chemical resistance, and electrical properties, as well as excellent tensile strength (stretched strength) and creep. Because it has good properties and mechanical properties such as rigidity, it is widely used in various packaging films and textiles. However, depending on the application, these properties may not be fully satisfied, which limits the expansion of specific applications.
例えば、ポリプロピレンの延伸テープやヤーンはポリエ
チレンに比較して耐クリープ性が大幅に優れ、且つ延伸
倍率基準の強度が大きく、しかも滑りにくいことからフ
レキシブルコンテナー基布、シート基布等に使用されて
いる。しかしながらポリプロピレンの剛性が不十分なも
の（アイソタクチックペンタッド分率の低いもの）は延
伸した場合、収縮しやすく、また、剛性が高いもの（ア
イソタクチックペンタッド分率の高いもの）は高延伸倍
率（り〜を倍以上）Ｋ延伸した場合、割れやすいという
欠点がある。For example, polypropylene stretched tapes and yarns have much better creep resistance than polyethylene, have greater strength based on the stretching ratio, and are less slippery, so they are used for flexible container base fabrics, sheet base fabrics, etc. . However, polypropylene with insufficient rigidity (low isotactic pentad fraction) tends to shrink when stretched, and polypropylene with high rigidity (high isotactic pentad fraction) has a high When it is stretched at a stretching ratio of K to more than 2 times, it has the disadvantage of being easily cracked.
ポリプロピレンの延伸強度及び剛性は延伸倍率及びその
構造によって大きく影響を受ける。The stretching strength and rigidity of polypropylene are greatly influenced by the stretching ratio and its structure.
ポリプロピレンにはプロピレンの単独重合体からなるベ
モポリマーと少量のエチレンを共重合させるランダム共
重合体とがあシ、延伸強度及び剛性はホモポリマーが優
れているので、延伸強度又は剛性を必要とする用途には
通常ホモポリマーを延伸して用いている。そして更に剛
性を改良する方法として■アイソタクチックインデック
ス（Ｌ工）が９ＬＤ％以上の４のを用いる方法（特開昭
３７−１０ＪＩｌｔ号公報）が提案されている。また、
ホモポリマーの延伸性を改良する方法として■ランダム
共重合体を用いる方法、例えば四塩化チタンを有機アル
ミニウム化合物で還元し、さらに活性化し九三塩化チタ
ンおよび有機アルミニウム化合物からなる触媒を用いて
プロビレｙｉｉ合時に少量のエチレンを供給してエチレ
ン含有量が０．／〜／、Ｏｆ量チのポリプロピレンを用
いる方法（特開昭！ｒＡ−Ｊコｊ／コ号公報）が提案さ
れている。Polypropylene has two types: bemopolymer, which is a propylene homopolymer, and random copolymer, which is made by copolymerizing a small amount of ethylene. Homopolymers have superior stretching strength and rigidity, so they are suitable for applications that require stretching strength or rigidity. Usually, stretched homopolymers are used. As a method for further improving the rigidity, a method (1) using a material having an isotactic index (L-engineering) of 9LD% or more (Japanese Patent Application Laid-Open No. 10/1983) has been proposed. Also,
As a method for improving the stretchability of homopolymers, 1) a method using a random copolymer, for example, reducing titanium tetrachloride with an organoaluminum compound, further activating it, and using a catalyst consisting of titanium trichloride and an organoaluminum compound to form a probylene yii At the same time, a small amount of ethylene is supplied to reduce the ethylene content to 0. A method using polypropylene in amounts of / to / and Of has been proposed (Japanese Patent Application Laid-Open No. 2003-120003A-J).
しかしながら上記■の方法では、ホモポリマーでいくら
工、工を高くしても、延伸強度又は剛性は改良されるが
、逆に割れ特性はますます低下するので高倍率の延伸が
困難となり、結果として左程延伸強度又は剛性に優れた
延伸物（テープ、ヤーンまたはフィルム）は得られない
。However, in the above method (■), no matter how high the processing strength or processing strength of the homopolymer is, the stretching strength or rigidity is improved, but on the contrary, the cracking properties are further deteriorated, making it difficult to stretch at high magnifications, and as a result, A stretched product (tape, yarn, or film) with superior stretching strength or rigidity cannot be obtained.
また、上記■の方法では、かかる従来の触媒を用いてラ
ンダム共重合体を製造しても、多少割れ特性は改良され
るが、極く少量のエチレンを共重合させるだけで急激に
工、■が低下し、引張強度及び剛性が低く、腰の弱い延
伸物（テープ、ヤーンまたはフィルム）しか得られない
。In addition, in the method (2) above, even if a random copolymer is produced using such a conventional catalyst, the cracking properties are improved to some extent, but copolymerization of only a small amount of ethylene causes a rapid increase in the process (2). This results in a reduced tensile strength and stiffness, resulting in only weak drawn products (tapes, yarns or films).
さらに１ポリプロピレンの延伸テープ及びヤーンは延伸
倍率基準の引張強度又は剛性を得るために、工、工をゾ
ロ％以上にし、かつ高延伸倍率（７倍以上）に延伸する
ことを試みたが、この場合には延伸テープ及びヤーンが
延伸方向に割れる現象が発生する。この割れ防止のため
に炭酸カルシウム、メルク等の無機フィラーをマスター
バッチで添加しても、マスターバンチの分散性が不良の
ため得られる延伸テープ及びヤーンは透明性が低下し、
かつ、安定したものが得られない。Furthermore, in order to obtain the tensile strength or stiffness based on the draw ratio, polypropylene stretched tapes and yarns were tried to be drawn at a ratio of 0% or more and at a high draw ratio (7 times or more). In some cases, the stretched tape and yarn may crack in the stretching direction. Even if an inorganic filler such as calcium carbonate or Merck is added to the master batch to prevent cracking, the resulting drawn tapes and yarns have reduced transparency due to poor dispersibility of the master bunch.
Moreover, it is not possible to obtain a stable product.
このようにポリプロピレンの引張強度、剛性、延伸性あ
るいは割れ防止をそれぞれ改良する方法は提案されてい
るものの引張強度、剛性、延伸性及び割れ防止の全てが
改良されたポリプロビレ／の一軸延伸物は未だ開発され
ていない。Although methods have been proposed to improve the tensile strength, stiffness, stretchability, and cracking prevention of polypropylene, there is still no polypropylene/uniaxially stretched product that has improved tensile strength, stiffness, stretchability, and cracking prevention. Not developed.
本発明者等は上記従来技術に鑑み、ポリプロピレン一軸
延伸物の機械的特性、延伸性及び割れ防止を改良すべく
、鋭意検討した結果、特定のポリプロピレンに特定の炭
化水素ポリマーを少量配合したものを用いて成形し、一
軸延伸物にすることＫよυ核ポリプロピレンの剛性を保
持したまま、延伸性、透明性及び割れ防止が大幅に改良
されたポリプロピレンの一軸延伸物が得られることを見
出し、本発明を完成した。In view of the above-mentioned prior art, the present inventors conducted intensive studies to improve the mechanical properties, stretchability, and prevention of cracking of uniaxially stretched polypropylene products. We have discovered that it is possible to obtain a uniaxially stretched polypropylene product that has significantly improved stretchability, transparency, and crack prevention while retaining the rigidity of K-core polypropylene. Completed the invention.
すなわち、本発明の要旨は沸騰ヘプタン不溶部の立体規
則性が”Ｃ−ＮＭＲで求められるアイソタクチックペン
タッド分率として０．９ＡＯ以上のポリプロビレンホそ
ポリマー１００Ｘｆｋ部に対し、末端に少くとも１個の
水酸基を有する主鎖の飽和した又は部分的に飽和した炭
化水素ポリマー０．０ ／−コ重量部を配合してなる組
成物を用いて未延伸物を成形し、次いで該未延伸物を縦
方向に２〜７０倍の延伸倍率で延伸してなることを特徴
とするポリプロピレン一軸延伸物の製造方法に存する。That is, the gist of the present invention is that the stereoregularity of the boiling heptane-insoluble portion is 100Xfk parts of a polypropylene polymer having an isotactic pentad fraction of 0.9AO or more as determined by C-NMR, at least 1 at the end. A composition prepared by blending 0.0/- parts by weight of a saturated or partially saturated hydrocarbon polymer with a main chain having hydroxyl groups is used to form an unstretched product, and then the unstretched product is molded. The present invention relates to a method for producing a uniaxially stretched polypropylene product, which comprises stretching in the longitudinal direction at a stretching ratio of 2 to 70 times.
以下、本発明につきさらに詳細に説明する。The present invention will be explained in more detail below.
本発明において用いられるポリプロピレンは、プロビレ
／の単独重合体のホモポリマーであって、沸騰ヘプタン
不溶部の立体規則性がＩＣ−ＮＭＲで求められるアイソ
タクチックペンタッド分率で０．２６０以上、好ましく
は０．９７０以上、さらに好ましくは０．９７３以上の
ものである。このようなポリプロピレンは特開昭３６−
３９２ｔ！及び特開昭、ｌｔ ？ −１３６３０号公報
等に記載された方法によって製造することができる。The polypropylene used in the present invention is a homopolymer of Propylene, and the stereoregularity of the boiling heptane insoluble portion is preferably 0.260 or more in terms of isotactic pentad fraction determined by IC-NMR. is 0.970 or more, more preferably 0.973 or more. Such polypropylene is disclosed in Japanese Unexamined Patent Application Publication No. 1983-
392t! and Tokukai Akira, lt? It can be produced by the method described in JP-A-13630 and the like.
上記ポリプロピレンのアイソタクチックペンタッド分率
が０．９６０未満では延伸物（フィルム、テープ及びヤ
ーン）の引張強度及び割れ防止の改良効果が少なくなる
ので好ましくない。If the isotactic pentad fraction of the polypropylene is less than 0.960, the effect of improving the tensile strength and crack prevention of drawn products (films, tapes, and yarns) will be reduced, which is not preferable.
本発明において、上記ポリプロピレンの沸騰ヘプタン不
溶部のアイソタクチックペンタッド分率は次のようにし
て求められる。In the present invention, the isotactic pentad fraction of the boiling heptane insoluble portion of the polypropylene is determined as follows.
ポリプロピレン！ｒＩＩを沸騰キシレン！００ｔｄに完
全に溶解させた後１．２０′ｃまで放冷する。polypropylene! Boil rII in xylene! After completely dissolving at 1.00td, the solution was allowed to cool to 1.20'c.
その後、戸別し２０℃キシレン可溶部と不溶部に分離す
る。次いで、コＯ℃キシレン不溶部をさらに沸騰ヘプタ
ンで６時間ソックスレー抽出残渣と抽出物に分離する。Thereafter, it is separated into a xylene soluble part and an insoluble part at 20°C. Then, the xylene-insoluble portion was further separated into a Soxhlet extraction residue and an extract using boiling heptane for 6 hours.
この抽出残渣を沸騰ヘプタン不溶部とする。This extraction residue is used as the boiling heptane insoluble part.
アイソタクチックペンタッド分率とはｌｌＣ−ＮＭＲを
使用して測定されるポリプロピレン分子鎖中のペンタッ
ド単位でのアイソタクチック−分率であシ、Ｍａｃｒｏ
ｍｏｌｅ ｃｕｂｅｓざｇｇ７（／デフｇ）に記載され
ている方法に基づいて測定される。Isotactic pentad fraction is the isotactic fraction in pentad units in a polypropylene molecular chain measured using IIC-NMR, Macro
It is measured based on the method described in Mole Cubes Zagg7 (/Defg).
具体的には、”Ｃ！−ＮＭＲスペクトルのメチル炭素領
域の全吸収ピーク中のｍｍｍｍピークの面積分率として
アイソタクチックペンタッド分率を測定する。Specifically, the isotactic pentad fraction is measured as the area fraction of the mmmm peak among the total absorption peaks in the methyl carbon region of the "C!-NMR spectrum."
本発明で使用するポリプロピレンのメルトフロレートイ
ンデックス（ＭＦｉと略称する）は延伸フィルム、延伸
テープ及びヤーン分野で用いられる任意のものでよいが
Ｊ工ＳＸ−り一１０の方法に従い、２３０℃、荷重２／
６０１１で測定した値でＯ，コ〜ｌθの範囲のものが好
壕しく、さらに好ましくはＯ，Ｓ〜乙の範囲のものであ
る。The melt fluorate index (abbreviated as MFi) of the polypropylene used in the present invention may be any one used in the fields of stretched films, stretched tapes, and yarns, but it was determined according to the method of J. 2/
6011, values in the range of O, C to lθ are preferable, and values in the range of O, S to B are more preferable.
一方、上記ポリプロピレンに配合して用いられる末端に
少なくとも７個の水酸基を有する主鎖の飽和した又は部
分的に飽和した炭化水素系ポリマーとは具体的には、例
えば次のようなものをいう。On the other hand, the hydrocarbon polymer with a saturated or partially saturated main chain having at least 7 hydroxyl groups at the end, which is blended into the polypropylene, specifically refers to the following, for example.
このポリマーは、少くとも末端に１個の水酸基を有し、
主鎖の飽和された、分子量２００〜：１ｏｏ、ｏｏｏの
常温で液体、半固体、固体のポリマーが含まれる。１分
子ａｂの平均水酸基数はｉ、ｚ−ｒ、ｏのものが好まし
い。また、本発明において用いられる末端に少くとも１
個の水酸基を有する主鎖の飽和した又は部分的に飽和し
た炭化水素系ポリマー（以下単Ｋ「末端に少くとも７個
の水酸基を有する主鎖の飽和した炭化水素系ポリマー」
と略す。）は、主鎖の炭化水素類が完全に或は部分的に
飽和されているものをいう。へ弘−ポリプタジエンにつ
いていえば、水添の割合は少くとも１０％、好ましくは
３０−以上、更に好ましくは１０４以上である。This polymer has at least one terminal hydroxyl group,
It includes polymers with a saturated main chain, a molecular weight of 200 to 100,000, and a liquid, semisolid, or solid at room temperature. The average number of hydroxyl groups in one molecule of ab is preferably i, z-r, or o. Furthermore, at least one terminal is used in the present invention.
A saturated or partially saturated hydrocarbon polymer with a main chain having at least 7 hydroxyl groups (hereinafter referred to as a "saturated hydrocarbon polymer with a main chain having at least 7 terminal hydroxyl groups")
It is abbreviated as ) means that the main chain hydrocarbons are completely or partially saturated. For Hehiro polyptadiene, the hydrogenation percentage is at least 10%, preferably 30 or more, more preferably 104 or more.
これら末端に少くとも１個の水酸基を有する主鎖の飽和
した炭化水素系ポリマーは、ジエンを原料として周知の
方法、例えばラジカル重合法、アニオン重合法などによ
って製造されたジエン系ポリマー及び／又はジエン系コ
ポリマーを、通常、水素添加することによシ得られる。These hydrocarbon polymers with a saturated main chain having at least one hydroxyl group at the end are diene polymers and/or diene polymers produced using dienes as raw materials by well-known methods such as radical polymerization and anionic polymerization. It is usually obtained by hydrogenating the copolymer.
しかしアニオン重合の場合には、条件によってポリジエ
ン骨格の交互炭素原子上に主要量の、たとえば３０％以
上、特にり０チ以上のビニル基を有し、主鎖が飽和した
炭化水素系ポリマー、すなわち、八−一ポリプタジエン
が得られるので、このものは更に水素添加する必要はな
い。However, in the case of anionic polymerization, depending on the conditions, hydrocarbon polymers with a major amount, for example 30% or more, especially 0 or more, of vinyl groups on alternating carbon atoms of the polydiene skeleton and whose main chain is saturated, i.e. , 8-1 polyptadiene is obtained, which does not require further hydrogenation.
末端に少くとも７個の水酸基を有するジエン系ポリマー
の製造法は、ラジカル重合による場合、過酸化水素を重
合開始剤としてジエン系モノマーを重合することにより
容易に得られる。A diene polymer having at least seven hydroxyl groups at its terminals can be easily produced by radical polymerization by polymerizing a diene monomer using hydrogen peroxide as a polymerization initiator.
アニオン重合法によって末端に水酸基を有するポリマー
を得るには、リビングポリマーに、例えば七ノエポキン
化合物、ホルムアルデヒド、アセトアルデヒドもしくは
アセトン、又はハロゲノアルキレンオキシド、ポリエポ
キシドを反応させれば良い。In order to obtain a polymer having a terminal hydroxyl group by anionic polymerization, a living polymer may be reacted with, for example, a heptanoepoquine compound, formaldehyde, acetaldehyde or acetone, or a halogenoalkylene oxide or polyepoxide.
なお、ここでいうリビングポリマーとは、周知の方法に
従って、共役ジエン単独又は共役ジエンとビニルモノマ
ーとをアニオン重合触媒、例えばアルカリ金属又は有機
アルカリ金属化合物を用いて重合させることによυ製造
されるポリマーであって、その両末端の少くとも一つに
アルカリ金屑が結合した構造を有するものをいう。The living polymer herein refers to a polymer produced by polymerizing a conjugated diene alone or a conjugated diene and a vinyl monomer using an anionic polymerization catalyst, such as an alkali metal or an organic alkali metal compound, according to a well-known method. A polymer having a structure in which alkali metal scraps are bonded to at least one of its ends.
これらポリマーの原料モノマーとしては少なくとも７種
類の共役ジエンモノマーが使用される。共役ジエンモノ
マーとしては、ブタジェン−／、、７、イソプレン、ク
ロロプレン、ペンタジェン−／、、？ 、コ、３−ジメ
チルブタジェンー八３、ｌ−フェニルブタジェンへ３等
が挙げられる。At least seven types of conjugated diene monomers are used as raw material monomers for these polymers. Conjugated diene monomers include butadiene-/, 7, isoprene, chloroprene, pentadiene-/, ? , co, 3-dimethylbutadiene-8, 3, l-phenylbutadiene, and the like.
一方、共役ジエン系コポリマーの共重合成分としては、
とニルモノマーが目的によ＃）７種又はコ種以上使用さ
れる。これらのビニルモノマーとしてはスチレン、α−
メチルスチレン、ビニルトルエン等のビニル芳香族化合
物；メチルアクリレート、ブチルアクリレート、メチル
メタクリレート等の（メタ）アクリル酸誘導体；アクリ
ロニトリル、メタクリレートリル等のニトリル化合物；
コービニルビリジン、弘−ビニルピリジン等のビニルピ
リジン；メチルビニルエーテル、λ−クロルエチルビニ
ルエーテル等のビニルエーテル；塩化ビニル、臭化ビニ
ル等のハロゲン化ビニル；酢酸ビニル等のビニルエステ
ル等が使用できる。また、コーヒドロキシエチルメタク
リレート、アクリル酸、アクリルアミドのような活性水
素を有するとニルモノマーも使用出来る。共役ジエン系
モノマーと併用する場合、ビニルモノマーの使用量は最
終目的物の物性を考慮した場合には総モノマー量に対し
ｈｏＩｌｘｓ以下が好ましい。On the other hand, as a copolymerization component of a conjugated diene copolymer,
Depending on the purpose, seven or more types of monomers are used. These vinyl monomers include styrene, α-
Vinyl aromatic compounds such as methylstyrene and vinyltoluene; (meth)acrylic acid derivatives such as methyl acrylate, butyl acrylate and methyl methacrylate; nitrile compounds such as acrylonitrile and methacrylaterile;
Vinyl pyridines such as co-vinylpyridine and Hiro-vinylpyridine; vinyl ethers such as methyl vinyl ether and λ-chloroethyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; and vinyl esters such as vinyl acetate. Furthermore, monomers containing active hydrogen such as co-hydroxyethyl methacrylate, acrylic acid, and acrylamide can also be used. When used in combination with a conjugated diene monomer, the amount of the vinyl monomer used is preferably hollxs or less based on the total monomer amount, considering the physical properties of the final target product.
これらジエン系ポリマー及び／又はジエン系コポリマー
の主鎖の不飽和二重結合は、全部又は部分的に水素添加
して使用される。しかじ主鎖に不飽和結合を実質的に含
まない八−結合のポリブタジェン１．７．ＩＩ結合のポ
リイソプレンポリマーの場合は、そのまま使用される。The unsaturated double bonds in the main chain of these diene polymers and/or diene copolymers are used after being completely or partially hydrogenated. Eight-bond polybutadiene with substantially no unsaturated bonds in the main chain 1.7. In the case of II bonded polyisoprene polymers, they are used as is.
上記の水素添加は、完全な水素化飽和でもよく、部分的
な水素添加でも差支えない。しかしながら、／４−ポリ
ブタジェンについていえば、水添の割合は、少なくとも
２０％、好ましくは３０％以上である。水添率が１０％
未満では接着性が不充分で、また多少の接着力があって
も接着面にむらがあって好ましくない。へダボリプタジ
エンは主鎖中に一重結合に関与する炭素原子は３０％存
在するので、本発明にあってはこれを７０％以下にする
ことが必要である。また、すでに前述したように、たと
えばへコ結合ｊ’Ｑ％の／、！ポリブタジェンは主鎖中
に一重結合に関与する炭素原子が３３％しか存在してい
ないので、このものは特に水添しなくともそのｔま本発
明に用いるポリマーとして使用することができる。The above hydrogenation may be complete hydrogenation saturation or partial hydrogenation. However, for /4-polybutadiene, the proportion of hydrogenation is at least 20%, preferably 30% or more. Hydrogenation rate is 10%
If it is less than that, the adhesiveness will be insufficient, and even if there is some adhesiveness, the adhesive surface will be uneven, which is not preferable. Since hedaboliptadiene has 30% of carbon atoms participating in single bonds in its main chain, it is necessary to reduce this to 70% or less in the present invention. Also, as already mentioned above, for example, the heco-bond j'Q% /,! Since polybutadiene has only 33% of the carbon atoms participating in single bonds in its main chain, it can be used as a polymer for the present invention even without hydrogenation.
水素化は一般に使用される接触水素化処理の手段を採用
することができる。即ち、水素添加触媒としては、古く
から使用されているニッケル触媒（たとえばラネーニッ
ケル）１．コバルト、白金、パラジウム、ルテニウム、
ロジウム触媒、これらの混合又は合金系触媒が使用でき
る。これらの触媒は単独で、固体又は可溶性均一錯体と
して、或いはカーボン、シリカ、珪そう土などに担持さ
れた形で使用できる。さらに、ニッケル、チタン、コバ
ルトなどを含む化合物を有機金属化合物（たとえばトリ
アルキルアルミニウム、アルキルリチウムなど）で還元
して得られる金属錯体を用いて水素添加してもよい。使
用水素としては、通常は分子状水素が用いられるが、触
媒毒となる物質を含まない限シ水素含有ガスを使用する
こともできる。水素圧は常圧ブローでも、加圧系のいず
れでも差支えない。For the hydrogenation, commonly used catalytic hydrogenation means can be employed. That is, as a hydrogenation catalyst, a nickel catalyst (for example, Raney nickel) which has been used for a long time is used.1. cobalt, platinum, palladium, ruthenium,
Rhodium catalysts and mixed or alloy catalysts can be used. These catalysts can be used alone, as solid or soluble homogeneous complexes, or supported on carbon, silica, diatomaceous earth, and the like. Furthermore, hydrogenation may be performed using a metal complex obtained by reducing a compound containing nickel, titanium, cobalt, etc. with an organometallic compound (for example, trialkylaluminum, alkyllithium, etc.). Molecular hydrogen is usually used as hydrogen, but hydrogen-containing gas can also be used as long as it does not contain substances that poison the catalyst. The hydrogen pressure can be either normal pressure blowing or pressurized system.
温度は室温〜、２００℃、好ましくは１ｔｒｏ℃以下で
ある。ジエン系ポリマー及び／又はジエン系コポリマー
は単独でも、或いは溶媒溶液としても使用できる。かか
る溶媒としては、脂肪族炭化水素、脂環族炭化水素、芳
香族炭化水素、アルコール類、脂肪族カルボン酸などが
単独で、或いは混合系で使用できる。The temperature is room temperature to 200°C, preferably 1 tro°C or less. The diene polymer and/or diene copolymer can be used alone or as a solution in a solvent. As such solvents, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, alcohols, aliphatic carboxylic acids, etc. can be used alone or in a mixed system.
本発明の組成物を調製するに当って使用される飽和炭化
水素系ポリマーのその他の製法としては、α−オレフィ
ンと他のモノマーとの共重合体を酸化・分解処理し、次
で還元する方法が挙げられる。たとえば、インブチレン
とブタジェン又はへ３−ペンタジェンをカチオン重合さ
せて得られるブチルゴム系の重合体をオゾン分解処理し
、次でリチウムアルミニウムハイドライドで還元すれば
ポリヒドロキシポリイソブチレンが得られる。また、エ
チレン単独で、又はプロピレンとの共存下でジエン類と
共重合させて得られる不飽和結合を有するポリ−α−オ
レフィンをオゾン分解処理し、次で還元することにより
ポリヒドロキシポリオレフィンが得られる０
本発明において、上記ポリプロピレンの割れ防止、透明
性を改良するために添加する上記の末端に少なくとも７
個の水酸基を有する主鎖の飽和した炭化水素系ポリマー
の配合量は該ポリプロピレン１００重量部に対し０．０
／−一重量部、通常０．／〜−２１１量部、好ましく
は０．３〜八、２重量部の範囲で使用される。上記末端
に少なくとも１個の水酸基を有する主鎖の飽和した炭化
水素系ポリマーの配合量が上記範囲未満ではボリプｉピ
レンの割れ防止及び透明性の改良効果が少なく、また上
記範囲を超えた場合には割れ防止及び透明性の改良効果
がそれ以上増加せず、逆に耐溶剤性が低下してくるので
好ましくない。Another method for producing the saturated hydrocarbon polymer used in preparing the composition of the present invention is a method in which a copolymer of α-olefin and other monomer is oxidized and decomposed, and then reduced. can be mentioned. For example, polyhydroxypolyisobutylene can be obtained by subjecting a butyl rubber-based polymer obtained by cationic polymerization of inbutylene and butadiene or he-3-pentadiene to ozone decomposition treatment, and then reducing it with lithium aluminum hydride. In addition, polyhydroxypolyolefins can be obtained by ozonolyzing poly-α-olefins containing unsaturated bonds obtained by copolymerizing ethylene alone or with dienes in the coexistence of propylene, and then reducing the poly-α-olefins. 0 In the present invention, at least 7% is added to the terminal end of the polypropylene to prevent cracking and improve transparency
The amount of the hydrocarbon polymer with a saturated main chain having hydroxyl groups is 0.0 parts by weight per 100 parts by weight of the polypropylene.
/-1 part by weight, usually 0. / to -211 parts by weight, preferably 0.3 to 8.2 parts by weight. If the amount of the hydrocarbon polymer with a saturated main chain having at least one hydroxyl group at the end is less than the above range, the effect of preventing cracking and improving the transparency of Voripyrene will be small, and if it exceeds the above range, This is not preferred because the effect of preventing cracking and improving transparency does not increase any further, and on the contrary, the solvent resistance decreases.
本発明！用いるポリプロビレ／樹脂組成物は前記したポ
リプロピレンと末端に少なくとも７個の水酸基を有する
主鎖の飽和した炭化水素系ポリマーをプレンダーなどで
トライブレンドするか、或はトライブレンドした後通常
の溶融混線法、例えば、バンバリーミキサ−、コンティ
ニュアスミキサー、ミキシングロール、押出機等によっ
て、ｌｆθ〜３００℃の温度で溶融混合しイレット化す
ることによシ得られる。This invention! The polypropylene/resin composition used is prepared by tri-blending the above-mentioned polypropylene and a saturated hydrocarbon polymer with a main chain having at least seven hydroxyl groups at the end using a blender, or by tri-blending and then using a conventional melt mixing method. For example, it can be obtained by melt-mixing and islet-forming at a temperature of lfθ to 300° C. using a Banbury mixer, a continuous mixer, a mixing roll, an extruder, or the like.
本発明で用いられるポリプロピレン樹脂組成物には、必
要に応じて熱安定剤、酸化防止剤、紫外線吸収剤、アン
チブロッキング剤、滑剤、その他の添加剤などポリプロ
ピレンに使用される公知の各種添加剤を加えてもよい。The polypropylene resin composition used in the present invention may contain various known additives used in polypropylene, such as heat stabilizers, antioxidants, ultraviolet absorbers, anti-blocking agents, lubricants, and other additives, as necessary. May be added.
本発明においては、上記で得られたポリプロピレン樹脂
組成物を用いて未延伸フィルムまたはシートを成形し、
次いで該未延伸フィルムまたはシートを特定の条件下で
一軸延伸して一軸延伸フイルム、テープまたはヤーンを
製造する。In the present invention, an unstretched film or sheet is formed using the polypropylene resin composition obtained above,
The unstretched film or sheet is then uniaxially stretched under specific conditions to produce a uniaxially stretched film, tape or yarn.
未延伸フィルムまたはシートの成形は通常のフィルムま
たはシートの成形装置及び成形方法、例えば円形ダイに
よるインフレーション成形法、ＴダイによるＴダイ成形
法等を採用し、上記の組成物を樹脂温度／９０〜５ｏｏ
ｃ、ドラフト率／−！ＴＯの範囲の成形条件で行なわれ
る。The unstretched film or sheet is formed using a conventional film or sheet forming apparatus and forming method, such as an inflation molding method using a circular die or a T-die molding method using a T-die, and the above composition is heated to a resin temperature of 90 to 90°C. 5oo
c, draft rate/-! The molding is carried out under molding conditions in the range of TO.
インフレーション成形する場合には樹脂温度をｉｔｏ〜
２り０℃、ブローアツプ比をハｊ〜弘、ドラフト率を／
−ｊｔＯの範囲の条件で行なうのが望ましい。When performing inflation molding, the resin temperature is
20℃, blow-up ratio, draft rate /
It is desirable to carry out the test under conditions in the range of -jtO.
なお、本発明においてドラフト率とは下記によって得ら
れる。Note that in the present invention, the draft rate is obtained as follows.
ρｍＣｋ ／
ドラフト率諺−・ −・□
ρｆ ｔ ＢＵＲ
式中、記号は下記の通シ
なお、Ｔダイ成形の場合はＢＵＲ−／とじて表わされる
。ρmCk / Draft rate proverb -・-・□ ρft BUR In the formula, the symbols are as follows, and in the case of T-die molding, it is expressed as BUR-/.
ドラフト率が７未満の場合には製膜フィルムの成形性が
不良となシ、また、ｇｏよシ大きい場合には延伸時に縦
裂けし易くなるので好ましくない。If the draft rate is less than 7, the formability of the formed film will be poor, and if it is too high, it will tend to tear longitudinally during stretching, which is not preferred.
また、τダイ成形する場合には樹脂温度を１９０〜３０
０℃、ドラフト率を／〜１０、冷却ロール温度をＪＯ〜
ｉ；ｔｏ℃の範囲の条件で行なうのが望ましい。In addition, when performing τ die molding, the resin temperature should be set to 190 to 30
0℃, draft rate /~10, cooling roll temperature JO~
It is desirable to carry out the process under conditions in the range of i; to °C.
上記のようにして得られた未延伸フィルムまたはシート
はそのまま或は所定の幅にスリットしたものをオープン
加熱、ロール加熱または熱板加熱法によυ縦方向に１段
または一段以上の多段で延伸を行う。The unstretched film or sheet obtained as above may be stretched as it is or after being slit to a predetermined width in one or more stages in the longitudinal direction by open heating, roll heating, or hot plate heating. I do.
延伸条件としては延伸温度１ｓｏ−２ｏｏ℃、好ましく
は７３３〜／７ｊｕ、延伸倍率２〜１０倍、好ましくは
ψ〜を倍の範囲である。The stretching conditions are a stretching temperature of 1so-2oo<0>C, preferably 733-/7ju, and a stretching ratio of 2-10 times, preferably ψ- times.
延伸温度がｉｚｏ℃未満では分子鎖の運動性が乏しいた
め、延伸時に切断しやすく、たとえ延伸できても延伸倍
率が上がらず、物性のすぐれた延伸物を得ることができ
ない。まｆ４２００℃より高い温度では該樹脂組成物が
一部溶けかがシ延伸配向を起すことができず、見かけ上
延伸されても延伸斑がひどく、また透明性も損なわれて
しまい、商品価値のある延伸物とはならない０
さらに、縦方向への延伸倍率が２倍未満では得られる延
伸フィルムの厚みムラが大きくなシ均一な延伸物が得ら
れず、また７０倍よシ大きいと延伸操作性が悪化し、滴
足した延伸物が得られないので好ましくない。When the stretching temperature is lower than Izo°C, the molecular chains have poor mobility and are easily broken during stretching, and even if stretching is possible, the stretching ratio cannot be increased and a stretched product with excellent physical properties cannot be obtained. At temperatures higher than 4,200°C, the resin composition partially melts and cannot be stretched and oriented, and even if stretched apparently, stretching unevenness is severe and transparency is impaired, reducing the commercial value. Furthermore, if the stretching ratio in the machine direction is less than 2 times, the thickness of the stretched film obtained will be large and a uniform stretched product will not be obtained, and if the stretching ratio is greater than 70 times, the stretching operability will be poor. This is not preferable because it deteriorates and a stretched stretched product cannot be obtained.
上記延伸処理して得られた延伸物（延伸フィルム、テー
プまたはヤーン）は伸びが大きく、且つ熱収縮しやすい
ので、通常５０〜ｉｒｏ℃の温度で０．１〜７０秒熱処
理（アニーリング）し、通常１０％以下、望ましくは３
〜７％熱収縮させておくのが望ましい。The stretched product (stretched film, tape, or yarn) obtained by the above stretching treatment has a large elongation and is easily heat-shrinkable, so it is usually heat-treated (annealed) at a temperature of 50 to iroC for 0.1 to 70 seconds, Usually less than 10%, preferably 3
It is desirable to heat shrink by ~7%.
以下、実施例によυ本発明につき爽に具体的に説明する
が、本発明はその要旨を超えない限シ、以下の実施例に
よって限定されるものではない。Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited by the following examples unless it exceeds the gist thereof.
実施例／〜ｑ
（１）末端に水酸基を有する飽和炭水素系ポリマーの製
造
容量ｌＯｔのオートクレーブにポリヒドロキシポリブタ
ジェン（Ａｒｅａ Ｃ！ｈｅｍ、社製Ｒ−９５ＨＴ、
（−ＯＨ） −０，ｇコｍｅｑ／１１、シス八ダニ１３
チ、トランス−へダニ３Ｓチ、ビニル：コク％）３に９
、シクロヘキサン３Ｋｙ及Ｕカーボン担持ルテニウム（
３％）触媒〔日本エンゲルハルト側製〕ＪＯＯＩを仕込
み、系内を精製アルゴンガスで置換した後、高純度水素
ガスをオートクレーブ内に供給し始め、同時に加熱を開
始する。約３０分を要してオートクレーブ内は定常条件
（内温１００℃、内圧／ ｓ ｏ Ｋｑ／ｌ−ｙ！ ）
に達した。この条件で７５時間経過後、水添反応を停止
し、以下常法に従ってポリマーを精製、乾燥した。Examples/~q (1) Production of a saturated hydrocarbon polymer having a hydroxyl group at the terminal In an autoclave with a capacity of 10t, polyhydroxypolybutadiene (R-95HT manufactured by Area C!hem, Inc.,
(-OH) -0, gcomeq/11, cis eight ticks 13
3S, vinyl: body%) 3 to 9
, cyclohexane 3Ky and U carbon-supported ruthenium (
3%) catalyst [manufactured by Engelhard Japan] After charging JOOI and replacing the inside of the system with purified argon gas, high-purity hydrogen gas is started to be supplied into the autoclave, and heating is started at the same time. It takes about 30 minutes to reach steady conditions inside the autoclave (internal temperature 100℃, internal pressure / so Kq/l-y!)
reached. After 75 hours under these conditions, the hydrogenation reaction was stopped, and the polymer was purified and dried according to a conventional method.
得られたポリマーは赤外吸収スペクトルによる分析の結
果、殆んど二重結合を含まぬ炭化水素系ポリマーであっ
た。水添物の−ＯＨ基は０．ｇ ／ ｍｅｑ／ｇであり
、蒸気工法で測定した分子量は３００θであった。As a result of analysis by infrared absorption spectrum, the obtained polymer was found to be a hydrocarbon polymer containing almost no double bonds. The -OH group of the hydrogenated product is 0. g/meq/g, and the molecular weight measured by the steam method was 300θ.
（２） ポリプロピレン樹脂組成物の製造及び−軸延
伸フィルムの製造
メルト７０レートインデツクスがコ＋ｊ 、９ ／７０
分及びアイソタクチックペンタッド分率が０．９ＩＯの
ポリプロピレンホモポリマー１００重量に上記（１）で
得られた末端に水酸基を有する飽和炭化水素系ポリマー
を第１表に示す配合量で添加し、これをトライブレンド
した後、シリンダー径ＩＩ Ｏｔａｎ Ｉｆの単軸押出
機で１９０℃の温度で溶融混練して押出ペレット化した
。(2) Production of polypropylene resin composition and -axis stretched film Melt 70 rate index is co+j, 9/70
The saturated hydrocarbon polymer having a hydroxyl group at the terminal obtained in the above (1) was added to 100 weight of polypropylene homopolymer having an isotactic pentad fraction of 0.9IO in the amount shown in Table 1, After tri-blending this, it was melt-kneaded at a temperature of 190° C. using a single-screw extruder with a cylinder diameter of II Otan If, and extruded into pellets.
得られたポリプロピレン樹脂組成物をＴ −ダイ式成形
機を用いて２６０℃の樹脂温度で冷却ロール温度９０℃
、巻取速度２．０ｍ１分、ドラフト率／、ｊの条件下で
シート状に押出し、厚み０．２ｒｍのシートを成形した
。このシートをロール延伸機を用いて、ｉｔ、ｏ℃で縦
方向に３倍延伸して厚み約ＩＩＯμの一軸延伸フイルム
を製造した。この際、下記方法により延伸性、剛性及び
透明性の測定を行った。その結果を第１表に示す。The obtained polypropylene resin composition was heated using a T-die molding machine at a resin temperature of 260°C and a cooling roll temperature of 90°C.
A sheet having a thickness of 0.2 rm was formed by extruding it into a sheet under the conditions of a winding speed of 2.0 ml/min and a draft rate of /, j. This sheet was stretched 3 times in the machine direction using a roll stretching machine at 0.degree. C. to produce a uniaxially stretched film having a thickness of about IIO.mu.. At this time, stretchability, rigidity, and transparency were measured by the following methods. The results are shown in Table 1.
■ アイソタクチックペンタッド分率の測定法
試料のＰＰ！１１をｒｏｏｃｒ、ｏｐ −＊’、ｔｖン
でｊ分間ｒｅｆｌｕｘ処理し、放冷后の析出分を一〇〇
ｃｃのＨ−ヘプタンでｉｓ ｈｒ ｒｅｆｌｕｘＭＲ
処理した不溶分をＯ−／Ｊ 測定に供した。■Measurement method of isotactic pentad fraction PP of sample! No. 11 was subjected to reflux treatment for j minutes using ROOCR, OP-*', and TV, and after cooling, the precipitated matter was treated with 100 cc of H-heptane. .
、、３ＮＭＨの測定法及びスペクトルの解析定量はＭａ
ｃｒｏｍｏｌｅｃｕｌｅｓ ｇ ４ｇ？ （ｔｑ７ｇ）
の示される方法に拠った。, , 3NMH measurement method and spectrum analysis quantification are Ma
Cromolecules g 4g? (tq7g)
Based on the method shown.
■ 延伸性の評価
上記（２）の−軸延伸フィルム製造時において、縦方向
延伸時の機械的応力を記録した。(2) Evaluation of Stretchability During the production of the -axis stretched film in (2) above, the mechanical stress during stretching in the longitudinal direction was recorded.
延伸応力が小さい程延伸性が優れている。The lower the stretching stress, the better the stretching property.
■ −軸延伸フィルムの剛性の測定
Ｊ ＆ ｗ Ｘ ／ダＯｗｍの短冊状のフィルム試験片
を用い引張試験機でクロスヘッドスピード／θｍＶｍで
引張シ初期弾性率を求めた。(2) - Measurement of rigidity of axially stretched film Using a J & W
（縦方向）
■ −軸延伸フィルムの透明性の測定
Ａ８ＴＭ Ｄ−１０ＯＪ−よ２Ｔに準じてヘーズメータ
で測定した。(Longitudinal direction) - Measurement of transparency of axially stretched film Measurement was carried out using a haze meter according to A8TM D-10OJ-Y2T.
比較例１
実施例／において、末端に水酸基を有する飽和炭化水素
系ポリマーを全く添加せずに行ったこと以外は実施例１
と同様に行った。Comparative Example 1 Example 1 except that Example 1 was carried out without adding any saturated hydrocarbon polymer having a hydroxyl group at the end.
I did the same thing.
その結果を第１表に示す。The results are shown in Table 1.
比較例コ
実施例７において、末端に水酸基を有する飽和炭化水素
系ポリマーの配合量を３重量部に変えたこと以外は実施
例／と同様に行った。Comparative Example Example 7 was carried out in the same manner as in Example 7, except that the amount of the saturated hydrocarbon polymer having a hydroxyl group at the end was changed to 3 parts by weight.
その結果を第１表に示す。The results are shown in Table 1.
比較例３
実施例１において、ポリプロピレンをＭＩＦｉが２．０
１／１０分でアイソタクチックペンタッド分率が０．’
？！、７のポリプロピレンホモポリマーにかえ、末端に
水酸基を有する飽和炭化水素系ポリマーを全く添加せず
に行ったこと以外は実施例／と同様に行った。Comparative Example 3 In Example 1, MIFi of polypropylene was 2.0.
The isotactic pentad fraction is 0 at 1/10 min. '
? ! The same procedure as in Example 1 was carried out except that instead of using the polypropylene homopolymer of , 7, and without adding any saturated hydrocarbon polymer having a hydroxyl group at the terminal.
その結果を第１表に示す。The results are shown in Table 1.
実施例ま〜／３
メルトフロレートインデックス及びアイソタクチックペ
ンタッド分率が第−表に示す物性であるポリプロピレン
ホモポリマー１００ｉｆｆｉに上記実施例／の（１）で
得られた末端に水酸基を有する飽和炭化水素系ポリマー
をｔｇ−表に示す配合量で添加し、これをトライブレン
ドした後、シリンダー径ｑｏ鴎ｆの単軸押出機で１９０
℃の温度で溶融混練して押出ベレット化した。Example 1~/3 Polypropylene homopolymer 100iffi whose melt fluorate index and isotactic pentad fraction have the physical properties shown in Table 1 was saturated with a hydroxyl group at the end obtained in Example 1 (1) above. After adding the hydrocarbon polymer in the amount shown in the tg-table and tri-blending it, it was heated to 190 ml using a single-screw extruder with a cylinder diameter of
The mixture was melt-kneaded and extruded into pellets at a temperature of °C.
得られたポリプロピレン樹脂組成物をＴ−ダイ式成形機
を用いて２２０℃の樹脂温度で冷却ロール温度ＳＯ℃、
巻取速度７ ｍ／％、ドラフト率コ、Ｑの条件下でシー
ト状に押出し、厚み１００μのフィルムを成形した。こ
のフィルムをロール延伸機を用いて、７３０℃で縦方向
に延伸し、次いで７３０℃で７二−リング処理して延伸
物を約６％収縮させた延伸テープを製造した。なお、第
４表に示す延伸倍率はアニーリング処理後の倍率を示す
。得られた延伸テープにつき、下記方法にて延伸強度及
び割れ特性を測定した。The obtained polypropylene resin composition was heated using a T-die molding machine at a resin temperature of 220°C and a cooling roll temperature of SO°C.
It was extruded into a sheet under the conditions of a winding speed of 7 m/% and a draft ratio of Q and Q to form a film with a thickness of 100 μm. This film was stretched in the longitudinal direction at 730° C. using a roll stretching machine, and then subjected to 7-ring treatment at 730° C. to produce a stretched tape in which the stretched product was shrunk by about 6%. Note that the stretching ratios shown in Table 4 indicate the ratios after annealing treatment. The stretching strength and cracking properties of the obtained stretched tape were measured by the following method.
その結果を第２表に示す。The results are shown in Table 2.
■ 延伸テープの引張強度の測定
延伸して得られた巾６簡×長さｌＩｋ Ｏｗ Ｘ厚み−
ざμ（１０００デニール）の延伸テープを用い、引張試
験機でクロスヘッドスピードＪ００−で引張シ、引張強
度を（ｙ／ａ ）求めた。■ Measurement of tensile strength of stretched tape Width 6 strips x length lIk Ow x thickness -
Using a stretched tape of 1000 denier, the tensile strength (y/a) was determined using a tensile tester at a crosshead speed of J00-.
■ 延伸テープの割れ特性の測定
各延伸倍率で延伸されているテープをｎ −１０本を両
端を開放した筒（内径ｉｏｏ〆ｗＸ長さ／ｊＯＯｗ）の
中を通し、片方より圧力空気を入れ、７０本中のテープ
の割れの発生本数を観察する。圧力空気はＱ、コＫｙ／
ｃｎｌＧ間隔にて上昇し測定する。筒の中の延伸テープ
の通過秒数はＯ，ダ〜コＯであるが、通常条件では約／
ｓｅａである。■ Measurement of cracking characteristics of stretched tapes N - 10 tapes stretched at various stretching ratios were passed through a tube with both ends open (inner diameter ioo〆wX length/jOOw), and pressurized air was introduced from one side. Observe the number of cracks among the 70 tapes. Pressure air is Q, KoKy/
It rises and is measured at the cnlG interval. The number of seconds for the stretched tape to pass through the cylinder is O, Dako O, but under normal conditions it is about /
It is sea.
比較例ダ〜６
実施例３において、末端に水酸基を有する飽和炭化水素
系ポリマーを全く添加せず延伸倍率を第−表に示す条件
で行ったこと以外は実施例ｊと同様に行った。Comparative Examples D to 6 The same procedure as in Example J was carried out in Example 3, except that no saturated hydrocarbon polymer having a hydroxyl group at the terminal was added and the stretching ratio was set as shown in Table 1.
その結果を第−表に示す。The results are shown in Table 1.
比較例７〜デ
実施例３において、末端に水酸基を有する飽和炭化水素
系ポリマーを全く添加せず炭酸カルシウムを重量％添加
し延伸倍率を第１表に示す条件で行ったこと以外は実施
例３と同様に行った０
その結果を第１表に示す。Comparative Examples 7 to Example 3 except that no saturated hydrocarbon polymer having a hydroxyl group at the end was added, calcium carbonate was added in a weight percent, and the stretching ratio was set as shown in Table 1. The results are shown in Table 1.
へニーｒ、’ｐＨ
・、１ノｌ；ごＪＵ
第１表よシ明らかな様に立体規則性の高いポリプロピレ
ンは延伸に要する応力が高いが、本発明に述べる「末端
に水酸基を有するポリマー」を配合することにより、延
伸応力を低減し、かつ、−軸延伸フィルムの剛性は維持
できさらに大巾に透明性を改良出来る。As is clear from Table 1, polypropylene with high stereoregularity requires high stress for stretching, but the "polymer having a hydroxyl group at the end" described in the present invention By blending, the stretching stress can be reduced, the rigidity of the -axis stretched film can be maintained, and the transparency can be greatly improved.
また、第−表よシ本発明方法で得られた延伸テープは上
記ポリプロピレンの高い延伸強度を保持したまま、割れ
特性が大幅に改良されている０
〔発明の効果〕
本発明によれば、特定のポリプロピレンに末端に少なく
とも７個の水酸基を有する主鎖に飽和した炭化水素ポリ
マーを特定量配合させ、特定条件で一軸延伸物にするこ
とによシ上記ポリプロピレンの高い延伸強度を保持させ
たまま、割れ特性及び透明性の著しく改良されたポリプ
ロピレン一軸延伸物を得るととが出来る。In addition, as shown in Table 1, the stretched tape obtained by the method of the present invention has significantly improved cracking properties while maintaining the high stretching strength of the polypropylene. A specific amount of a hydrocarbon polymer saturated in the main chain having at least seven hydroxyl groups at the end is blended into the polypropylene, and the polypropylene is uniaxially stretched under specific conditions, thereby maintaining the high stretching strength of the polypropylene. It is possible to obtain a uniaxially oriented polypropylene product with significantly improved cracking properties and transparency.
従って本発明で得られるポリプロピレン一軸延伸物（例
えば延伸フィルム、延伸テープまたはヤーン）は包装用
フィルム、フレコン基布、シート基布等の用途に好適に
用いることが出来る０
さらに本発明の最大の用途は、高１工ｉ料にて展開して
いるジュータン用のヤーンといえる。Therefore, the polypropylene uniaxially stretched products (for example, stretched films, stretched tapes, or yarns) obtained in the present invention can be suitably used for packaging films, flexible container base fabrics, sheet base fabrics, etc. Furthermore, the greatest use of the present invention is This can be said to be a yarn for jutan, which is developed as a high-grade I material.
ジュータン用のヤーンは、後収縮によるねじれ防止の為
、高エエの（デざ、３以上）ポリプロピレン（ホモ）を
原料としている〇
従って従来より割れが問題となっておシ、本発明によシ
大巾な改良が期待出来る。Yarn for jutan is made from polypropylene (homo) with a high density (degradation of 3 or more) in order to prevent twisting due to post-shrinkage. Significant improvements can be expected.
出 願 人 三菱化成工業株式会社 代 理 人 弁理士長各州 − （ほか１名）Sender: Mitsubishi Chemical Industries, Ltd. Representative Chief Patent Attorney in each state - (1 other person)
Claims (1)
ＮＭＲで求められるアイソタクチックペンタッド分率と
して０．９６０以上のポリプロピレンホモポリマー１０
０重量部に対し、末端に少くとも１個の水酸基を有する
主鎖の飽和した又は部分的に飽和した炭化水素ポリマー
０．０１〜２重量部を配合してなる組成物を用いて未延
伸物を成形し、次いで該未延伸物を縦方向に２〜１０倍
の延伸倍率で延伸してなることを特徴とするポリプロピ
レン一軸延伸物の製造方法(1) The stereoregularity of the boiling heptane insoluble part is ^1^3C-
Polypropylene homopolymer 10 with an isotactic pentad fraction of 0.960 or more as determined by NMR
An unstretched product is produced using a composition comprising 0.01 to 2 parts by weight of a saturated or partially saturated hydrocarbon polymer with a main chain having at least one hydroxyl group at the terminal. A method for producing a uniaxially stretched polypropylene product, which comprises molding the unstretched product, and then stretching the unstretched product in the longitudinal direction at a stretching ratio of 2 to 10 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61056681A JPH0694163B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniaxially stretched polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61056681A JPH0694163B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniaxially stretched polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62212125A true JPS62212125A (en) | 1987-09-18 |
| JPH0694163B2 JPH0694163B2 (en) | 1994-11-24 |
Family
ID=13034168
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61056681A Expired - Lifetime JPH0694163B2 (en) | 1986-03-14 | 1986-03-14 | Method for producing uniaxially stretched polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0694163B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5431871A (en) * | 1990-10-08 | 1995-07-11 | Sumitomo Heavy Industries, Ltd. | Method for manufacturing three-dimensional parts from a fiber-reinforced resin composite |
| US5573723A (en) * | 1990-10-02 | 1996-11-12 | Hoechst Aktiengesellschaft | Process for preparing biaxially oriented polypropylene film suitable for twist wrapping |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090734A (en) * | 1983-10-25 | 1985-05-21 | Toray Ind Inc | Stretched polypropylene film |
| JPS60210647A (en) * | 1984-04-03 | 1985-10-23 | Toray Ind Inc | Polypropylene film |
-
1986
- 1986-03-14 JP JP61056681A patent/JPH0694163B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090734A (en) * | 1983-10-25 | 1985-05-21 | Toray Ind Inc | Stretched polypropylene film |
| JPS60210647A (en) * | 1984-04-03 | 1985-10-23 | Toray Ind Inc | Polypropylene film |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5573723A (en) * | 1990-10-02 | 1996-11-12 | Hoechst Aktiengesellschaft | Process for preparing biaxially oriented polypropylene film suitable for twist wrapping |
| US5431871A (en) * | 1990-10-08 | 1995-07-11 | Sumitomo Heavy Industries, Ltd. | Method for manufacturing three-dimensional parts from a fiber-reinforced resin composite |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0694163B2 (en) | 1994-11-24 |
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