JPH0551494A - Polyolefin composition - Google Patents
Polyolefin compositionInfo
- Publication number
- JPH0551494A JPH0551494A JP2344892A JP2344892A JPH0551494A JP H0551494 A JPH0551494 A JP H0551494A JP 2344892 A JP2344892 A JP 2344892A JP 2344892 A JP2344892 A JP 2344892A JP H0551494 A JPH0551494 A JP H0551494A
- Authority
- JP
- Japan
- Prior art keywords
- block copolymer
- conjugated diene
- hydrogenated
- hydrogenated block
- molecular weight
- 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
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 14
- 229920001400 block copolymer Polymers 0.000 claims abstract description 62
- -1 vinyl aromatic compound Chemical class 0.000 claims abstract description 49
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 15
- 150000001993 dienes Chemical group 0.000 claims abstract description 10
- 229920005672 polyolefin resin Polymers 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000004743 Polypropylene Substances 0.000 description 10
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 229920001155 polypropylene Polymers 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000008878 coupling Effects 0.000 description 7
- 238000010168 coupling process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 238000012937 correction Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000005060 rubber Substances 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
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- PKZCRWFNSBIBEW-UHFFFAOYSA-N 2-n,2-n,2-trimethylpropane-1,2-diamine Chemical compound CN(C)C(C)(C)CN PKZCRWFNSBIBEW-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
- OCTVDLUSQOJZEK-UHFFFAOYSA-N 4,5-diethylocta-1,3-diene Chemical compound CCCC(CC)C(CC)=CC=C OCTVDLUSQOJZEK-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- FKSJCZAVZLBVHS-UHFFFAOYSA-N [Ti]C1=CC=CC1 Chemical compound [Ti]C1=CC=CC1 FKSJCZAVZLBVHS-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920005676 ethylene-propylene block copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、衝撃強度、特に低温時
における耐衝撃性、流動加工性、外観特性（光沢）に優
れた特定構造の水素添加ブロック共重合体を含むポリオ
レフィン組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyolefin composition containing a hydrogenated block copolymer having a specific structure which is excellent in impact strength, particularly impact resistance at low temperature, flow processability, and appearance characteristics (gloss).
【０００２】[0002]
【従来の技術】ポリオレフィン系樹脂は、一般に耐薬品
性、機械的特性に優れているため、機械部品、自動車部
品から家庭用品、各種容器など広範に使用されている。
しかしながら、耐衝撃強度、特に低温時における衝撃強
度が不足しており、使用目的が限定されることもある。2. Description of the Related Art Polyolefin resins are generally used for a wide variety of purposes such as mechanical parts, automobile parts, household products, and various containers because they are excellent in chemical resistance and mechanical properties.
However, the impact resistance, especially the impact strength at low temperature, is insufficient, and the purpose of use may be limited.
【０００３】そこで、この問題点を改良する目的でゴム
成分をポリオレフィンに添加する提案が数多くなされて
いる。例えば、特公昭４２−１９９３５号公報、特公昭
４６−８５８５号公報、特公昭４６−１６４２９号公
報、特公昭４７−２６３６９号公報には、ポリオレフィ
ン系樹脂に、スチレン−ブタジエンブロック共重合体、
熱可塑性エラストマーを添加することにより、耐衝撃性
や耐ストレスクラッキング性が改良されることが示され
ている。Therefore, many proposals have been made to add a rubber component to polyolefin for the purpose of improving this problem. For example, Japanese Patent Publication No. 42-19935, Japanese Patent Publication No. 46-8585, Japanese Patent Publication No. 46-16429 and Japanese Patent Publication No. 47-26369 disclose a polyolefin resin, a styrene-butadiene block copolymer,
It has been shown that the addition of thermoplastic elastomers improves impact resistance and stress cracking resistance.
【０００４】しかし、これらの方法では通常のブロック
共重合体を用いているため、耐衝撃性の改良が十分でな
く、なお一層の改善が要望されていた。また、ゴム成分
を添加する弊害として流動加工性の低下、外観特性、特
に光沢度の低下をもたらすことがある。これらの点を改
良する目的で、ゴム成分に水添ジエン系ランダム共重合
体を用いた特開平２−１５８６４３号公報、特定分子量
のブロック共重合体を用いた特開平３−７６７４４号公
報が示されている。しかしながら、このようにして改良
された組成物は、実際に必要とされる低温時の耐衝撃性
については十分なものではなく、さらに一層の改良が要
望されていた。However, since the conventional block copolymers are used in these methods, the impact resistance is not sufficiently improved, and further improvement has been demanded. Further, as a harmful effect of adding the rubber component, there is a case where flow processability is deteriorated and appearance characteristics, particularly glossiness are deteriorated. For the purpose of improving these points, JP-A-2-158643 using a hydrogenated diene random copolymer as a rubber component and JP-A-3-76744 using a block copolymer having a specific molecular weight are disclosed. Has been done. However, the composition improved in this way is not sufficient in the impact resistance at low temperature actually required, and further improvement has been demanded.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、耐衝
撃性、特に実用的な低温時の耐衝撃性と外観特性に優
れ、かつ射出成形や押出成形に適した優れた流動加工性
を有する優れたポリオレフィン組成物を提供することに
ある。SUMMARY OF THE INVENTION The object of the present invention is to provide excellent impact resistance, in particular, impact resistance at low temperature and practical appearance characteristics, and excellent flow processability suitable for injection molding and extrusion molding. Another object of the present invention is to provide an excellent polyolefin composition.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、ビニル芳
香族化合物ブロック−共役ジエン化合物ブロック共重合
体の水素添加物のポリマー構造とポリオレフィン組成物
の物性との相関について、鋭意検討を進めた結果、低温
衝撃強度、外観特性かつ流動加工性に優れた組成物を得
るために、特定構造の水素添加ブロック共重合体をポリ
オレフィン系樹脂に混合することによりその目的が達成
されることを見出し、本発明を完成するに至った。[Means for Solving the Problems] The present inventors have made earnest studies on the correlation between the polymer structure of the hydrogenated product of the vinyl aromatic compound block-conjugated diene compound block copolymer and the physical properties of the polyolefin composition. As a result, in order to obtain a composition excellent in low-temperature impact strength, appearance characteristics and flow processability, it was found that the purpose can be achieved by mixing a hydrogenated block copolymer having a specific structure with a polyolefin resin. The present invention has been completed.
【０００７】即ち、本発明は、 （１）ポリオレフィン系樹脂 ９５〜５０重量部 （２）（ａ）少なくとも２個のビニル芳香族化合物を主
体とする重合体ブロックＡと少なくとも１個の共役ジエ
ン化合物を主体とする重合体ブロックＢを有し、その共
役ジエン部分の８０％以上が水素添加され、水添前のビ
ニル結合量が４０〜６０％である水素添加ブロック共重
合体 （ｂ）少なくとも１個のビニル芳香族化合物を主体とす
る重合体ブロックＣと少なくとも１個の共役ジエン化合
物を主体とする重合体ブロックＤを有し、その共役ジエ
ン部分の８０％以上が水素添加され、水添前のビニル結
合量が４０〜６０％である（ａ）よりも低分子量の水素
添加ブロック共重合体からなり （ａ）と（ｂ）の重量％の割合が４０／６０〜９０／１
０ （ａ）と（ｂ）との数平均分子量（ＭN ）の算術平均が
４０，０００〜２００，０００ （ａ）と（ｂ）の分子量比（（ａ）のＭN ／（ｂ）のＭ
N ）が１．１〜４．５である水素添加ブロック共重合体
５〜５０重量部 よりなるポリオレフィン組成物である。That is, the present invention comprises: (1) 95 to 50 parts by weight of a polyolefin resin (2) (a) A polymer block A mainly composed of at least two vinyl aromatic compounds and at least one conjugated diene compound. A hydrogenated block copolymer having a polymer block B mainly composed of 80% or more of a conjugated diene portion thereof being hydrogenated and having a vinyl bond content of 40 to 60% before hydrogenation (b) at least 1 Of a vinyl aromatic compound-based polymer block C and at least one conjugated diene compound-based polymer block D, 80% or more of the conjugated diene portion being hydrogenated and before hydrogenation Of a hydrogenated block copolymer having a lower molecular weight than that of (a) having a vinyl bond content of 40 to 60%, and the ratio by weight of (a) and (b) is 40/60 to 90/1.
0 The arithmetic average of the number average molecular weight (M N ) of (a) and (b) is 40,000 to 200,000 (a) and the molecular weight ratio of (b) (of M N / (b) of (a)) M
A polyolefin composition comprising 5 to 50 parts by weight of a hydrogenated block copolymer having N ) of 1.1 to 4.5.
【０００８】本発明の組成物の（２）成分である水素添
加ブロック共重合体は高分子量ブロック共重合体（ａ）
と低分子量ブロック共重合体（ｂ）の構造、ビニル芳香
族化合物量や水添前のビニル結合量等のミクロ構造は、
同一であってもよいし、異なるものであっても、前記の
範囲内であれば、かまわない。ビニル芳香族化合物を主
体とする重合体ブロックＡ又はＣは、ビニル芳香族化合
物と共役ジエン化合物との重量比が１００／０〜５１／
４９、好ましくは１００／０〜７０／３０の組成範囲か
らなる重合体ブロックであり、ビニル芳香族化合物と共
役ジエン化合物が共重合した場合、このブロックにおけ
る共役ジエン化合物の分布は、ランダム、テーパー（分
子鎖に沿ってモノマー成分が増加または減少するも
の）、一部ブロック状またはこれらの任意の組合せのい
ずれでもあってよい。The hydrogenated block copolymer which is the component (2) of the composition of the present invention is a high molecular weight block copolymer (a).
And the structure of the low molecular weight block copolymer (b), the microstructure such as the amount of vinyl aromatic compound and the amount of vinyl bond before hydrogenation,
It may be the same or different, as long as it is within the above range. In the polymer block A or C mainly containing a vinyl aromatic compound, the weight ratio of the vinyl aromatic compound and the conjugated diene compound is 100/0 to 51 /
It is a polymer block having a composition range of 49, preferably 100/0 to 70/30. When a vinyl aromatic compound and a conjugated diene compound are copolymerized, the distribution of the conjugated diene compound in this block is random or tapered ( Increase or decrease in the monomer component along the molecular chain), partially block-like, or any combination thereof.
【０００９】また、共役ジエン化合物を主体とする重合
体ブロックＢ又はＤは、ビニル芳香族化合物と共役ジエ
ン化合物との重量比が０／１００〜４９／５１、好まし
くは０／１００〜３０／７０の組成範囲からなる重合体
ブロックであり、共役ジエン化合物とビニル芳香族化合
物が共重合した場合、このブロックにおけるビニル芳香
族化合物の分布は、ランダム、テーパー（分子鎖に沿っ
てモノマー成分が増加または減少するもの）、一部ブロ
ック状またはこれらの任意の組合せのいずれであっても
よい。ここで供するビニル芳香族化合物としては、スチ
レン、α−メチルスチレン、ｐ−メチルスチレンやｐ−
ターシャリブチルスチレン等のアルキルスチレン、パラ
メトキシスチレン、ビニルナフタレン等のうちから１種
または２種以上が選ばれ、中でもスチレン、ｐ−メチル
スチレンが特に好ましい。また共役ジエン化合物として
は、ブタジエン、イソプレン、ピペリレン、メチルペン
タジエン、フェニルブタジエン、３，４−ジメチル−
１，３−ヘキサジエン、４，５−ジエチル−１，３−オ
クタジエン等のうちから１種または２種以上が選ばれ、
中でもブタジエンおよび／またはイソプレンが特に好ま
しい。In the polymer block B or D mainly composed of the conjugated diene compound, the weight ratio of the vinyl aromatic compound to the conjugated diene compound is 0/100 to 49/51, preferably 0/100 to 30/70. When the conjugated diene compound and the vinyl aromatic compound are copolymerized, the distribution of the vinyl aromatic compound in this block is random or tapered (the monomer component increases along the molecular chain or Decrease), partial block, or any combination thereof. Examples of the vinyl aromatic compound provided here include styrene, α-methylstyrene, p-methylstyrene and p-
One or two or more types are selected from alkyl styrenes such as tertiary butyl styrene and the like, paramethoxy styrene, vinyl naphthalene and the like, and among them, styrene and p-methyl styrene are particularly preferable. Further, as the conjugated diene compound, butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-
One or more selected from 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, etc.,
Of these, butadiene and / or isoprene are particularly preferable.
【００１０】ビニル芳香族化合物の含有量は、１０〜５
０重量％の範囲が好ましく、１０〜３０重量％の範囲が
更に好ましい。ビニル芳香族化合物の含有量が５０重量
％を越える場合は、ポリオレフィン組成物の耐衝撃性の
改良が得られないことがあり、また１０重量％未満の場
合は、剛性の低下が著しくなる傾向となる。共役ジエン
部分のミクロ構造は、水添前のビニル結合量が４０〜６
０％である必要があり、さらに、４５〜５５％の範囲内
にあるのが特に好ましい。ここに、ビニル結合量とは、
ブロック共重合体中に１，２−結合、３，４−結合及び
１，４−結合の結合様式で組込まれている共役ジエン化
合物のうち、１，２−結合及び３，４−結合で組込まれ
ているものの割合とする。ビニル結合量が４０％未満で
あると、ポリオレフィン組成物にした際、低温における
衝撃強度と流動加工性の改良が不十分であり、またそれ
が６０％を越えると、再び、低温における衝撃強度が低
下してくる。共役ジエン部分のミクロ構造は、核磁気共
鳴装置（ＮＭＲ）により分析できる。The content of vinyl aromatic compound is 10 to 5
The range of 0% by weight is preferable, and the range of 10 to 30% by weight is more preferable. When the content of the vinyl aromatic compound exceeds 50% by weight, the impact resistance of the polyolefin composition may not be improved, and when it is less than 10% by weight, the rigidity tends to be remarkably lowered. Become. The microstructure of the conjugated diene portion has a vinyl bond content of 40 to 6 before hydrogenation.
It must be 0%, and particularly preferably in the range of 45 to 55%. Here, the vinyl bond content is
Of the conjugated diene compounds incorporated in the block copolymer in the form of 1,2-bonds, 3,4-bonds, and 1,4-bonds, 1,2-bonds and 3,4-bonds are incorporated. Percentage of items that are listed. If the vinyl bond content is less than 40%, the impact strength at low temperature and the flow processability will not be sufficiently improved when the composition is made into a polyolefin, and if it exceeds 60%, the impact strength at low temperature will be low again. It is decreasing. The microstructure of the conjugated diene moiety can be analyzed by nuclear magnetic resonance (NMR).
【００１１】本発明の水素添加ブロック共重合体は、
（ａ）と（ｂ）とからなる水素添加ブロック共重合体
で、（ｂ）成分が（ａ）成分よりも低分子量であり、
（ａ）／（ｂ）の割合が４０／６０〜９０／１０（重量
％）であることが必要である。そして、（ａ）と（ｂ）
の数平均分子量の算術平均が４０，０００〜２００，０
００の範囲である。また、（ａ）と（ｂ）との数平均分
子量の比（（ａ）のＭN ／（ｂ）のＭN ）は１．１〜
４．５の範囲であり、好ましくは、１，２〜２．２であ
る。The hydrogenated block copolymer of the present invention is
A hydrogenated block copolymer comprising (a) and (b), wherein the component (b) has a lower molecular weight than the component (a),
It is necessary that the ratio of (a) / (b) is 40/60 to 90/10 (% by weight). And (a) and (b)
Number average molecular weight of 40,000-200,0
The range is 00. Further, (a) the ratio of the number average molecular weight of (b) ((M N / (b) of the M N of a)) is 1.1 to
It is in the range of 4.5, preferably 1, 2 to 2.2.
【００１２】（ａ）と（ｂ）の個々の数平均分子量は、
ゲルパーミュエーションクロマトグラフィー（ＧＰＣ）
で常法により測定できる。その製法は、例えば、別々に
（ａ）の水素添加ブロック共重合体と（ｂ）の水素添加
ブロック共重合体を製造し、ブレンドしてもよい。ま
た、低分子量のブロック共重合体をカップリング反応さ
せ、カップリング率を上記範囲にコントロールして、そ
の後水素添加して製造してもかまわない。ポリオレフィ
ン組成物にした場合、（ａ）の割合が４０重量％未満で
あると、耐衝撃性が不足したものとなり、９０重量％以
上になると流動加工性が低下すると同時に、低温時の面
衝撃強度が劣ってしまう。また、数平均分子量の平均が
４０，０００未満であると、耐衝撃性も含め、引張強度
等の機械的強度が低いものとなり、２００，０００を越
えると、流動加工性が著しく低下し、さらに外観特性が
劣ったものになってしまう。The individual number average molecular weights of (a) and (b) are
Gel permeation chromatography (GPC)
Can be measured by a conventional method. In the production method, for example, the hydrogenated block copolymer of (a) and the hydrogenated block copolymer of (b) may be separately produced and blended. Further, it may be produced by subjecting a low-molecular weight block copolymer to a coupling reaction, controlling the coupling rate within the above range, and then hydrogenating. In the case of a polyolefin composition, if the proportion of (a) is less than 40% by weight, the impact resistance becomes insufficient, and if it exceeds 90% by weight, the flow processability deteriorates and at the same time, the surface impact strength at low temperature. Is inferior. Further, when the average number average molecular weight is less than 40,000, mechanical strength such as tensile strength including impact resistance becomes low, and when it exceeds 200,000, flow processability is remarkably lowered, and further, The appearance characteristics will be inferior.
【００１３】また、上記ブロック共重合体の分子構造
は、直鎖状、分岐状、放射状またはこれらの組合わせな
どいずれでもよい。そして、ビニル芳香族化合物を主体
とする重合体ブロックあるいは共役ジエンを主体とする
ブロックのそれぞれは、同一の構造であってもよいし、
モノマー成分含有量、それらの分子鎖における分布、ブ
ロックの分子量、ミクロ構造などの各構造が異なるもの
であってもよい。The molecular structure of the block copolymer may be linear, branched, radial, or a combination thereof. Then, each of the polymer block mainly composed of a vinyl aromatic compound or the block mainly composed of a conjugated diene may have the same structure,
The respective structures such as the content of the monomer component, the distribution in their molecular chains, the molecular weight of the block, and the microstructure may be different.
【００１４】ブロック共重合体の製造法としては、例え
ば特公昭３６−１９２８６号公報、特公昭４３−１４９
７９号公報、特公昭４９−３６９５７号公報などに記載
された方法が挙げられる。これらは、炭化水素溶剤中で
アニオン重合開始剤として有機リチウム化合物等を用
い、ビニル化剤としてジエチルエーテル、テトラヒドロ
フランの如きエーテル化合物、トリエチルアミン、Ｎ，
Ｎ，Ｎ′，Ｎ′−テトラメチルエチレンジアミンの如き
第３級アミン、必要に応じカップリング剤としてエポキ
シ化ダイズ油、四塩化ケイ素の如き多官能性化合物を用
い、ビニル芳香族化合物と共役ジエン化合物をブロック
共重合する方法であり、直鎖状、分岐状あるいは放射状
の構造を有するブロック共重合体として得られる。本発
明においては、いかなる重合法で得られたものであって
も、上記のものであれば使用可能である。The block copolymer can be produced by, for example, JP-B-36-19286 and JP-B-43-149.
79, Japanese Patent Publication No. 49-36957 and the like. In these, an organic lithium compound or the like is used as an anionic polymerization initiator in a hydrocarbon solvent, an ether compound such as diethyl ether or tetrahydrofuran as a vinylating agent, triethylamine, N,
Tertiary amines such as N, N ', N'-tetramethylethylenediamine, epoxidized soybean oil as a coupling agent, and polyfunctional compounds such as silicon tetrachloride are used as needed, and vinyl aromatic compounds and conjugated diene compounds are used. Is a block copolymer and is obtained as a block copolymer having a linear, branched or radial structure. In the present invention, any polymer obtained by any polymerization method can be used as long as it is as described above.
【００１５】上記のブロック共重合体を、公知の方法、
例えば、特公昭４２−８７０４号公報に記載の方法で水
添することにより水添ブロック共重合体は得られる。本
発明は、共役ジエン部分の８０％以上を水素添加させる
必要がある。水素添加の割合が低いと、ポリオレフィン
系樹脂との相溶性が不十分で耐衝撃性が低いものとな
り、また、混合、成形時の熱劣化を受けやすく好ましく
ない。水素添加率は、核磁気共鳴装置（ＮＭＲ）を用い
た機器分析により分析できる。The above block copolymer is prepared by a known method,
For example, a hydrogenated block copolymer can be obtained by hydrogenating according to the method described in JP-B-42-8704. The present invention requires 80% or more of the conjugated diene moieties to be hydrogenated. When the proportion of hydrogenation is low, the compatibility with the polyolefin resin is insufficient and the impact resistance is low, and it is not preferable because it is susceptible to thermal deterioration during mixing and molding. The hydrogenation rate can be analyzed by instrumental analysis using a nuclear magnetic resonance apparatus (NMR).
【００１６】本発明で用いる水素添加ブロック共重合体
は、不飽和カルボン酸またはその誘導体との付加反応に
より変性させ、官能基を含有したものでもかまわない。
変性した水素添加ブロック共重合体は、塗装を必要とす
る場合に有利である。本発明の組成物の（１）成分であ
るポリオレフィン系樹脂は、α−オレフィン、例えば、
エチレン、プロピレン、１−ブテン、イソブチレン、４
−メチル−１−ペンテン等を重合して得られる樹脂であ
ればいずれでもよいが、なかでも、ポリエチレン、ポリ
プロピレン、ポリブテン、ポリメチルペンテン、エチレ
ン−プロピレンブロック共重合体またはこれらの混合物
が挙げられる。特に好ましいのは、ポリプロピレンであ
る。The hydrogenated block copolymer used in the present invention may be modified by an addition reaction with an unsaturated carboxylic acid or a derivative thereof to contain a functional group.
Modified hydrogenated block copolymers are advantageous when painting is required. The polyolefin resin which is the component (1) of the composition of the present invention is an α-olefin, for example,
Ethylene, propylene, 1-butene, isobutylene, 4
Any resin may be used as long as it is a resin obtained by polymerizing -methyl-1-pentene and the like. Among them, polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene block copolymer or a mixture thereof can be mentioned. Especially preferred is polypropylene.
【００１７】本発明のポリオレフィン組成物において、
その組成は、（１）成分のポリオレフィン系樹脂が９５
〜５０重量部、（２）成分の水素添加ブロックの共重合
体が５〜５０重量部、好ましくは１０〜３０重量部であ
る。（（２）成分は、（ａ）の水素添加ブロック共重合
体と（ａ）よりも低分子量の水素添加ブロック共重合体
とからなり、その割合は４０／６０〜９０／１０であ
る。）水素添加ブロック共重合体の割合が５重量部未満
の場合には、耐衝撃性、特に低温時における耐衝撃性の
改善効果がそれほど顕著でなく、また、５０重量部を越
えると、剛性等が低い成形材料となってしまい、実用的
でなくなる。In the polyolefin composition of the present invention,
The composition of the (1) component polyolefin resin is 95
˜50 parts by weight, 5 to 50 parts by weight, preferably 10 to 30 parts by weight of the copolymer of the hydrogenated block of the component (2). (The component (2) is composed of the hydrogenated block copolymer of (a) and a hydrogenated block copolymer having a lower molecular weight than that of (a), and the ratio thereof is 40/60 to 90/10.) If the proportion of the hydrogenated block copolymer is less than 5 parts by weight, the effect of improving impact resistance, especially at low temperature, is not so remarkable, and if it exceeds 50 parts by weight, the rigidity and the like are not improved. It becomes a low molding material and becomes impractical.
【００１８】本発明の組成物は、その各成分の組成比に
応じて通常の高分子物質の混合に供される装置によって
調製できる。それら混合装置としては、例えば、押出
機、ミキシングロール、ニーダー等があげられ、特に、
本発明では押出機による溶融混合法が好ましい。また、
本発明のポリオレフィン組成物には、その性質を損わな
い程度に、炭酸カルシウム、タルク、シリカ、カーボン
ブラック、ガラス繊維、クレーなどの補強剤ないしは充
填剤を添加することも可能である。また、その他の添加
剤、例えば、熱安定剤、酸化防止剤、紫外線吸収剤、着
色剤、顔料などを添加してもよく、更に本発明の組成物
に発泡剤を加えて発泡体とすることも可能である。The composition of the present invention can be prepared by an apparatus which is usually used for mixing polymer substances depending on the composition ratio of each component. Examples of the mixing device include an extruder, a mixing roll, a kneader, and the like.
In the present invention, the melt mixing method using an extruder is preferable. Also,
To the polyolefin composition of the present invention, it is possible to add a reinforcing agent or a filler such as calcium carbonate, talc, silica, carbon black, glass fiber or clay to the extent that the properties are not impaired. Further, other additives such as a heat stabilizer, an antioxidant, an ultraviolet absorber, a colorant and a pigment may be added, and a foaming agent is further added to the composition of the present invention to form a foam. Is also possible.
【００１９】本発明は、ポリオレフィン系樹脂と特定構
造の水素添加ブロック共重合体からなる組成物であり、
衝撃強度、特に低温時における耐衝撃性、流動加工性、
外観特性に優れている。本発明のポリオレフィン組成物
は、従来からの各種の成形法、例えば射出成形、押出成
形等により成形が可能であり、成形品、シート等、各種
分野において広い利用範囲があり、有用である。The present invention is a composition comprising a polyolefin resin and a hydrogenated block copolymer having a specific structure,
Impact strength, especially impact resistance at low temperature, flow processability,
Excellent appearance characteristics. The polyolefin composition of the present invention can be molded by various conventional molding methods such as injection molding and extrusion molding, and is useful in a wide range of applications in various fields such as molded articles and sheets.
【００２０】本発明の組成物は、安価であり、かつ上記
の通常の成形法で製品が得られ、日用部品、包装材料か
ら自動車内外装品等の自動車部品まで広範囲に利用でき
るものであり、産業上の利用価値は極めて大きい。The composition of the present invention is inexpensive, and a product can be obtained by the above-mentioned ordinary molding method, and can be widely used from daily parts and packaging materials to automobile parts such as automobile interior and exterior parts. , Its industrial utility value is extremely high.
【００２１】[0021]
【実施例】本発明をより具体的かつ詳細に説明するため
に、次に実施例を示すが、本発明はこれらの例によって
何ら限定されるものではない。尚、実施例及び比較例に
示した物性の測定規格、試験法は以下の通りである。 耐衝撃性（低温） 組成物を射出成形により厚さ３ｍｍ、２０ｃｍ×２０ｃ
ｍのシートを成形し、−３０℃の状態でホルダーに固定
し、これに重さ１３．７ｋｇのミサイル型の重りを１．
５ｍの高さより落下（５．４ｍ／ｓｅｃ）させ、シート
が脆性破壊するか延性破壊するかを確認した。EXAMPLES In order to describe the present invention more specifically and in detail, the following examples are shown, but the present invention is not limited to these examples. The measurement standards and test methods for physical properties shown in Examples and Comparative Examples are as follows. Impact resistance (low temperature) The composition is injection molded to have a thickness of 3 mm, 20 cm x 20 c.
m sheet was molded and fixed to a holder at −30 ° C., and a 13.7 kg missile type weight was added to the holder.
It was dropped from a height of 5 m (5.4 m / sec), and it was confirmed whether the sheet was brittle fracture or ductile fracture.
【００２２】 流動性（ＭＦＲ） ＪＩＳ Ｋ７２１０ に従って測定。 （２３０℃、
２．１６ｋｇ荷重） 表面光沢 ＪＩＳ Ｋ７１０５ に従って測定。 （入射角：６０
゜） 曲げ弾性率 ＪＩＳ Ｋ７２０３ に従って測定。 （Ｉ）水素添加ブロック共重合体の調整 （１）ｎ−ブチルリチウムを重合触媒とし、シクロヘキ
サン溶中で、テトラヒドロフランをビニル含有量調節剤
として、スチレンとブタジエンをアニオンブロック共重
合することにより、表１，２に示したようなブロック共
重合体を合成した。尚、ポリマー構造は、モノマーの仕
込み、分子量は、触媒量、ビニル含量はビニル含量調節
剤剤を変化させることによりコントロールした。また、
ｃ−１は、重合終了後、カップリング剤としてジグリシ
ジルアニリンを、ｃ−２、ｃ−５は、炭酸ジエチル、ｃ
−３、ｃ−４は、四塩化ケイ素を添加してさらにカップ
リング反応を行った。[0022] Flowability (MFR) Measured according to JIS K7210. (230 ℃,
2.16 kg load) Surface gloss Measured according to JIS K7105. (Incident angle: 60
°) Flexural modulus Measured according to JIS K7203. (I) Preparation of Hydrogenated Block Copolymer (1) By using n-butyllithium as a polymerization catalyst and cyclohexane in solution, tetrahydrofuran as a vinyl content modifier and styrene and butadiene as an anion block copolymer, The block copolymers shown in 1 and 2 were synthesized. The polymer structure was controlled by changing the charge of the monomer, the molecular weight of the catalyst, and the vinyl content of the vinyl content modifier. Also,
c-1 is diglycidyl aniline as a coupling agent after completion of the polymerization, c-2 and c-5 are diethyl carbonate, c
-3 and c-4 were subjected to a coupling reaction by adding silicon tetrachloride.
【００２３】スチレン含有量は、紫外分光光度計（Ｕ
Ｖ）を、ビニル含量は、核磁気共鳴装置（ＮＭＲ）を、
数平均分子量は、ゲルパーミュエーションクロマトグラ
フィーを用いて測定した。 （２）次に各ブロック共重合体をジ−ｐ−トリスビス
（１−シクロペンタジエニル）チタニウムとｎ−ブチル
リチウムを水添触媒として、水素圧５ｋｇ／ｃｍ2 、温
度５０℃で２時間水素添加を行った。各サンプルの水素
添加率（水添率）を表１の右欄に示した。ブタジエンブ
ロック部分の二重結合の９０％以上は水素添加され、ス
チレンブロック部分のベンゼン環はほとんど水添されな
いで残った。尚、ｃ−５は、ｃ−２と同じポリマーで、
水素添加反応を行なわなかったものである。The styrene content is measured by an ultraviolet spectrophotometer (U
V), vinyl content, nuclear magnetic resonance (NMR),
The number average molecular weight was measured using gel permeation chromatography. (2) Next, each block copolymer was hydrogenated at a hydrogen pressure of 5 kg / cm 2 and a temperature of 50 ° C. for 2 hours using di-p-trisbis (1-cyclopentadienyl) titanium and n-butyllithium as a hydrogenation catalyst. The addition was made. The hydrogenation rate (hydrogenation rate) of each sample is shown in the right column of Table 1. 90% or more of the double bonds in the butadiene block portion were hydrogenated, and the benzene ring in the styrene block portion remained almost unhydrogenated. Incidentally, c-5 is the same polymer as c-2,
The hydrogenation reaction was not performed.
【００２４】水素添加率は、核磁気共鳴装置（ＮＭＲ）
を用いて測定した。 (II)ポリプロピレン組成物の調整と物性測定 市販ポリプロピレン (旭化成（社）製 Ｍ８６１９ ＜
ＭＦＲ＝１４（ｇ／１０分）＞）に、得られた水素添加
ブロック共重合体を表３，４，５，６に示した割合で加
え、３０ｍｍの２軸押出機により２２０℃の温度で溶融
混練を行い、ペレット化した。The hydrogenation rate is measured by a nuclear magnetic resonance apparatus (NMR).
Was measured. (II) Preparation of polypropylene composition and measurement of physical properties Commercially available polypropylene (M8619 manufactured by Asahi Kasei Corporation)
MFR = 14 (g / 10 min)>), and the resulting hydrogenated block copolymer was added at a ratio shown in Tables 3, 4, 5 and 6 at a temperature of 220 ° C. using a twin screw extruder of 30 mm. Melt-kneading was performed and pelletized.
【００２５】得られたペレットを２３０℃で射出成形
し、シートとテストピース（タンザク片）を作成し、低
温（−３０℃）での耐衝撃性、表面光沢、曲げ弾性率等
の物性を測定した。以下の実施例１〜９の結果を表３，
４に示した。The pellets thus obtained are injection-molded at 230 ° C. to prepare a sheet and a test piece (tanzaku piece), and the physical properties such as impact resistance at low temperature (−30 ° C.), surface gloss and flexural modulus are measured. did. The results of Examples 1 to 9 below are shown in Table 3.
Shown in FIG.
【００２６】[0026]
【実施例１】水素添加ブロック共重合体（ａ−１）とジ
ブロック構造の低分子量水素添加ブロック共重合体（ｂ
−１）を５０／５０にブレンドしたもの１０重量部と９
０重量部のポリプロピレン（Ｍ８６１９）との組成物の
物性を測定した。低温における耐衝撃性が優れ、かつ流
動性と外観特性も優れたものであった。Example 1 Hydrogenated block copolymer (a-1) and low molecular weight hydrogenated block copolymer (b) having a diblock structure
-1) 50/50 blended 10 parts by weight and 9
The physical properties of the composition with 0 part by weight of polypropylene (M8619) were measured. The impact resistance at low temperature was excellent, and the fluidity and appearance characteristics were also excellent.
【００２７】[0027]
【実施例２】実施例１で、（ｂ−１）に代えてトリブロ
ック構造の低分子量水素添加ブロック共重合体（ｂ−
２）を用いた例である。Example 2 In Example 1, instead of (b-1), a low molecular weight hydrogenated block copolymer having a triblock structure (b-
This is an example using 2).
【００２８】[0028]
【実施例３】実施例１で、（ａ−１）を代えて水素添加
ブロック共重合体（ａ−２）を用い、ブレンド比率を５
５／４５にした例である。Example 3 In Example 1, the hydrogenated block copolymer (a-2) was used in place of (a-1), and the blend ratio was 5
This is an example of 5/45.
【００２９】[0029]
【実施例４】実施例３で、（ａ）／（ｂ）の比率を７５
／２５にした例である。Fourth Embodiment In the third embodiment, the ratio of (a) / (b) is set to 75.
/ 25 is an example.
【００３０】[0030]
【実施例５】実施例３で、水素添加ブロック共重合体の
配合を２０重量部にした例である。Example 5 This is an example of Example 3 in which the hydrogenated block copolymer was blended in an amount of 20 parts by weight.
【００３１】[0031]
【実施例６】実施例２で、（ａ−１）に代えて（ａ−
３）を用いた例である。Sixth Embodiment Instead of (a-1) in the second embodiment, (a-
This is an example using 3).
【００３２】[0032]
【実施例７】２官能のカップリング剤を用い、カップリ
ング率が７５％の水素添加ブロック共重合体（ｃ−１）
＜２５％のジブロック構造の低分子量水素添加ブロック
共重合体／７５％のトリブロック構造の水素添加ブロッ
ク共重合体＞１０重量部と９０重量部のポリプロピレン
の組成物の物性を測定した例である。Example 7 Hydrogenated block copolymer (c-1) having a coupling ratio of 75% using a bifunctional coupling agent.
<25% low molecular weight hydrogenated block copolymer having a diblock structure / 75% hydrogenated block copolymer having a triblock structure> In an example of measuring physical properties of a composition of 10 parts by weight and 90 parts by weight of polypropylene. is there.
【００３３】[0033]
【実施例８】実施例６で、３官能のカップリング剤を用
い、カップリング率が７２％の水素添加ブロック共重合
体（ｃ−２）＜２８％のジブロック構造の低分子量水素
添加ブロック共重合体／７２％の分岐構造の水素添加ブ
ロック共重合体＞を（ｃ−１）に代えて用いた。[Example 8] A hydrogenated block copolymer (c-2) having a coupling rate of 72% and a low molecular weight hydrogenated block having a diblock structure with a coupling ratio of 72% in Example 6 was used. Copolymer / hydrogenated block copolymer having a branched structure of 72%> was used instead of (c-1).
【００３４】[0034]
【実施例９】実施例６で、４官能のカップリング剤を用
い、カップリング率が６５％の水素添加ブロック共重合
体（ｃ−３）＜３５％のジブロック構造の低分子量水素
添加ブロック共重合体／６５％のラジアル構造の水素添
加ブロック共重合体＞を（ｃ−１）に替えて用いた。Example 9 A hydrogenated block copolymer (c-3) having a coupling ratio of 65% and a low molecular weight hydrogenated block having a diblock structure with a coupling ratio of 65% in Example 6 was used. Copolymer / hydrogenated block copolymer having a radial structure of 65%> was used instead of (c-1).
【００３５】これらの実施例は、全て本発明の構成に含
まれる組成物であり、低温における耐衝撃性と外観特性
に優れ、かつ流動加工性に優れたものである。その特性
のすばらしさは、以下の比較例と比較することにより、
一層深いものとなる。以下の比較例１〜８の結果を表
５，６に示した。All of these examples are compositions included in the constitution of the present invention, and are excellent in impact resistance at low temperature and appearance characteristics, and excellent in flow processability. The splendor of its characteristics, by comparing with the following comparative examples,
It will be deeper. The results of Comparative Examples 1 to 8 below are shown in Tables 5 and 6.
【００３６】[0036]
【比較例１】ポリプロピレン単独の評価であり、低温で
の耐衝撃性が著しく低いものである。[Comparative Example 1] This is an evaluation of polypropylene alone, and the impact resistance at low temperature is extremely low.
【００３７】[0037]
【比較例２】通常の単一のトリブロック構造の水素添加
ブロック共重合体（ａ−４）１０重量部と９０重量部の
ポリプロピレンとの組成物の物性を測定した。低温での
耐衝撃性が劣り、流動性も低いものである。Comparative Example 2 The physical properties of a composition of 10 parts by weight of an ordinary hydrogenated block copolymer (a-4) having a single triblock structure and 90 parts by weight of polypropylene were measured. It has poor impact resistance at low temperatures and low fluidity.
【００３８】[0038]
【比較例３】比較例２の水素添加ブロック共重合体を
（ａ−４）／（ｂ−３）＝７５／２５にブレンドしたも
のに代え、耐衝撃性、流動性共に改善されてきている
が、満足できるものではない。これは、水素添加ブロッ
ク共重合体のビニル量が低いことに起因しているものと
考えられる。[Comparative Example 3] The hydrogenated block copolymer of Comparative Example 2 was replaced with a blend of (a-4) / (b-3) = 75/25, and both impact resistance and fluidity have been improved. However, I am not satisfied. This is considered to be due to the low vinyl content of the hydrogenated block copolymer.
【００３９】[0039]
【比較例４】高ビニルの水素添加ブロック共重合体とポ
リプロピレンの組成物であるが、低温時の耐衝撃性と外
観特性、流動性共に劣ったものである。Comparative Example 4 A composition of a high vinyl hydrogenated block copolymer and polypropylene, which is inferior in impact resistance at low temperature, appearance characteristics and fluidity.
【００４０】[0040]
【比較例５】比較例４の水素添加ブロック共重合体３０
重量％に対し、本発明の実施例で用いた低分子量の水素
添加ブロック共重合体７０重量％をブレンドしたブロッ
ク共重合体とポリプロピレンの組成物であるが、実施例
３，４に比べ低分子量の水素添加ブロック共重合体の比
率が多いために、低温時の耐衝撃性が著しく劣ったもの
である。Comparative Example 5 Hydrogenated block copolymer 30 of Comparative Example 4
A composition of polypropylene and a block copolymer obtained by blending 70% by weight of the low molecular weight hydrogenated block copolymer used in the examples of the present invention with respect to% by weight, but having a lower molecular weight than Examples 3 and 4. The impact resistance at low temperature is remarkably inferior due to the large proportion of the hydrogenated block copolymer.
【００４１】[0041]
【比較例６】カップリングタイプの水素添加ブロック共
重合体を用いたが、平均分子量が高過ぎるため、流動性
と外観特性が低下しているが、さらに耐衝撃性も低下し
てしまった。[Comparative Example 6] A coupling type hydrogenated block copolymer was used, but since the average molecular weight was too high, the flowability and the appearance properties were degraded, but the impact resistance was also reduced.
【００４２】[0042]
【比較例７】本発明の実施例３と同じ水素添加ブロック
共重合体を用いたが、ブロック共重合の比率が多いため
に、曲げ弾性率が著しく低下し、実用的でない。Comparative Example 7 The same hydrogenated block copolymer as that used in Example 3 of the present invention was used, but the flexural modulus was remarkably lowered due to a large block copolymerization ratio, which was not practical.
【００４３】[0043]
【比較例８】本発明の実施例７と同じベースポリマー
で、水素添加していないブロック共重合（ｃ−５）を用
いたが、低温時の耐衝撃性が劣ったものであった。Comparative Example 8 The same base polymer as in Example 7 of the present invention was used, but the block copolymer (c-5) not hydrogenated was used, but the impact resistance at low temperature was poor.
【００４４】[0044]
【表１】 [Table 1]
【００４５】[0045]
【表２】 [Table 2]
【００４６】[0046]
【表３】 [Table 3]
【００４７】[0047]
【表４】 [Table 4]
【００４８】[0048]
【表５】 [Table 5]
【００４９】[0049]
【表６】 [Table 6]
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年２月２６日[Submission date] February 26, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４６[Correction target item name] 0046
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４６】[0046]
【表３】 [Table 3]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００４９[Correction target item name] 0049
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００４９】[0049]
【表６】 [Table 6]
【発明の効果】本発明の組成物は、衝撃強度、特に低温
時における耐衝撃性、流動加工性、外観特性に優れ、日
用部品から自動車部品等に利用できる成形材料である。INDUSTRIAL APPLICABILITY The composition of the present invention is a molding material which is excellent in impact strength, particularly impact resistance at low temperature, flow processability, and appearance characteristics, and can be used for daily parts, automobile parts and the like.
Claims (1)
５０重量部 （２） （ａ）少なくとも２個のビニル芳香族化合物を
主体とする重合体ブロックＡと少なくとも１個の共役ジ
エン化合物を主体とする重合体ブロックＢを有し、その
共役ジエン部分の８０％以上が水素添加され、水添前の
ビニル結合量が４０〜６０％である水素添加ブロック共
重合体と （ｂ）少なくとも１個のビニル芳香族化合物を主体とす
る重合体ブロックＣと少なくとも１個の共役ジエン化合
物を主体とする重合体ブロックＤを有し、その共役ジエ
ン部分の８０％以上が水素添加され、水添前のビニル結
合量が４０〜６０％であり、（ａ）よりも低分子量の水
素添加ブロック重合体とからなり （ａ）と（ｂ）の重量％の割合が４０／６０〜９０／１
０ （ａ）と（ｂ）との数平均分子量（ＭN ) の算術平均が
４０，０００〜２００，０００ （ａ）と（ｂ）の分子量比（（ａ）のＭN ／（ｂ）のＭ
N ）が１．１〜４．５ である水素添加ブロック共重合体 ５〜５０重量部 よりなるポリオレフィン組成物。(1) Polyolefin resin 95-
50 parts by weight (2) (a) having at least two vinyl aromatic compound-based polymer blocks A and at least one conjugated diene compound-based polymer block B 80% or more hydrogenated block copolymer having a hydrogen bond content before hydrogenation of 40 to 60%, and (b) at least one polymer block C mainly composed of a vinyl aromatic compound It has a polymer block D mainly composed of one conjugated diene compound, 80% or more of its conjugated diene portion is hydrogenated, and the vinyl bond amount before hydrogenation is 40 to 60%. Also comprises a low molecular weight hydrogenated block polymer, and the weight percentage of (a) and (b) is 40/60 to 90/1.
0 The arithmetic average of the number average molecular weight (M N ) of (a) and (b) is 40,000 to 200,000 (a) and the molecular weight ratio of (b) (of M N / (b) of (a)) M
A polyolefin composition comprising 5 to 50 parts by weight of a hydrogenated block copolymer having a N ) of 1.1 to 4.5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4023448A JP2513958B2 (en) | 1991-05-16 | 1992-02-10 | Polyolefin composition |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3-111850 | 1991-05-16 | ||
| JP11185091 | 1991-05-16 | ||
| JP4023448A JP2513958B2 (en) | 1991-05-16 | 1992-02-10 | Polyolefin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0551494A true JPH0551494A (en) | 1993-03-02 |
| JP2513958B2 JP2513958B2 (en) | 1996-07-10 |
Family
ID=26360803
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4023448A Expired - Lifetime JP2513958B2 (en) | 1991-05-16 | 1992-02-10 | Polyolefin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2513958B2 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05163388A (en) * | 1991-11-12 | 1993-06-29 | Asahi Chem Ind Co Ltd | Polyolefin resin composition excellent in impact resistance |
| US5492967A (en) * | 1993-11-03 | 1996-02-20 | Shell Oil Company | Impact modification of polypropylene with styrene/isoprene tetrablock copolymers |
| WO1996031567A1 (en) * | 1995-04-07 | 1996-10-10 | Mitsui Petrochemical Industries, Ltd. | Automobile steering wheel |
| USH1798H (en) * | 1994-12-22 | 1999-07-06 | Shell Oil Company | Soft compounds containing elastomeric metallocene polyolefins and styrenic block copolymers |
| WO2005005533A1 (en) * | 2003-07-10 | 2005-01-20 | Toyo Seikan Kaisha, Ltd. | Oxygen-absorbing resin composition |
| CN100424125C (en) * | 2003-07-10 | 2008-10-08 | 东洋制罐株式会社 | Oxygen-absorbing resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187442A (en) * | 1982-04-28 | 1983-11-01 | Asahi Chem Ind Co Ltd | Polyolefin polymeric composition |
| JPS6057463A (en) * | 1983-09-08 | 1985-04-03 | Sanyo Electric Co Ltd | Automatic addition system of computer for demand of insurance |
| JPH05163388A (en) * | 1991-11-12 | 1993-06-29 | Asahi Chem Ind Co Ltd | Polyolefin resin composition excellent in impact resistance |
-
1992
- 1992-02-10 JP JP4023448A patent/JP2513958B2/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58187442A (en) * | 1982-04-28 | 1983-11-01 | Asahi Chem Ind Co Ltd | Polyolefin polymeric composition |
| JPS6057463A (en) * | 1983-09-08 | 1985-04-03 | Sanyo Electric Co Ltd | Automatic addition system of computer for demand of insurance |
| JPH05163388A (en) * | 1991-11-12 | 1993-06-29 | Asahi Chem Ind Co Ltd | Polyolefin resin composition excellent in impact resistance |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05163388A (en) * | 1991-11-12 | 1993-06-29 | Asahi Chem Ind Co Ltd | Polyolefin resin composition excellent in impact resistance |
| US5492967A (en) * | 1993-11-03 | 1996-02-20 | Shell Oil Company | Impact modification of polypropylene with styrene/isoprene tetrablock copolymers |
| USH1798H (en) * | 1994-12-22 | 1999-07-06 | Shell Oil Company | Soft compounds containing elastomeric metallocene polyolefins and styrenic block copolymers |
| WO1996031567A1 (en) * | 1995-04-07 | 1996-10-10 | Mitsui Petrochemical Industries, Ltd. | Automobile steering wheel |
| US5901615A (en) * | 1995-04-07 | 1999-05-11 | Mitsui Chemicals, Inc. | Steering wheel for motor vehicles |
| WO2005005533A1 (en) * | 2003-07-10 | 2005-01-20 | Toyo Seikan Kaisha, Ltd. | Oxygen-absorbing resin composition |
| CN100424125C (en) * | 2003-07-10 | 2008-10-08 | 东洋制罐株式会社 | Oxygen-absorbing resin composition |
| US7709567B2 (en) | 2003-07-10 | 2010-05-04 | Toyo Seikan Kaisha, Ltd. | Oxygen-absorbing resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2513958B2 (en) | 1996-07-10 |
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