JP7391516B2 - Propylene polymer composition and method for producing the same - Google Patents
Propylene polymer composition and method for producing the same Download PDFInfo
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- JP7391516B2 JP7391516B2 JP2019017693A JP2019017693A JP7391516B2 JP 7391516 B2 JP7391516 B2 JP 7391516B2 JP 2019017693 A JP2019017693 A JP 2019017693A JP 2019017693 A JP2019017693 A JP 2019017693A JP 7391516 B2 JP7391516 B2 JP 7391516B2
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- propylene polymer
- propylene
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- 229920001155 polypropylene Polymers 0.000 title claims description 180
- 239000000203 mixture Substances 0.000 title claims description 109
- 238000004519 manufacturing process Methods 0.000 title claims description 35
- 238000006116 polymerization reaction Methods 0.000 claims description 55
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 51
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 51
- 150000001875 compounds Chemical class 0.000 claims description 22
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005227 gel permeation chromatography Methods 0.000 claims description 17
- 239000011949 solid catalyst Substances 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000004711 α-olefin Substances 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 8
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 7
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
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- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 5
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 3
- YYUODOUSPSBQCB-UHFFFAOYSA-N cyclohexyl-dimethoxy-(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(OC)C1CCCCC1 YYUODOUSPSBQCB-UHFFFAOYSA-N 0.000 claims description 2
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 claims description 2
- VHPUZTHRFWIGAW-UHFFFAOYSA-N dimethoxy-di(propan-2-yl)silane Chemical compound CO[Si](OC)(C(C)C)C(C)C VHPUZTHRFWIGAW-UHFFFAOYSA-N 0.000 claims description 2
- KOFGHHIZTRGVAF-UHFFFAOYSA-N n-ethyl-n-triethoxysilylethanamine Chemical compound CCO[Si](OCC)(OCC)N(CC)CC KOFGHHIZTRGVAF-UHFFFAOYSA-N 0.000 claims description 2
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
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- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
- XYGKGASSKJWLTN-UHFFFAOYSA-N CCCCCCC.CCCCCCC Chemical compound CCCCCCC.CCCCCCC XYGKGASSKJWLTN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 235000019399 azodicarbonamide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、プロピレン系重合体組成物、およびその製造方法に関する。 The present invention relates to a propylene polymer composition and a method for producing the same.
ポリプロピレン樹脂の重要な成形加工法の一つとして、発泡成形がある。押出発泡成形や射出発泡成形で得られた各種の成形体は、断熱性や遮音性、クッション性、エネルギー吸収特性などの優れた特性を生かし、幅広い用途で使用されている。発泡成形体の発泡倍率が高くなるほど、緩衝性、断熱性に優れ、連続気泡率が高いほど吸音性に優れることが一般に知られているため、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体が要望されている。 Foam molding is one of the important molding methods for polypropylene resin. Various molded bodies obtained by extrusion foam molding and injection foam molding are used in a wide range of applications due to their excellent properties such as heat insulation, sound insulation, cushioning properties, and energy absorption properties. It is generally known that the higher the expansion ratio of a foam molded product, the better the cushioning and heat insulation properties, and the higher the open cell ratio, the better the sound absorption property. Therefore, foam molding with a high expansion ratio and a high open cell ratio The body is in demand.
発泡成形性を改善するために樹脂を高溶融張力化するための手法として、多段重合により高分子量成分を付与する手法がある（特許文献１、２参照）。
特許文献１では、１３５℃、デカリン中における極限粘度[η]が８～１３ｄｌ／ｇの高分子量プロピレン系重合体を１５～５０質量％含有するポリプロピレン系樹脂組成物が開示されている。ここに示されている１３５℃、デカリン中における極限粘度[η]８～１３ｄｌ／ｇを、日刊工業新聞社「ポリプロピレン樹脂」に記載されている１３５℃デカリン中、及び１３５℃テトラリン中での極限粘度[η]と重量平均分子量の関係式を用い、ポリプロピレンの１３５℃、テトラリン中での極限粘度[η]に換算すると、５．８～９．５ｄｌ／ｇとなる。ポリプロピレン系樹脂組成物に含まれる高分子量プロピレン系重合体の極限粘度がかかる範囲のポリプロピレン系樹脂組成物は、この範囲では、高分子量プロピレン系重合体の極限粘度[η]が低いので、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体を得ることが困難である。
As a method for increasing the melt tension of a resin in order to improve foam moldability, there is a method of imparting a high molecular weight component through multistage polymerization (see Patent Documents 1 and 2).
Patent Document 1 discloses a polypropylene resin composition containing 15 to 50% by mass of a high molecular weight propylene polymer having an intrinsic viscosity [η] of 8 to 13 dl/g in decalin at 135°C. The intrinsic viscosity [η] 8 to 13 dl/g in decalin at 135°C shown here is the limit value in decalin at 135°C and in tetralin at 135°C described in Nikkan Kogyo Shimbun's "Polypropylene Resin". Using the relational expression between viscosity [η] and weight average molecular weight, when converted to the intrinsic viscosity [η] of polypropylene in tetralin at 135°C, it is 5.8 to 9.5 dl/g. A polypropylene resin composition in which the intrinsic viscosity of the high molecular weight propylene polymer contained in the polypropylene resin composition falls within this range has a low intrinsic viscosity [η] of the high molecular weight propylene polymer, so that high foaming is possible. It is difficult to obtain a foam molded product having a high magnification and a high open cell ratio.
また、特許文献２では１３５℃、テトラリン中における極限粘度[η]が１０ｄｌ／ｇ超の高分子量プロピレン系重合体を含有するポリプロピレン系樹脂組成物が開示されているが、当該高分子量プロピレン系重合体の含有量が５～２０質量％と少ないため、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体を得ることが困難である。 Further, Patent Document 2 discloses a polypropylene resin composition containing a high molecular weight propylene polymer having an intrinsic viscosity [η] of more than 10 dl/g in tetralin at 135°C. Since the content of the coalesce is as low as 5 to 20% by mass, it is difficult to obtain a foam molded product having a high expansion ratio and a high open cell ratio.
本発明は、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体を得るに好適なプロピレン系重合体組成物を得ることを目的とするものである。 The object of the present invention is to obtain a propylene polymer composition suitable for obtaining a foamed molded article having a high expansion ratio and a high open cell ratio.
本発明者らは、鋭意検討を重ねた結果、高分子量プロピレン系重合体の極限粘度[η]を適切に調整したプロピレン系重合体組成物を、その他のプロピレン系樹脂とブレンドすることで、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体が得られることを見出し、本発明を完成させた。 As a result of extensive studies, the present inventors have found that by blending a propylene polymer composition in which the intrinsic viscosity [η] of a high molecular weight propylene polymer is appropriately adjusted with other propylene resins, a high It was discovered that a foamed molded article having a high expansion ratio and a high open cell ratio can be obtained, and the present invention was completed.
すなわち、本発明は、１３５℃、テトラリン溶媒中で測定される極限粘度[η]が１０～１２ｄｌ／ｇの範囲にあるプロピレン系重合体（ａ１）を２０～５０質量％、および１３５℃、テトラリン中で測定される極限粘度[η]が０．５～３ｄｌ／ｇの範囲にあるプロピレン系重合体（ａ２）を５０～８０質量％〔但し、プロピレン系重合体（ａ１）とプロピレン系重合体（ａ２）の合計量を１００質量％とする。〕含むことを特徴とするプロピレン系重合体組成物に係る。 That is, the present invention provides 20 to 50% by mass of a propylene polymer (a1) having an intrinsic viscosity [η] of 10 to 12 dl/g measured in tetralin solvent at 135°C, and 50 to 80% by mass of a propylene polymer (a2) having an intrinsic viscosity [η] measured in the range of 0.5 to 3 dl/g [However, if the propylene polymer (a1) and the propylene polymer The total amount of (a2) is 100% by mass. ] It relates to a propylene-based polymer composition characterized by comprising.
本発明によれば、本発明に係わるプロピレン系重合体組成物を、例えば、プロピレン系重合体と混合することにより、高い発泡倍率、ならびに高い連続気泡率を有する発泡成形体を得ることができる。 According to the present invention, by mixing the propylene-based polymer composition according to the present invention with, for example, a propylene-based polymer, a foamed molded article having a high expansion ratio and a high open cell ratio can be obtained.
以下、本発明に係るプロピレン系重合体組成物およびそれを用いてなる成形体並びにその製造方法にについて具体的に記載する。
発泡成形における気泡成長過程は、（１）気泡核生成、（２）気泡成長、（３）破泡、（４）気泡安定化の４つの過程を経る。高い発泡倍率の発泡成形体を得るためには破泡を抑制することが重要である。一方、高い連続気泡率の発泡成形体を得るためには破泡を進行させることが重要である。プロピレン系重合体組成物に付与される高分子量成分の極限粘度[η]が大きいほど溶融張力が向上し破泡が抑制されるため、高い発泡倍率、ならびに高い連続気泡率の発泡成形体を得るためには、高分子量成分の極限粘度[η]を適切な値に調整する必要がある。
Hereinafter, the propylene polymer composition according to the present invention, a molded article using the same, and a method for producing the same will be specifically described.
The cell growth process in foam molding goes through four processes: (1) cell nucleation, (2) cell growth, (3) cell breaking, and (4) cell stabilization. In order to obtain a foam molded product with a high expansion ratio, it is important to suppress foam breakage. On the other hand, in order to obtain a foamed molded article with a high open cell ratio, it is important to advance the foaming process. The larger the intrinsic viscosity [η] of the high molecular weight component added to the propylene polymer composition, the higher the melt tension and the more suppressed bubble breakage, resulting in a foamed molded product with a high expansion ratio and a high open cell ratio. In order to achieve this, it is necessary to adjust the intrinsic viscosity [η] of the high molecular weight component to an appropriate value.
＜プロピレン系重合体組成物＞
本発明に係わるプロピレン系重合体組成物は、１３５℃、テトラリン溶媒中で測定される極限粘度[η]（以下、単に「極限粘度[η]」と呼称する場合がある。）が１０～１２ｄｌ／ｇの範囲にあるプロピレン系重合体（ａ１）を２０～５０質量％、１３５℃、テトラリン溶媒中で測定される極限粘度[η]（以下、単に「極限粘度[η]」と呼称する場合がある。）が０．５～３ｄｌ／ｇの範囲にあるプロピレン系重合体（ａ２）を５０～８０質量％を５０～８０質量％〔但し、プロピレン系重合体（ａ１）とプロピレン系重合体（ａ２）の合計量を１００質量％とする。〕含むことを特徴とするプロピレン系重合体組成物である。
<Propylene polymer composition>
The propylene polymer composition according to the present invention has an intrinsic viscosity [η] (hereinafter sometimes simply referred to as "intrinsic viscosity [η]") of 10 to 12 dl as measured in a tetralin solvent at 135°C. Propylene polymer (a1) in the range of 20 to 50% by mass, 135 ° C., intrinsic viscosity [η] measured in tetralin solvent (hereinafter simply referred to as "intrinsic viscosity [η]") 50 to 80% by mass of propylene polymer (a2) in the range of 0.5 to 3 dl/g [however, propylene polymer (a1) and propylene polymer The total amount of (a2) is 100% by mass. ] A propylene-based polymer composition characterized by comprising:
《プロピレン系重合体（ａ１）》
本発明に係わるプロピレン系重合体組成物に含まれるプロピレン系重合体（ａ１）の極限粘度[η]は、好ましくは１０．５～１１．５ｄｌ／ｇの範囲にある。また、プロピレン系重合体（ａ１）の質量分率は、好ましくは２０～４５質量％、より好ましくは２０～４０質量％の範囲にある。
<<Propylene polymer (a1)>>
The intrinsic viscosity [η] of the propylene polymer (a1) contained in the propylene polymer composition according to the present invention is preferably in the range of 10.5 to 11.5 dl/g. Further, the mass fraction of the propylene polymer (a1) is preferably in the range of 20 to 45% by mass, more preferably 20 to 40% by mass.
本発明に係わるプロピレン系重合体組成物において、プロピレン系重合体（Ａ）に含まれるプロピレン系重合体（ａ１）は、プロピレンの単独重合体、あるいは、プロピレンと炭素数２～８のα－オレフィンとの共重合体であってもよい。炭素数２～８のα－オレフィンとしては、例えばエチレン、１－ブテン、１－ヘキセン、１－オクテン、４－メチル－１－ペンテン等が挙げられる。これらα－オレフィンとしてはエチレンが好ましい。 In the propylene polymer composition according to the present invention, the propylene polymer (a1) contained in the propylene polymer (A) is a homopolymer of propylene, or a combination of propylene and an α-olefin having 2 to 8 carbon atoms. It may also be a copolymer with Examples of α-olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Ethylene is preferred as these α-olefins.
本発明に係わるプロピレン系重合体組成物に含まれるプロピレン系重合体（ａ１）の極限粘度[η]が上記範囲外の成分、例えば、極限粘度[η]が１２ｄｌ／ｇを超えると、得られる発泡成形体の連続気泡率が低くなる。また、極限粘度[η]が１０ｄｌ／ｇ未満のプロピレン系重合体含む場合は、得られる重合体組成物の溶融張力が不十分であり、得られる発泡成形体の発泡倍率が低くなる。また、プロピレン系重合体（ａ１）の質量分率が２０質量％未満では、溶融張力が不十分であるため発泡倍率が低くなり、５０質量％を超えると、得られる組成物を押出し成形する際にメルトフラクチャーの発生が激しく、押出成形時の不良現象の原因となる。 When the intrinsic viscosity [η] of the propylene polymer (a1) contained in the propylene polymer composition according to the present invention is outside the above range, for example, when the intrinsic viscosity [η] exceeds 12 dl/g, The open cell rate of the foamed molded product becomes low. Furthermore, if a propylene polymer having an intrinsic viscosity [η] of less than 10 dl/g is contained, the melt tension of the obtained polymer composition will be insufficient, and the expansion ratio of the obtained foam molded product will be low. Furthermore, if the mass fraction of the propylene polymer (a1) is less than 20% by mass, the melt tension will be insufficient and the expansion ratio will be low; if it exceeds 50% by mass, the resulting composition will be difficult to extrude. Melt fracture occurs frequently, causing defects during extrusion molding.
《プロピレン系重合体（ａ２）》
本発明に係わるプロピレン系重合体組成物に含まれるプロピレン系重合体（ａ２）の極限粘度[η]は、好ましくは０．６～２．５ｄｌ／ｇ、より好ましくは０．８～１．５ｄｌ／ｇの範囲にある。また、プロピレン系重合体（ａ２）の質量分率は、好ましくは５５～８０質量％、より好ましくは６０～８０質量％の範囲にある。
<<Propylene polymer (a2)>>
The intrinsic viscosity [η] of the propylene polymer (a2) contained in the propylene polymer composition according to the present invention is preferably 0.6 to 2.5 dl/g, more preferably 0.8 to 1.5 dl. /g range. Furthermore, the mass fraction of the propylene polymer (a2) is preferably in the range of 55 to 80% by mass, more preferably 60 to 80% by mass.
本発明に係わるプロピレン系重合体組成物において、プロピレン系重合体組成物に含まれるプロピレン系重合体（ａ２）は、プロピレンの単独重合体、あるいは、プロピレンと炭素数２～８のα－オレフィンとの共重合体であってもよい。炭素数２～８のα－オレフィンとしては、例えばエチレン、１－ブテン、１－ヘキセン、１－オクテン、４－メチル－１－ペンテン等が挙げられる。これらα－オレフィンとしてはエチレンが好ましい。 In the propylene polymer composition according to the present invention, the propylene polymer (a2) contained in the propylene polymer composition is a propylene homopolymer, or a mixture of propylene and an α-olefin having 2 to 8 carbon atoms. It may be a copolymer of Examples of α-olefins having 2 to 8 carbon atoms include ethylene, 1-butene, 1-hexene, 1-octene, and 4-methyl-1-pentene. Ethylene is preferred as these α-olefins.
極限粘度[η]が０．５ｄｌ／ｇ未満のプロピレン重合体を含む場合は、得られる重合体組成物の溶融張力が不十分であり、３．０ｄｌ／ｇを超えると、粘度が高く、押出し不良となる。また、成分（２）の質量分率が５０質量％未満では、押出し不良となり、８０質量％を超えると、溶融張力が不十分であるため発泡倍率が低くなる。 If a propylene polymer with an intrinsic viscosity [η] of less than 0.5 dl/g is contained, the resulting polymer composition will have insufficient melt tension; if it exceeds 3.0 dl/g, the viscosity will be high and extrusion will be difficult. It becomes defective. Furthermore, if the mass fraction of component (2) is less than 50% by mass, extrusion will be poor, and if it exceeds 80% by mass, the foaming ratio will be low due to insufficient melt tension.
本発明のプロピレン系重合体組成物は、２３０℃、２．１６ｋｇ荷重で測定されるＭＦＲが、通常、０．０１ｇ／１０分～５ｇ／１０分、好ましくは０．０５ｇ／１０分～４ｇ／１０分、より好ましくは０．１ｇ／１０分～３ｇ／１０分の範囲にある。 The propylene polymer composition of the present invention has an MFR measured at 230°C and a load of 2.16 kg, which is usually 0.01 g/10 minutes to 5 g/10 minutes, preferably 0.05 g/10 minutes to 4 g/10 minutes. 10 minutes, more preferably in the range of 0.1 g/10 minutes to 3 g/10 minutes.
プロピレン系重合体組成物のＭＦＲが上記範囲にあると、押出し成形性に優れ、且つ、発泡倍率が高い発泡成形体が得られ得る。
本発明に係わるプロピレン系重合体組成物は、２３０℃で測定される溶融張力（ＭＴ）が５～３０ｇ、好ましくは７ｇ～２５ｇ、より好ましく１０ｇ～２０ｇの範囲にある。
When the MFR of the propylene-based polymer composition is within the above range, a foam molded article with excellent extrudability and a high expansion ratio can be obtained.
The propylene polymer composition according to the present invention has a melt tension (MT) measured at 230° C. in the range of 5 to 30 g, preferably 7 g to 25 g, more preferably 10 g to 20 g.
プロピレン系重合体組成物のＭＴが上記範囲にあると、押出し成形性に優れ、且つ発泡倍率が高い発泡成形体が得られ得る。
本発明のプロピレン系重合体組成物は、好ましくは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された分子量分布曲線で囲まれる領域の全面積に占める分子量１５０万以上の高分子量領域の割合が７質量％以上、好ましくは１０質量％以上、さらに好ましくは１２質量％以上である。前記高分子量領域の割合が特定の割合以上を占めているということは、プロピレン系重合体組成物中に分子量１５０万以上の高分子量成分が含有されていることを意味している。この高分子量成分の少なくとも一部は極限粘度[η]が１０～１２ｄｌ／ｇの高分子量成分である。したがって、前記高分子量成分の割合が７質量％未満であると、溶融張力が不十分であるため発泡倍率が低くなる虞がある。
When the MT of the propylene polymer composition is within the above range, a foamed molded article with excellent extrudability and a high expansion ratio can be obtained.
Preferably, in the propylene polymer composition of the present invention, the ratio of the high molecular weight region having a molecular weight of 1.5 million or more to the total area of the region surrounded by the molecular weight distribution curve measured by gel permeation chromatography (GPC) is 7. The content is at least 10% by mass, preferably at least 10% by mass, and more preferably at least 12% by mass. The fact that the proportion of the high molecular weight region occupies a specific proportion or more means that a high molecular weight component having a molecular weight of 1.5 million or more is contained in the propylene polymer composition. At least a part of this high molecular weight component has an intrinsic viscosity [η] of 10 to 12 dl/g. Therefore, if the proportion of the high molecular weight component is less than 7% by mass, there is a risk that the foaming ratio will be low due to insufficient melt tension.
本発明のプロピレン系重合体組成物は、好ましくはゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された分子量分布曲線が２つのピークを有し、高分子量側のピーク分子量ＭＨと低分子量側のピーク分子量ＭＬの比（ＭＨ／ＭＬ）が５０以上、好ましくは７０以上、より好ましくは９０以上である。分子量分布曲線が２つのピークを有し、ＭＨ／ＭＬが特定の値以上になるということは、高分子量成分の含有量が多く、その極限粘度[η]も高いことを示す。したがって、分子量分布曲線が単一ピークを有する場合や、２つのピークを有していてもＭＨ／ＭＬが５０未満の場合は、発泡倍率が低くなる場合がある。 Preferably, the propylene polymer composition of the present invention has two peaks in the molecular weight distribution curve measured by gel permeation chromatography (GPC), a peak molecular weight MH on the high molecular weight side and a peak molecular weight MH on the low molecular weight side. The ratio of ML (MH/ML) is 50 or more, preferably 70 or more, more preferably 90 or more. The fact that the molecular weight distribution curve has two peaks and MH/ML is greater than a specific value indicates that the content of high molecular weight components is high and the intrinsic viscosity [η] is also high. Therefore, if the molecular weight distribution curve has a single peak, or even if it has two peaks but MH/ML is less than 50, the foaming ratio may become low.
本発明のプロピレン系重合体組成物のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された分子量分布曲線の低分子量側のピーク分子量ＭＬは、１０万以下、好ましくは８万以下、より好ましくは５万以下である。１０万を超えると粘度が高く、押出し不良となる。 The peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve measured by gel permeation chromatography (GPC) of the propylene polymer composition of the present invention is 100,000 or less, preferably 80,000 or less, more preferably 50,000 or less. It is as follows. If it exceeds 100,000, the viscosity will be high, resulting in poor extrusion.
本発明のプロピレン系重合体組成物は、ＦＥ個数（２５ｍｍΦのＴダイ製膜機で製膜した厚さ５０μｍのフィルムについて、ＦＥカウンターを用いて測定されるＦＥ個数を単位面積〔３０００ｃｍ2〕当たりの個数に換算した値）が、通常、１００個以下、好ましくは７０個以下、より好ましくは５０個以下である。ＦＥ個数１００個を超えると、発泡成形体の外観が不良となる場合がある。本発明のプロピレン系重合体組成物のＦＥ個数を上記範囲内とすることで外観が良好な成形体が得られる。 In the propylene polymer composition of the present invention, the number of FEs (the number of FEs measured using an FE counter for a 50 μm thick film formed with a 25 mmΦ T-die film forming machine per unit area [3000 cm 2 ]) ) is usually 100 or less, preferably 70 or less, and more preferably 50 or less. If the number of FE exceeds 100, the appearance of the foamed molded product may become poor. By controlling the number of FEs in the propylene polymer composition of the present invention within the above range, a molded article with a good appearance can be obtained.
本発明に係わるプロピレン系重合体組成物は、種々公知の製造方法、例えば、夫々、上記物性を満たすプロピレン系重合体（ａ１）およびプロピレン系重合体（ａ２）を夫々重合した後、上記範囲で、プロピレン系重合体（ａ１）とプロピレン系重合体（ａ２）とを混合、あるいは溶融混練してプロピレン系重合体組成物を得る方法、あるいは、上記物性を満たすプロピレン系重合体（ａ１）およびプロピレン系重合体（ａ２）を一つの重合系あるいは二つ以上の重合系で重合する方法等を例示できる。
中でも２段以上の多段重合により、相対的に高分子量のプロピレン系重合体から相対的に低分子量のプロピレン系重合体を含むように製造するのが好ましい。
The propylene polymer composition according to the present invention can be produced by various known production methods, for example, by polymerizing a propylene polymer (a1) and a propylene polymer (a2) that satisfy the above-mentioned physical properties, respectively. , a method for obtaining a propylene polymer composition by mixing or melt-kneading the propylene polymer (a1) and the propylene polymer (a2), or a propylene polymer (a1) and propylene that satisfy the above physical properties. Examples include a method of polymerizing the system polymer (a2) using one polymerization system or two or more polymerization systems.
Among these, it is preferable to produce the polymer by multi-stage polymerization of two or more stages so that a propylene-based polymer having a relatively high molecular weight contains a propylene-based polymer having a relatively low molecular weight.
本発明のプロピレン系重合体組成物の好ましい製造方法として、例えば高立体規則性ポリプロピレン製造用触媒の存在下に、プロピレンを単独で、またはプロピレンと他のモノマーとを２段以上の多段重合で重合させて製造する方法をあげることができる。具体的には、第１段目の重合において、実質的に水素の非存在下でプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとを重合させて、１３５℃テトラリン中で測定した極限粘度[η]が１０～１２ｄｌ／ｇ、好ましくは１０．５～１１．５ｄｌ／ｇの相対的に高分子量のプロピレン系重合体（ａ１）を、全重合体（組成物）中の１０～５０質量％、好ましくは１５～４５質量％、さらに好ましくは２０～４０質量％製造し、第２段目の重合において、相対的に低分子量のプロピレン系重合体（ａ２）を製造する。第２段目以降の重合において製造する相対的に低分子量のプロピレン系重合体（ａ２）の極限粘度[η]は０．５～３ｄｌ／ｇ、好ましくは０．６～２．５ｄｌ／ｇ、より好ましくは０．８～１．５ｄｌ／ｇ（この極限粘度[η]は、その段単独で製造されるプロピレン系重合体の極限粘度[η]であり、その段の前段までのプロピレン系重合体を含むプロピレン系重合体組成物全体の極限粘度[η]ではない。）で、かつ最終的に得られるプロピレン系重合体組成物のＭＦＲが０．０１～５ｇ／１０分、好ましくは０．０５～４ｇ／１０分、さらに好ましくは０．１～３ｇ／１０分となるように調整する。第２段目以降で製造するプロピレン系重合体の極限粘度[η]の調整方法は特に制限されないが、分子量調整剤として水素を使用する方法が好ましい。 As a preferred method for producing the propylene polymer composition of the present invention, for example, propylene alone or propylene and other monomers are polymerized in two or more stages of multistage polymerization in the presence of a catalyst for producing highly stereoregular polypropylene. For example, a method for manufacturing the same may be mentioned. Specifically, in the first stage polymerization, propylene or propylene and an α-olefin having 2 to 8 carbon atoms are polymerized in the substantial absence of hydrogen, and the limit measured in tetralin at 135°C is A relatively high molecular weight propylene polymer (a1) having a viscosity [η] of 10 to 12 dl/g, preferably 10.5 to 11.5 dl/g is added to the total polymer (composition) in an amount of 10 to 50 dl/g. % by mass, preferably 15 to 45% by mass, more preferably 20 to 40% by mass, and in the second stage polymerization, a relatively low molecular weight propylene polymer (a2) is produced. The intrinsic viscosity [η] of the relatively low molecular weight propylene polymer (a2) produced in the second stage and subsequent polymerizations is 0.5 to 3 dl/g, preferably 0.6 to 2.5 dl/g, More preferably 0.8 to 1.5 dl/g (this intrinsic viscosity [η] is the intrinsic viscosity [η] of the propylene polymer produced in that stage alone, and ) of the entire propylene polymer composition including coalescence, and the MFR of the propylene polymer composition finally obtained is 0.01 to 5 g/10 min, preferably 0. It is adjusted to 0.05 to 4 g/10 minutes, more preferably 0.1 to 3 g/10 minutes. The method for adjusting the intrinsic viscosity [η] of the propylene polymer produced in the second and subsequent stages is not particularly limited, but a method using hydrogen as a molecular weight regulator is preferred.
プロピレン系重合体（ａ１）とプロピレン系重合体（ａ２）の製造順序（重合順序）としては、第１段目で、実質的に水素の非存在下で、相対的に高分子量のプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとを重合した後、第２段目以降で相対的に低分子量のプロピレンを製造するのが好ましい。製造順序を逆にすることもできるが、第１段目で相対的に低分子量のプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとを重合した後、第２段目以降で相対的に高分子量のプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとを重合するためには、第１段目の反応生成物中に含まれる水素などの分子量調整剤を、第２段目以降の重合開始前に限りなく除去する必要があるため、重合装置が複雑になり、また第２段目以降の極限粘度[η]が上がりにくい。 The production order (polymerization order) of the propylene polymer (a1) and the propylene polymer (a2) is that in the first stage, relatively high molecular weight propylene or After polymerizing propylene and an α-olefin having 2 to 8 carbon atoms, it is preferable to produce propylene having a relatively low molecular weight in the second stage or later. The production order can be reversed, but after polymerizing relatively low molecular weight propylene or propylene and an α-olefin having 2 to 8 carbon atoms in the first stage, relatively low molecular weight propylene is polymerized in the second and subsequent stages. In order to polymerize high molecular weight propylene, or propylene and an α-olefin having 2 to 8 carbon atoms, a molecular weight regulator such as hydrogen contained in the reaction product of the first stage is added to the second stage. Since it is necessary to remove as much as possible before starting the subsequent polymerization, the polymerization apparatus becomes complicated and it is difficult to increase the intrinsic viscosity [η] in the second and subsequent stages.
プロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとの重合はスラリー重合、バルク重合など、公知の方法で行うことができる。また、各段の重合は連続的に行うこともできるし、バッチ式に行うこともできるが、バッチ式に行うことが好ましい。プロピレン系多段重合体を連続重合方法によって製造する場合、滞留時間分布によって重合粒子間の組成ムラが生じ、ＦＥ個数がより増加するからである。バッチ式で重合することにより、ＦＥ個数の少ないプロピレン系重合体組成物を得ることができる。 Polymerization of propylene or propylene and an α-olefin having 2 to 8 carbon atoms can be carried out by known methods such as slurry polymerization and bulk polymerization. Moreover, although the polymerization at each stage can be carried out continuously or batchwise, it is preferable to carry out batchwise. This is because when a propylene-based multistage polymer is produced by a continuous polymerization method, compositional unevenness occurs between polymer particles due to the residence time distribution, and the number of FEs increases. By polymerizing in batch mode, a propylene polymer composition with a small number of FEs can be obtained.
本発明のプロピレン系重合体組成物の製造に使用する触媒としては、マグネシウム、チタン、及びハロゲンを必須成分とする固体触媒成分、有機アルミニウム化合物等の有機金属化合物触媒成分、及び有機ケイ素化合物等の電子供与体化合物触媒成分から形成することができるが、代表的なものとして、以下のような触媒成分が使用できる。 The catalyst used in the production of the propylene polymer composition of the present invention includes a solid catalyst component containing magnesium, titanium, and halogen as essential components, an organometallic compound catalyst component such as an organoaluminum compound, and an organosilicon compound. Although it can be formed from an electron donor compound catalyst component, the following catalyst components can be typically used.
固体触媒成分の好ましい担体となるものは、金属マグネシウムとアルコールとハロゲン及び／ 又はハロゲン含有化合物から得られる。この場合、金属マグネシウムは、顆粒状、リボン状、粉末状等のマグネシウムを用いることができる。また、この金属マグネシウムは、表面に酸化マグネシウム等の被覆が生成されていないものが好ましい。 A preferred support for the solid catalyst component is obtained from magnesium metal, an alcohol, and a halogen and/or a halogen-containing compound. In this case, magnesium metal may be in the form of granules, ribbons, powder, or the like. Further, it is preferable that this metallic magnesium is not coated with magnesium oxide or the like on its surface.
アルコールとしては、炭素数１～６の低級アルコールを用いるのが好ましく、特に、エタノールを用いると、触媒性能の発現を著しく向上させる上記担体が得られる。
ハロゲンとしては、塩素、臭素、又はヨウ素が好ましく、特にヨウ素を好適に使用できる。また、ハロゲン含有化合物としては、ＭｇＣｌ2、ＭｇＩ2が好適に使用できる。
As the alcohol, it is preferable to use a lower alcohol having 1 to 6 carbon atoms, and in particular, when ethanol is used, the above-mentioned carrier can be obtained which significantly improves the expression of catalytic performance.
As the halogen, chlorine, bromine, or iodine is preferable, and iodine can be particularly preferably used. Further, as the halogen-containing compound, MgCl 2 and MgI 2 can be suitably used.
アルコールの量は、金属マグネシウム１モルに対して好ましくは２～１００モル、特に好ましくは５～５０モルである。
ハロゲン又はハロゲン含有化合物の使用量は、金属マグネシウム１グラム原子に対して、ハロゲン原子又はハロゲン含有化合物中のハロゲン原子が、０．０００１グラム原子以上、好ましくは０．０００５グラム原子以上、さらに好ましくは、０．００１グラム原子以上である。ハロゲン及びハロゲン含有化合物はそれぞれ１種を単独で使用してもよく、２種以上を併用してもよい。
The amount of alcohol is preferably 2 to 100 mol, particularly preferably 5 to 50 mol, per 1 mol of magnesium metal.
The amount of halogen or halogen-containing compound to be used is 0.0001 gram atom or more, preferably 0.0005 gram atom or more, more preferably 0.0005 gram atom or more, per 1 gram atom of metal magnesium. , 0.001 gram atom or more. One type of halogen and a halogen-containing compound may be used alone, or two or more types may be used in combination.
金属マグネシウムとアルコールとハロゲン及び／又はハロゲン含有化合物との反応方法は、例えば、金属マグネシウムとアルコールとハロゲン及び／またはハロゲン含有化合物とを、還流下（約７９℃）で水素ガスの発生が認められなくなるまで（通常２０～３０時間）反応させて、担体を得る方法である。これは、不活性ガス（例えば窒素ガス、アルゴンガス）雰囲気下で行うことが好ましい。 A method for reacting metallic magnesium, alcohol, and a halogen and/or halogen-containing compound is, for example, a reaction method in which metallic magnesium, alcohol, and a halogen and/or halogen-containing compound are heated under reflux (about 79°C) until generation of hydrogen gas is observed. In this method, the carrier is obtained by reacting until it disappears (usually for 20 to 30 hours). This is preferably carried out under an inert gas (eg nitrogen gas, argon gas) atmosphere.
得られた担体を次の固体触媒成分の合成に用いる場合、乾燥させたものを用いてもよく、また濾別後ヘプタン等の不活性溶媒で洗浄したものを用いてもよい。また、この担体は粒状に近く、しかも粒径分布がシャープである。さらには、粒子一つ一つをとってみても、粒形度のばらつきは非常に小さい。この場合、下記の式（Ｉ）で表される球形度（Ｓ） が１．６０未満、特に１．４０未満であり、かつ下記の式（ＩＩ）で表される粒径分布指数（Ｐ）が５．０未満、特に４．０未満であることが好ましい。
Ｓ＝（Ｅ１／Ｅ２）２・・・（Ｉ）
（ここで、Ｅ１は粒子の投影の輪郭長、Ｅ２は粒子の投影面積に等しい円の周長を示す。）
Ｐ＝Ｄ９０／Ｄ１０・・・（ＩＩ）
（ここで、Ｄ９０は質量累積分率が９０％に対応する粒子径をいう。すなわち、Ｄ９０で表される粒子径より小さい粒子群の質量和が全粒子総質量和の９０％であることを示している。Ｄ１０も同様である。）
When the obtained carrier is used for the next synthesis of the solid catalyst component, it may be dried or it may be filtered and washed with an inert solvent such as heptane. Furthermore, this carrier is nearly granular and has a sharp particle size distribution. Furthermore, even when looking at individual particles, the variation in particle size is extremely small. In this case, the sphericity (S) expressed by the following formula (I) is less than 1.60, particularly less than 1.40, and the particle size distribution index (P) expressed by the following formula (II) is less than 1.60, particularly less than 1.40. is preferably less than 5.0, particularly less than 4.0.
S=(E1/E2)2...(I)
(Here, E1 is the projected contour length of the particle, and E2 is the circumference of a circle equal to the projected area of the particle.)
P=D90/D10...(II)
(Here, D90 refers to the particle diameter corresponding to a mass cumulative fraction of 90%. In other words, the sum of the masses of the particle group smaller than the particle diameter expressed by D90 is 90% of the total mass of all particles. The same applies to D10.)
固体触媒成分の製造のため、上記の担体に少なくともチタン化合物を接触させている。
このチタン化合物としては、一般式（ＩＩＩ）
ＴｉＸ1ｎ（ＯＲ1）４－ｎ・・・（ＩＩＩ）
（式中、Ｘ1はハロゲン原子、特に塩素原子が好ましく、Ｒ1は炭素数１～１０の炭化水素基、特に直鎖または分岐鎖のアルキル基であり、Ｒ1が複数存在する場合にはそれらは互いに同じでも異なってもよい。ｎは０～４の整数である。）で表されるチタン化合物を用いることができる。
In order to produce a solid catalyst component, at least a titanium compound is brought into contact with the above-mentioned carrier.
As this titanium compound, general formula (III)
TiX 1 n(OR 1 )4-n...(III)
(In the formula, X 1 is preferably a halogen atom, especially a chlorine atom, R 1 is a hydrocarbon group having 1 to 10 carbon atoms, especially a straight-chain or branched alkyl group, and when there is a plurality of R 1 They may be the same or different from each other. n is an integer from 0 to 4.) A titanium compound represented by the following can be used.
具体的には、Ｔｉ（Ｏ－ｉ－Ｃ3Ｈ7）4、Ｔｉ（Ｏ－Ｃ4Ｈ9）4、ＴｉＣｌ（Ｏ－Ｃ2Ｈ5）3、ＴｉＣｌ（Ｏ－ｉ－Ｃ3Ｈ7）3、ＴｉＣｌ（Ｏ－Ｃ4Ｈ9）3、ＴｉＣｌ2（Ｏ－Ｃ4Ｈ9）2、ＴｉＣｌ2（Ｏ－ｉ－Ｃ3Ｈ7）2、ＴｉＣｌ4等を挙げることができるが、特にＴｉＣｌ4が好ましい。 Specifically, Ti(O-i-C 3 H 7 ) 4 , Ti(O-C 4 H 9 ) 4 , TiCl(O-C 2 H 5 ) 3 , TiCl(O-i-C 3 H 7 ) 3 , TiCl (O-C 4 H 9 ) 3 , TiCl 2 (O-C 4 H 9 ) 2 , TiCl 2 (O-i-C 3 H 7 ) 2 , TiCl 4 and the like. Particularly preferred is TiCl4 .
固体触媒成分は、上記の担体にさらに電子供与性化合物を接触させて得られる。この電子供与性化合物としては、フタル酸ジ－ｎ－ブチルを用いる。
また、上記の担体にチタン化合物と電子供与性化合物を接触させる際に、四塩化ケイ素等のハロゲン含有ケイ素化合物を接触させるとよい。
The solid catalyst component is obtained by further contacting the above-mentioned carrier with an electron-donating compound. Di-n-butyl phthalate is used as the electron-donating compound.
Further, when bringing the titanium compound and the electron-donating compound into contact with the above-mentioned carrier, it is preferable to bring a halogen-containing silicon compound such as silicon tetrachloride into contact with the titanium compound and the electron-donating compound.
上記の固体触媒成分は、公知の方法で調製することができる。例えば、ペンタン、ヘキサン、ペプタン又はオクタン等の不活性炭化水素を溶媒に、上記の担体、電子供与性化合物及びハロゲン含有ケイ素化合物を投入し、攪拌しながらチタン化合物を投入する方法である。通常は、マグネシウム原子換算で担体１モルに対して電子供与性化合物は、０．０１～１０モル、好ましくは０．０５～５モルを加え、また、マグネシウム原子換算で担体１モルに対してチタン化合物は、１～５０モル、好ましくは２～２０モルを加え、０～２００℃にて、５分～１０時間の条件、好ましくは３０～１５０℃にて３０分～５時間の条件で接触反応を行えばよい。
なお、反応終了後は不活性炭化水素（例えば、ｎ－ヘキサン、ｎ－ヘプタン）で、生成した固体触媒成分を洗浄するのが好ましい。
The solid catalyst component described above can be prepared by a known method. For example, the above-mentioned carrier, electron-donating compound, and halogen-containing silicon compound are added to an inert hydrocarbon such as pentane, hexane, peptane, or octane as a solvent, and the titanium compound is added while stirring. Usually, 0.01 to 10 mol, preferably 0.05 to 5 mol, of the electron-donating compound is added to 1 mol of the carrier in terms of magnesium atoms, and titanium is added to 1 mol of the carrier in terms of magnesium atoms. The compound is added in an amount of 1 to 50 mol, preferably 2 to 20 mol, and subjected to a catalytic reaction at 0 to 200°C for 5 minutes to 10 hours, preferably at 30 to 150°C for 30 minutes to 5 hours. All you have to do is
Note that after the reaction is completed, it is preferable to wash the produced solid catalyst component with an inert hydrocarbon (eg, n-hexane, n-heptane).
また、触媒成分の内、有機金属化合物触媒成分としては、有機アルミニウム化合物を好適に用いることができる。
この有機アルミニウム化合物としては、一般式（ＩＶ）
ＡｌＲ2
nＸ2
3-n・・・（ＩＶ）
（式中、Ｒ2は炭素数１～１０のアルキル基、シクロアルキル基またはアリール基であり、Ｘ2はハロゲン原子であり、塩素原子または臭素原子が好ましい。ｎは１～３の整数である。）で表される化合物が広く用いられる。具体的には、トリアルキルアルミニウム化合物、例えば、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、ジエチルアルミニウムモノクロリド、ジイソブチルアルミニウムモノクロリド、ジエチルアルミニウムモノエトキシド、エチルアルミニウムセスキクロリド等が挙げることができる。これらは、１種を単独で用いてもよく、２種以上を併用してもよい。さらに、触媒成分の内、重合系に供する電子供与性化合物成分としては、ジシクロペンチルジメトキシシラン、シクロヘキシルメチルジメトキシシラン、ジエチルアミノトリエトキシシラン、ジイソプロピルジメトキシシラン、シクロヘキシルイソブチルジメトキシシランからなる群から選ばれる少なくとも１つの有機ケイ素化合物を用いる。
Further, among the catalyst components, an organoaluminum compound can be suitably used as the organometallic compound catalyst component.
As this organoaluminum compound, general formula (IV)
AlR 2 n X 2 3-n ...(IV)
(In the formula, R 2 is an alkyl group, cycloalkyl group, or aryl group having 1 to 10 carbon atoms, and X 2 is a halogen atom, preferably a chlorine atom or a bromine atom. n is an integer of 1 to 3. ) are widely used. Specific examples include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, diethylaluminium monochloride, diisobutylaluminum monochloride, diethylaluminum monoethoxide, and ethylaluminum sesquichloride. These may be used alone or in combination of two or more. Furthermore, among the catalyst components, at least one electron donating compound component to be supplied to the polymerization system is selected from the group consisting of dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, and cyclohexylisobutyldimethoxysilane. Two organosilicon compounds are used.
上記の固体触媒成分は、前処理してから、重合に用いるとよい。例えば、ペンタン、ヘキサン、ペプタン又はオクタン等の不活性炭化水素を溶媒に、上記の固体触媒成分、有機金属化合物触媒成分及び電子供与性化合物成分を投入し、攪拌しながら、プロピレンを供給し、反応させる。また、通常、有機金属化合物触媒成分は、固体触媒成分中のチタン原子１モルに対して０．０１～２０モル、好ましくは０．０５～１０モルを加え、電子供与性化合物成分は、固体触媒成分中のチタン原子１モルに対して０．０１～２０モル、好ましくは０．１～５モルを加えるとよい。プロピレンは、大気圧よりも高いプロピレンの分圧下で供給し、０～１００℃にて、０．１～２４時間前処理するとよい。なお、反応終了後は不活性炭化水素（例えば、ｎ－ヘキサン、ｎ－ヘプタン）で、前処理したものを洗浄するのが好ましい。 The above-mentioned solid catalyst component is preferably pretreated before being used in the polymerization. For example, the above-mentioned solid catalyst component, organometallic compound catalyst component, and electron-donating compound component are added to an inert hydrocarbon such as pentane, hexane, peptane, or octane as a solvent, and while stirring, propylene is supplied and the reaction is carried out. let Further, the organometallic compound catalyst component is added in an amount of 0.01 to 20 mol, preferably 0.05 to 10 mol, per 1 mol of titanium atom in the solid catalyst component, and the electron donating compound component is added to the solid catalyst It is advisable to add 0.01 to 20 moles, preferably 0.1 to 5 moles, per mole of titanium atoms in the component. Propylene is preferably supplied under a partial pressure of propylene higher than atmospheric pressure, and pretreated at 0 to 100° C. for 0.1 to 24 hours. Note that after the reaction is completed, it is preferable to wash the pretreated product with an inert hydrocarbon (eg, n-hexane, n-heptane).
本発明のプロピレン系重合体組成物の製造方法において、プロピレン系重合体（ａ１）の製造条件としては、水素不存在下で、原料モノマーを重合温度として、好ましくは２０～８０℃、より好ましくは４０～７０℃、重合圧力として、一般に常圧～９．８ＭＰａ、好ましくは０．２～４．９ＭＰａの条件下でバルク重合して製造することが好ましい。 In the method for producing a propylene polymer composition of the present invention, the conditions for producing the propylene polymer (a1) include the polymerization temperature of the raw material monomer in the absence of hydrogen, preferably 20 to 80°C, more preferably It is preferable to carry out bulk polymerization at a temperature of 40 to 70°C and a polymerization pressure of generally normal pressure to 9.8 MPa, preferably 0.2 to 4.9 MPa.
また、プロピレン系重合体（ａ２）の製造条件としては、上記オレフィン重合用触媒を使用すること以外は特に制限されないが、原料モノマーを、重合温度として、好ましくは２０～８０℃、より好ましくは４０～７０℃、重合圧力として、一般に常圧～９．８ＭＰａ、好ましくは０．２～４．９ＭＰａ、分子量調節剤としての水素が存在する条件下で重合して製造することが好ましい。 Further, the conditions for producing the propylene polymer (a2) are not particularly limited other than using the above catalyst for olefin polymerization, but the polymerization temperature of the raw material monomer is preferably 20 to 80°C, more preferably 40°C. It is preferable to produce the polymer by polymerizing at ~70°C, the polymerization pressure generally being normal pressure ~9.8 MPa, preferably 0.2 ~ 4.9 MPa, and in the presence of hydrogen as a molecular weight regulator.
本発明のプロピレン系重合体組成物には、必要に応じて、酸化防止剤、中和剤、難燃剤、結晶核剤等の添加剤を含むことができる。添加剤の割合は特に制限されず、適宜調節することが可能である。 The propylene polymer composition of the present invention may contain additives such as antioxidants, neutralizers, flame retardants, crystal nucleating agents, and the like, if necessary. The proportion of additives is not particularly limited and can be adjusted as appropriate.
＜発泡成形体の製造方法＞
本発明のプロピレン系重合体組成物は、プロピレン系重合体組成物をプロピレン系重合体組成物とは異なるプロピレン系重合体に配合することにより、高発泡で連続気泡を有する発泡成形体を容易に得ることができる。
<Method for manufacturing foam molded product>
The propylene polymer composition of the present invention can easily produce a foamed molded article with high foaming and open cells by blending the propylene polymer composition with a propylene polymer different from the propylene polymer composition. Obtainable.
本発明のプロピレン系重合体組成物を用いてなる発泡成形体は、例えば、本発明のプロピレン系重合体組成物とプロピレン系重合体とをドライブレンドや押出機内での溶融混練等の通常の方法で混合した後、押出発泡成形により発泡シート、パイプ等の各種発泡成形体に成形することができる。成形方法としては、環状ダイ成形、Ｔ型ダイ成形等の一般的な成形方法を用いることができる。 A foamed molded article using the propylene polymer composition of the present invention can be produced by a conventional method such as dry blending or melt-kneading the propylene polymer composition of the present invention and a propylene polymer in an extruder. After mixing, the mixture can be formed into various foam molded products such as foam sheets and pipes by extrusion foam molding. As the molding method, general molding methods such as annular die molding and T-shaped die molding can be used.
本発明に係わるプロピレン系重合体は、得られる組成物が発泡可能であれば特に限定はされず種々公知のプロピレン系重合体を用い得る。
本発明に係わるプロピレン系重合体としては、好ましくは２３０℃におけるメルトフローレート(ＭＦＲ)が１～３０ｇ／１０分、かつ、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）が好ましくは６以下、より好ましくは５．５以下、さらに好ましくは５以下および、ＭＦＲが好ましくは３ｇ／１０分～２５ｇ／１０分、より好ましくは５ｇ／１０分～２０ｇ／１０分の範囲にある。
The propylene polymer according to the present invention is not particularly limited as long as the resulting composition can be foamed, and various known propylene polymers can be used.
The propylene polymer according to the present invention preferably has a melt flow rate (MFR) of 1 to 30 g/10 min at 230°C and a ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw /Mn) is preferably 6 or less, more preferably 5.5 or less, even more preferably 5 or less, and MFR is preferably 3 g/10 minutes to 25 g/10 minutes, more preferably 5 g/10 minutes to 20 g/10 minutes. within the range of
本発明に係わるプロピレン系重合体は、その構造は特に制限はなく、プロピレン単独重合体、ブロックタイプのプロピレン重合体（プロピレン単独重合体あるいはプロピレン・α－オレフィンランダム共重合体と非晶性あるいは低結晶性のプロピレン・α－オレフィンランダム共重合体との混合物）、プロピレン・α－オレフィンランダム共重合体、ランダムブロックポリプロピレン等が挙げられる。 The structure of the propylene polymer according to the present invention is not particularly limited, and may include propylene homopolymer, block type propylene polymer (propylene homopolymer or propylene/α-olefin random copolymer, and amorphous or low-crystalline polymer). Examples include mixtures with crystalline propylene/α-olefin random copolymers), propylene/α-olefin random copolymers, and random block polypropylene.
また、プロピレン系重合体は、プロピレン系重合体を有機過酸化物存在下に溶融混練していてもよい。
本発明のプロピレン系重合体組成物を前記プロピレン系重合体に混合して用いる場合は、得られる発泡成形体の用途により、所望の配合量をすることができるが、本発明のプロピレン系重合体組成物を２～５０質量％、好ましくは５～４０質量％、および前記プロピレン系重合体を５０～９８質量％、好ましくは６０～９５質量％〔但し、プロピレン系重合体組成物）とプロピレン系重合体の合計量を１００質量％とする。〕含む組成物とすることが好ましい。
Further, the propylene polymer may be melt-kneaded in the presence of an organic peroxide.
When the propylene polymer composition of the present invention is mixed with the propylene polymer, the desired amount can be determined depending on the use of the resulting foam molded product. 2 to 50% by mass of the composition, preferably 5 to 40% by mass, and 50 to 98% by mass, preferably 60 to 95% by mass of the propylene-based polymer (provided that the propylene-based polymer composition) and the propylene-based polymer The total amount of polymer is 100% by mass. ] It is preferable to set it as a composition containing.
本発明のプロピレン系重合体組成物を含む発泡成形体は、３．５倍以上の発泡倍率、ならびに６０％以上の連続気泡率を有する発泡成形体の成形に特に優れている。
発泡成形体の発泡倍率や連続気泡率は、発泡剤の添加量等により変更することが可能であるが、樹脂構造や溶融物性により、十分に発泡しない場合や、発泡しても目的の連続気泡率に到達しないことがある。本発明のプロピレン系重合体組成物を含む組成物（混合物）では、目的とする発泡倍率、ならびに連続気泡率を有する発泡成形体を得ることができる。
The foam molded article containing the propylene polymer composition of the present invention is particularly excellent in forming a foam molded article having an expansion ratio of 3.5 times or more and an open cell ratio of 60% or more.
The expansion ratio and open cell ratio of a foam molded product can be changed by adjusting the amount of blowing agent added, etc. However, depending on the resin structure and melt properties, there may be cases where sufficient foaming is not achieved, or even if foaming occurs, the desired open cell size may not be achieved. rate may not be reached. With the composition (mixture) containing the propylene polymer composition of the present invention, a foamed molded article having the desired expansion ratio and open cell ratio can be obtained.
本発明に係わる発泡成形体からなる成形品は通常の発泡成形により製造できる。例えば発泡シートは、上記したような本発明のプロピレン系樹脂組成物を含む組成物（混合物）と発泡剤とを押出機内で溶融混練した後、この溶融混練物を押出機先端に取り付けた、環状のリップを有する環状ダイスを用い、このダイスのリップより押出発泡して円筒状の発泡体を得、次いでこの円筒状発泡成形体を切り開いてシート状とする等して容易に製造される。 A molded article made of a foam molded article according to the present invention can be manufactured by ordinary foam molding. For example, a foamed sheet is produced by melt-kneading a composition (mixture) containing the propylene-based resin composition of the present invention as described above and a foaming agent in an extruder, and then attaching the melt-kneaded product to the tip of the extruder. It is easily produced by extrusion foaming through the lip of the die to obtain a cylindrical foam, and then cutting open the cylindrical foam molded product to form a sheet.
図１は、発泡成形体の成形が可能な押出発泡成形機の一例を示す概略図である。図１に示すように、押出発泡成形機１００は、樹脂原料が投入されるホッパー１１０と、樹脂原料を溶融混練する押出機としてのシリンダー１２０と、シリンダー１２０に発泡ガス等の発泡剤を導入する発泡剤導入路１３０と、冷却用のマンドレル１５０と、円筒状の発泡成形体１４０をカットする切断部材１６０と、切断されたシートを巻き取る巻き取りローラ１７０を備えている。シリンダー１２０は略円筒状に形成され、シリンダー１２０の内径よりも小さい径をもつ略円柱状のスクリュー１２１を有している。スクリュー１２１は、その外周面にらせん状の羽１２２を有しており、スクリュー１２１の軸を中心として回転可能に支持されている。シリンダー１２０の内部でスクリュー１２１が回転することにより、シリンダー１２０内の樹脂原料が溶融混練される。発泡剤導入路１３０は、シリンダー１２０の内部につながる流路であり、例えば、発泡ガスが導入される。シリンダー１２０の先端には図示していない環状ダイス（丸ダイ）が取り付けられており、シリンダー１２０内で発泡ガスと混練された樹脂原料が丸ダイから発泡しつつ押し出されることで、円筒状の発泡成形体１４０が形成される。マンドレル１５０で冷却された後、カッター等の切断部材１６０で切断され、シート状にして巻き取りローラ１７０にて巻き取られる。
FIG. 1 is a schematic diagram showing an example of an extrusion foam molding machine capable of molding a foam molded article. As shown in FIG. 1, the extrusion
本発明の発泡成形体を得るにあたり、発泡剤としては、無機発泡剤、揮発性発泡剤、分解型発泡剤等を用いることができる。無機発泡剤としては、二酸化炭素、空気、窒素等が挙げられる。揮発性発泡剤としては、プロパン、ｎ－ブタン、ｉ－ブタン、ｎ－ブタンとｉ－ブタンとの混合物、ペンタン、ヘキサン等の鎖状脂肪族炭化水素、シクロブタン、シクロペンタン等の環状脂肪族炭化水素等が挙げられる。さらに、分解型発泡剤としては、アゾジカルボンアミド、ジニトロソペンタメチレンテトラミン、アゾビスイソブチロニトリル、重炭酸ナトリウム等が挙げられる。これらの発泡剤は適宜混合して用いることができる。特に、二酸化炭素が好ましく使用される。 In obtaining the foam molded article of the present invention, an inorganic foaming agent, a volatile foaming agent, a decomposable foaming agent, etc. can be used as the foaming agent. Examples of inorganic blowing agents include carbon dioxide, air, nitrogen, and the like. Volatile blowing agents include propane, n-butane, i-butane, mixtures of n-butane and i-butane, chain aliphatic hydrocarbons such as pentane and hexane, and cycloaliphatic hydrocarbons such as cyclobutane and cyclopentane. Examples include hydrogen. Furthermore, examples of the decomposable blowing agent include azodicarbonamide, dinitrosopentamethylenetetramine, azobisisobutyronitrile, and sodium bicarbonate. These blowing agents can be used in a suitable mixture. In particular, carbon dioxide is preferably used.
本発明に係わる発泡成形体を得るにあたり、必要に応じて紫外線吸収剤、酸化防止剤、帯電防止剤、着色剤等の添加剤を添加することもできる。 In obtaining the foam molded article according to the present invention, additives such as ultraviolet absorbers, antioxidants, antistatic agents, and colorants may be added as necessary.
以下、本発明の実施例を説明するが、本発明はこれらの実施例によって限定されるものではない。尚、各例で得られた樹脂、成形体の各種特性の測定、評価は下記の通り行った。 Examples of the present invention will be described below, but the present invention is not limited to these Examples. The various properties of the resins and molded bodies obtained in each example were measured and evaluated as follows.
（１） 一段階目のプロピレン重合体成分（プロピレン系重合体（ａ１））及び二段階目のプロピレン重合体成分（プロピレン系重合体（ａ２））の質量分率
重合時に連続的に供給するプロピレンの流量計積算値を用いた物質収支から求めた。
(1) Mass fraction of the first stage propylene polymer component (propylene polymer (a1)) and the second stage propylene polymer component (propylene polymer (a2)) Propylene continuously supplied during polymerization It was determined from the mass balance using the integrated value of the flow meter.
（２）極限粘度[η]（ｄｌ／ｇ）
１３５℃、テトラリン中で行った。
尚、成分（２）の極限粘度[η]２は、下記式よりより計算した値である。
[η]２＝（[η]ｔｏｔａｌ×１００－[η]１×Ｗ１）／Ｗ２
[η]ｔｏｔａｌ：プロピレン重合体全体の極限粘度
[η]１：成分（１）の極限粘度
Ｗ１：成分（１）の質量分率（質量％）
Ｗ２：成分（２）の質量分率（質量％）
(2) Intrinsic viscosity [η] (dl/g)
It was carried out in Tetralin at 135°C.
Note that the intrinsic viscosity [η]2 of component (2) is a value calculated from the following formula.
[η]2=([η]total×100−[η]1×W1)/W2
[η]total: Intrinsic viscosity of the entire propylene polymer
[η]1: Intrinsic viscosity of component (1) W1: Mass fraction (mass%) of component (1)
W2: mass fraction (mass%) of component (2)
（３）メルトフローレート（ＭＦＲ）（ｇ／１０分）
ＪＩＳ－Ｋ７２１０に準拠し、測定温度２３０℃、荷重２．１６ｋｇｆ（２１．２Ｎ）にて測定した。
(3) Melt flow rate (MFR) (g/10 min)
Measurement was conducted in accordance with JIS-K7210 at a measurement temperature of 230°C and a load of 2.16 kgf (21.2 N).
（４）溶融張力（ＭＴ）
以下の装置及び条件で測定した。
装置：東洋精機社製キャピログラフ１Ｃ（商品名）
温度：２３０℃
オリフィス：Ｌ＝８ｍｍ、Ｄ＝２．０９５ｍｍ
押出速度：１５ｍｍ／ｍｉｎ
引取速度：１５ｍ／ｍｉｎ
(4) Melt tension (MT)
Measurement was performed using the following equipment and conditions.
Equipment: Toyo Seiki Co., Ltd. Capillograph 1C (product name)
Temperature: 230℃
Orifice: L=8mm, D=2.095mm
Extrusion speed: 15mm/min
Pick-up speed: 15m/min
（５）分子量１５０万以上の高分子量領域の割合
下記の装置及び条件のゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された分子量分布曲線で囲まれる領域の全面積に占める分子量１５０万以上の高分子量領域の割合
ＧＰＣ測定装置
カラム：ＴＯＳＯＧＭＨＨＲ－Ｈ（Ｓ）ＨＴ
検出器：Ｗａｔｅｒｓ製液体クロマトグラム用ＲＩ検出器 ＷＡＴＥＲＳ１５０Ｃ（商品名）
測定条件
溶媒：１，２，４－トリクロロベンゼン
温度：１４５℃
(5) Ratio of high molecular weight region with molecular weight of 1.5 million or more The high molecular weight of molecular weight of 1.5 million or more in the total area of the region surrounded by the molecular weight distribution curve measured by gel permeation chromatography (GPC) using the following equipment and conditions. Area ratio GPC measurement device Column: TOSOGMHHR-H(S)HT
Detector: Waters liquid chromatogram RI detector WATERS150C (product name)
Measurement conditions Solvent: 1,2,4-trichlorobenzene Temperature: 145°C
（６）ＭＬ，ＭＨ／ＭＬ
ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定された分子量分布曲線の高分子量側のピーク分子量ＭＨと低分子量側のピーク分子量ＭＬから算出
(6) ML, MH/ML
Calculated from the peak molecular weight MH on the high molecular weight side and the peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve measured by gel permeation chromatography (GPC)
（７）ＦＥ個数
（株）プラスチック工学研究所製の２５ｍｍΦのＴダイ成膜機で作成した厚さ５０μｍのフィルムのＦＥの個数を、ジェルカウンターとして（株）ヒューテック製のフィッシュアイカウンター（商標）を用いて測定した。測定数を、フィルム単位面積（３０００ｃｍ2）あたりのＦＥ個数として示した。
フィルム作成条件は次の通りである。
Ｔダイ製膜機： （株）プラスチック工学研究所製
型式： ＧＴ－２５－Ａ
スクリュー直径：２５ｍｍ、Ｌ／Ｄ＝２４
スクリュー回転数：６０ｒｐｍ
シリンダー温度設定：Ｃ１＝２３０℃、Ｃ２＝２６０℃
ヘッド温度設定：２６０℃
Ｔダイ温度設定：Ｄ１～Ｄ３＝２６０℃
Ｔダイ幅：２３０ｍｍ，リップ開度＝１ｍｍ
フィルム巻取速度：４ｍ／ｓ
ロール温度：６５℃
ジェルカウンターの測定条件は次の通りである。
装置構成
（１）受光器（４０９６画素）
（２）投光器
（３）信号処理装置
（４）パルスジェネレーター
（５）装置間ケーブル
(7) Number of FEs Calculate the number of FEs in a 50 μm thick film produced using a 25 mmΦ T-die film forming machine manufactured by Plastic Engineering Research Institute Co., Ltd. using a gel counter as a fisheye counter (trademark) manufactured by Hutech Co., Ltd. Measured using The number of measurements was shown as the number of FEs per unit area of the film (3000 cm 2 ).
The conditions for making the film are as follows.
T-die film forming machine: Made by Plastic Engineering Research Institute Co., Ltd. Model: GT-25-A
Screw diameter: 25mm, L/D=24
Screw rotation speed: 60rpm
Cylinder temperature setting: C1=230℃, C2=260℃
Head temperature setting: 260℃
T-die temperature setting: D1 to D3 = 260℃
T-die width: 230mm, lip opening = 1mm
Film winding speed: 4m/s
Roll temperature: 65℃
The measurement conditions of the gel counter are as follows.
Device configuration (1) Photoreceiver (4096 pixels)
(2) Floodlight (3) Signal processing device (4) Pulse generator (5) Inter-device cable
（８）発泡倍率
発泡成形体の質量を、水没法により求めた体積で除することにより密度を求め、未発泡品の密度で除することにより、発泡倍率として算出した。
(8) Expansion ratio The density was determined by dividing the mass of the foamed molded article by the volume determined by the submersion method, and the expansion ratio was calculated by dividing the mass by the density of the unfoamed product.
（９）連続気泡率
空気比較式比重計１０００型（東京サイエンス（株）製）を用いて、１－２－１気圧法により体積を測定した。そして、次式により連続気泡率を求めた。
連続気泡率（％）＝（見かけ体積－空気比較式比重計での測定体積）／見かけ体積×１００
(9) Open cell rate The volume was measured by the 1-2-1 atm method using an air comparison hydrometer model 1000 (manufactured by Tokyo Science Co., Ltd.). Then, the open cell ratio was determined using the following formula.
Open cell rate (%) = (apparent volume - measured volume with air comparison type hydrometer) /
（１０）押出発泡成形
下記条件により発泡シートを成形した。
成形機：東芝機械社製二軸押出機 ＴＥＭ－４１ＳＳ（商品名）
ダイ部形状：丸ダイ
ダイ部寸法：６５ｍｍ
押出量：４０ｋｇ／ｈ
スクリュ回転数：１００ｒｐｍ
シリンダー設定温度：２１０℃
ダイ部設定温度：１８０℃
発泡剤：永和化成工業社製 ＥＥ２０５（商品名） ０．５部
炭酸ガス量：２８０ｇ／ｈ
(10) Extrusion foam molding A foam sheet was molded under the following conditions.
Molding machine: Toshiba Machine Co., Ltd. twin screw extruder TEM-41SS (product name)
Die shape: Round die Die dimension: 65mm
Extrusion amount: 40kg/h
Screw rotation speed: 100rpm
Cylinder setting temperature: 210℃
Die part setting temperature: 180℃
Foaming agent: Eiwa Kasei Kogyo Co., Ltd. EE205 (trade name) 0.5 part Carbon dioxide amount: 280 g/h
＜プロピレン重合体組成物の製造＞
〔実施例１〕
（１）マグネシウム化合物の調製
攪拌機付き反応槽（内容積５００リットル）を窒素ガスで充分に置換し、エタノール９７．２ｋｇ、ヨウ素６４０ｇ、および金属マグネシウム６．４ｋｇを投入し、攪拌しながら還流条件下で系内から水素ガスの発生が無くなるまで反応させ、固体状反応生成物を得た。この固体状反応生成物を含む反応液を減圧乾燥させることにより目的のマグネシウム化合物（固体触媒の担体）を得た。
<Production of propylene polymer composition>
[Example 1]
(1) Preparation of magnesium compound A reaction tank equipped with a stirrer (inner volume 500 liters) was sufficiently replaced with nitrogen gas, 97.2 kg of ethanol, 640 g of iodine, and 6.4 kg of metallic magnesium were added, and the mixture was heated under reflux conditions while stirring. The reaction was carried out until no hydrogen gas was generated from the system, and a solid reaction product was obtained. The target magnesium compound (solid catalyst carrier) was obtained by drying the reaction solution containing this solid reaction product under reduced pressure.
（２）固体状触媒成分の調製
窒素ガスで充分に置換した撹拌機付き反応槽（内容積５００リットル）に、前期マグネシウム化合物（粉砕していないもの）３０ｋｇ、精製ヘプタン（ｎ－ヘプタン）１５０リットル、四塩化ケイ素４．５リットル、およびフタル酸ジ-n-ブチル５．４リットルを加えた。系内を９０℃に保ち、攪拌しながら四塩化チタン１４４リットルを投入して１１０℃で２時間反応させた後、固体成分を分離して８０℃の精製ヘプタンで洗浄した。さらに、四塩化チタン２２８リットルを加え、１１０℃で２時間反応させた後、精製ヘプタンで充分に洗浄し、固体触媒成分を得た。
(2) Preparation of solid catalyst component In a reaction tank with a stirrer (inner volume: 500 liters) that was sufficiently purged with nitrogen gas, 30 kg of the previous magnesium compound (unpulverized) and 150 liters of purified heptane (n-heptane) were placed. , 4.5 liters of silicon tetrachloride, and 5.4 liters of di-n-butyl phthalate were added. The inside of the system was maintained at 90°C, and 144 liters of titanium tetrachloride was added while stirring, and the reaction was carried out at 110°C for 2 hours.The solid components were separated and washed with purified heptane at 80°C. Further, 228 liters of titanium tetrachloride was added, and the mixture was reacted at 110° C. for 2 hours, and then thoroughly washed with purified heptane to obtain a solid catalyst component.
（３）前重合触媒の製造
ヘプタン２００ｍＬ中にトリエチルアルミニウム１０ｍｍｏｌ、ジシクロペンチルジメトキシシラン２ｍｍｏｌ、および（2）で得られた固体状触媒成分をチタン原子換算で１ｍｍｏｌ添加した。内温を２０℃に保持し、攪拌しながらプロピレンを連続的に導入した。６０分後、攪拌を停止し、結果的に固体触媒１ｇあたり４．０ｇのプロピレンが重合した予備重合触媒を得た。
(3) Production of prepolymerization catalyst 10 mmol of triethylaluminum, 2 mmol of dicyclopentyldimethoxysilane, and 1 mmol of the solid catalyst component obtained in (2) in terms of titanium atoms were added to 200 mL of heptane. The internal temperature was maintained at 20° C., and propylene was continuously introduced while stirring. After 60 minutes, stirring was stopped, and as a result, a prepolymerized catalyst in which 4.0 g of propylene was polymerized per 1 g of solid catalyst was obtained.
（４）本重合
６００リットルのオートクレーブ中にプロピレン３３６リットル装入し、６０℃に昇温した。その後、トリエチルアルミニウム８．７ｍＬ、ジシクロペンチルジメトキシシラン１１．４ｍＬ、（３）で得られた前重合触媒を２．９ｇ装入して重合を開始した。重合開始より７５分後に、１０分間かけて５０℃まで降温した（第１段目の重合終了）。
(4) Main polymerization 336 liters of propylene was charged into a 600 liter autoclave, and the temperature was raised to 60°C. Thereafter, 8.7 mL of triethylaluminum, 11.4 mL of dicyclopentyldimethoxysilane, and 2.9 g of the prepolymerization catalyst obtained in (3) were charged to start polymerization. 75 minutes after the start of polymerization, the temperature was lowered to 50° C. over 10 minutes (completion of first stage polymerization).
第１段目で得られたと同様の条件にて重合したプロピレン系重合体（ａ１）の極限粘度[η]は１１ｄｌ／ｇであった。
降温後、圧力が３．３ＭＰａＧで一定となるよう水素を連続的に投入し、１５１分間重合を行った。次いでベントバルブを開け、未反応のプロピレンを積算流量計を経由させてパージした（第２段目の重合終了）。
The propylene polymer (a1) polymerized under the same conditions as those obtained in the first stage had an intrinsic viscosity [η] of 11 dl/g.
After the temperature was lowered, hydrogen was continuously introduced so that the pressure was kept constant at 3.3 MPaG, and polymerization was carried out for 151 minutes. Next, the vent valve was opened, and unreacted propylene was purged through the integrating flow meter (completion of second stage polymerization).
こうして、５１．８ｋｇのパウダー状のプロピレン系重合体組成物を得た。
この重合体に、酸化防止剤として、イルガノックス１０１０〔チバ・スペシャルティ・ケミカルズ（株）製〕２０００ｐｐｍ、イルガホス１６８〔チバ・スペシャルティ・ケミカルズ（株）製〕２０００ｐｐｍ、サンドスタブＰ－ＥＰＱ〔クラリアントジャパン社製〕１０００ｐｐｍ、中和剤として、ステアリン酸カルシウム１０００ｐｐｍを添加し、二軸押出機で溶融混錬しペレット状のプロピレン系多段重合体を得た。このようにして最終的に得られたプロピレン系重合体組成物全体のＭＦＲは１．２ｇ／１０分であった。また、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は２５質量％であった。
実施例１で得たプロピレン系重合体組成物の物性を表１に示す。
In this way, 51.8 kg of a powdery propylene polymer composition was obtained.
To this polymer, as antioxidants, 2000 ppm of Irganox 1010 [manufactured by Ciba Specialty Chemicals Co., Ltd.], 2000 ppm of Irgafos 168 [manufactured by Ciba Specialty Chemicals Co., Ltd.], and 2000 ppm of Sandstub P-EPQ [manufactured by Clariant Japan Co., Ltd.] were added to this polymer. [1000 ppm] and 1000 ppm of calcium stearate were added as a neutralizing agent, and the mixture was melt-kneaded in a twin-screw extruder to obtain a pellet-shaped propylene multistage polymer. The MFR of the entire propylene polymer composition finally obtained in this manner was 1.2 g/10 minutes. Further, the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the material balance was 25% by mass.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 1.
〔実施例２〕
実施例１において、本重合の内、１段目の重合時間を８３分間、２段目の重合温度を４５℃、重合時間を１１２分間とした以外は同様の方法で重合を行った。その結果、３５．３ｋｇのプロピレン系重合体組成物を得た。ＭＦＲは０．２ｇ／１０分で、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は３８質量％であった。
実施例２で得られたプロピレン系重合体組成物の物性を表１に示す。
[Example 2]
In Example 1, polymerization was carried out in the same manner as in the main polymerization except that the first stage polymerization time was 83 minutes, the second stage polymerization temperature was 45° C., and the polymerization time was 112 minutes. As a result, 35.3 kg of a propylene polymer composition was obtained. The MFR is 0.2 g/10 min, and the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the mass balance is 38 mass %Met.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 2.
〔実施例３〕
実施例１において、本重合の内、２段目の重合時間を１６０分間とした以外は同様の方法で重合を行った。その結果、５４．４ｋｇのプロピレン系重合体組成物を得た。ＭＦＲは１．９ｇ／１０分で、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は２４質量％であった。
実施例３で得られたプロピレン系重合体組成物の物性を表１に示す。
[Example 3]
Polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization time in the main polymerization was changed to 160 minutes. As a result, 54.4 kg of a propylene polymer composition was obtained. The MFR is 1.9 g/10 min, and the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the mass balance is 24 mass %Met.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 3.
〔実施例４〕
実施例１において、本重合の内、２段目の重合時間を１４９分間とした以外は同様の方法で重合を行った。その結果、４７．６ｋｇのプロピレン系重合体組成物を得た。ＭＦＲは３．６ｇ／１０分で、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は２２質量％であった。
実施例４で得られたプロピレン系重合体組成物の物性を表１に示す。
[Example 4]
Polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization time in the main polymerization was changed to 149 minutes. As a result, 47.6 kg of a propylene polymer composition was obtained. The MFR is 3.6 g/10 minutes, and the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the mass balance is 22 mass %Met.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 4.
〔実施例５〕
実施例１において、本重合の内、２段目の重合時間を１２５分間とした以外は同様の方法で重合を行った。その結果、４７．９ｋｇのプロピレン系重合体組成物を得た。ＭＦＲは０．７ｇ／１０分で、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は３１質量％であった。
実施例５で得られたプロピレン系重合体組成物の物性を表１に示す。
[Example 5]
Polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization time in the main polymerization was changed to 125 minutes. As a result, 47.9 kg of a propylene polymer composition was obtained. The MFR is 0.7 g/10 min, and the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the mass balance is 31 mass %Met.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 5.
〔実施例６〕
実施例１において、本重合の内、２段目の重合時間を１４１分間とした以外は同様の方法で重合を行った。その結果、４８．５ｋｇのプロピレン系重合体組成物を得た。ＭＦＲは１．５ｇ／１０分で、物質収支から算出した最終的に得られたプロピレン系重合体組成物に占める第１段目の重合で生成したプロピレン系重合体（ａ１）の割合は２３質量％であった。
実施例６で得られたプロピレン系重合体組成物の物性を表１に示す。
[Example 6]
Polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization time in the main polymerization was changed to 141 minutes. As a result, 48.5 kg of a propylene polymer composition was obtained. The MFR is 1.5 g/10 min, and the proportion of the propylene polymer (a1) produced in the first stage polymerization in the finally obtained propylene polymer composition calculated from the mass balance is 23 mass %Met.
Table 1 shows the physical properties of the propylene polymer composition obtained in Example 6.
〔比較例１〕
比較例１として、市販品であるプライムポリマー社製：商品名「ＶＰ１０３Ｗ」を示す。
プロピレン系重合体（ａ１）：極限粘度[η]＝８ｄｌ／ｇ、成分量＝２０質量％
プロピレン系重合体（ａ２）：極限粘度[η]＝１．４４ｄｌ／ｇ、成分量＝８０質量％
ＭＦＲ＝３ｇ／１０分
[Comparative example 1]
As Comparative Example 1, a commercially available product manufactured by Prime Polymer Co., Ltd. under the trade name "VP103W" is shown.
Propylene polymer (a1): Intrinsic viscosity [η] = 8 dl/g, component amount = 20% by mass
Propylene polymer (a2): Intrinsic viscosity [η] = 1.44 dl/g, component amount = 80% by mass
MFR=3g/10min
〔比較例２〕
国際公開第２００５／０９７８４２号の実施例６に記載された製造方法に準じた製造方法で重合体組成物を得た。
プロピレン系重合体（ａ１）：極限粘度[η]＝１５ｄｌ／ｇ、成分量＝１４質量％
プロピレン系重合体（ａ２）：極限粘度[η]＝１．３ｄｌ／ｇ、成分量＝８６質量％
ＭＦＲ＝２ｇ／１０分
実施例１、実施例２、比較例１｛市販品｝、および比較例２で得たプロピレン系重合体組成物の物性を表１に示す。
[Comparative example 2]
A polymer composition was obtained by a manufacturing method similar to that described in Example 6 of International Publication No. 2005/097842.
Propylene polymer (a1): Intrinsic viscosity [η] = 15 dl/g, component amount = 14% by mass
Propylene polymer (a2): Intrinsic viscosity [η] = 1.3 dl/g, component amount = 86% by mass
MFR=2 g/10 min Table 1 shows the physical properties of the propylene polymer compositions obtained in Example 1, Example 2, Comparative Example 1 (commercially available product), and Comparative Example 2.
〔製造例１〕
プライムポリマー社製；商品名「Ｅ－１００ＧＰＬ」（ホモＰＰ）（ＭＦＲ＝０．９ｇ／１０分）：１００質量部に対し、有機過酸化物としてＡＤ－１１（化薬アクゾ社製）０．５質量部を加え、撹拌を十分に行った。これを、プラコー６５ｍｍ単軸押出機（プラコー製）を用い、シリンダー温度２３０℃、押出量４０ｋｇ／ｈで溶融混練した。得られたプロピレン系重合体のＭＦＲは７ｇ／１０分であった。
[Manufacture example 1]
Manufactured by Prime Polymer Co., Ltd.; trade name "E-100GPL" (homo PP) (MFR = 0.9 g/10 min): 100 parts by mass, as an organic peroxide AD-11 (manufactured by Kayaku Akzo) 0. 5 parts by mass were added and stirred thoroughly. This was melt-kneaded using a Placo 65 mm single screw extruder (manufactured by Placo) at a cylinder temperature of 230°C and an extrusion rate of 40 kg/h. The MFR of the obtained propylene polymer was 7 g/10 minutes.
〔製造例２〕
有機過酸化物の量を調整する以外は製造例１と同様の方法で溶融混練し、得られたプロピレン系重合体のＭＦＲは８ｇ／１０分であった。
[Production example 2]
Melt-kneading was carried out in the same manner as in Production Example 1 except that the amount of organic peroxide was adjusted, and the MFR of the obtained propylene-based polymer was 8 g/10 minutes.
〔製造例３〕
製造例１で用いたプライムポリマー社製「Ｅ－１００ＧＰＬ」に替えて、プライムポリマー社製；商品名「Ｅ－７０２Ｇ」（ブロックＰＰ）（ＭＦＲ＝０．９ｇ／１０分）を用い製造例１と同様の方法で溶融混練し、得られたプロピレン系重合体のＭＦＲは６．９ｇ／１０分であった。
[Manufacture example 3]
Production Example 1: Instead of "E-100GPL" manufactured by Prime Polymer Co., Ltd. used in Production Example 1, "E-702G" (trade name) (block PP) (MFR = 0.9 g/10 min) manufactured by Prime Polymer Co., Ltd. was used. The MFR of the propylene polymer obtained by melt-kneading in the same manner as above was 6.9 g/10 minutes.
〔参考例１〕
実施例１で得られたプロピレン系重合体組成物と、製造例１で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 1]
The propylene polymer composition obtained in Example 1 and the propylene polymer obtained in Production Example 1 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例２〕
実施例２で得られたプロピレン系重合体組成物と、製造例１で得られたプロピレン重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 2]
The propylene polymer composition obtained in Example 2 and the propylene polymer obtained in Production Example 1 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例３〕
実施例１で得られたプロピレン系重合体組成物と、製造例３で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 3]
The propylene polymer composition obtained in Example 1 and the propylene polymer obtained in Production Example 3 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例４〕
実施例３で得られたプロピレン系重合体組成物と、製造例３で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 4]
The propylene polymer composition obtained in Example 3 and the propylene polymer obtained in Production Example 3 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例５〕
実施例４で得られたプロピレン系重合体組成物と、製造例３で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 5]
The propylene polymer composition obtained in Example 4 and the propylene polymer obtained in Production Example 3 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例６〕
実施例５で得られたプロピレン系重合体組成物と、製造例３で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 6]
The propylene polymer composition obtained in Example 5 and the propylene polymer obtained in Production Example 3 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔参考例７〕
実施例６で得られたプロピレン系重合体組成物と、製造例３で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。
[Reference example 7]
The propylene polymer composition obtained in Example 6 and the propylene polymer obtained in Production Example 3 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions.
〔比較参考例１〕
比較例１で得られたプロピレン系重合体組成物と、製造例１で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。比較例１はプロピレン系重合体（ａ１）の極限粘度[η]が低いため、発泡倍率が不十分であった。
[Comparative reference example 1]
The propylene polymer composition obtained in Comparative Example 1 and the propylene polymer obtained in Production Example 1 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions. Comparative Example 1 had an insufficient expansion ratio because the propylene polymer (a1) had a low intrinsic viscosity [η].
〔比較参考例２〕
比較例１で得られたプロピレン系重合体組成物と、製造例２で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。比較例１はプロピレン系重合体（ａ１）の極限粘度[η]が低いため、発泡倍率が不十分であった。
[Comparative reference example 2]
The propylene polymer composition obtained in Comparative Example 1 and the propylene polymer obtained in Production Example 2 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions. Comparative Example 1 had an insufficient expansion ratio because the propylene polymer (a1) had a low intrinsic viscosity [η].
〔比較参考例３〕
比較例２で得られたプロピレン系重合体組成物と、製造例２で得られたプロピレン系重合体とを１５：８５の質量比でブレンドし、前記成形条件で発泡シートの成形を行った。比較例２はプロピレン系重合体（ａ１）の極限粘度[η]が高いため、連続気泡率が不十分であった。
参考例１～７、および比較参考例１～３の発泡特性（発泡倍率、連続気泡率）を表２に示す。
[Comparative reference example 3]
The propylene polymer composition obtained in Comparative Example 2 and the propylene polymer obtained in Production Example 2 were blended at a mass ratio of 15:85, and a foamed sheet was molded under the above molding conditions. In Comparative Example 2, the open cell ratio was insufficient because the propylene polymer (a1) had a high intrinsic viscosity [η].
Table 2 shows the foaming properties (expansion ratio, open cell ratio) of Reference Examples 1 to 7 and Comparative Reference Examples 1 to 3.
本発明により得られた発泡成形体は、緩衝性、断熱性、吸音性に優れたものであることにより、建築材料や自動車内装材等に好適に利用でき、産業上の利用可能性が高い。 The foamed molded article obtained by the present invention has excellent cushioning properties, heat insulation properties, and sound absorption properties, so that it can be suitably used for building materials, automobile interior materials, etc., and has high industrial applicability.
１００ 押出発泡成形機１１０ ホッパー１２０ シリンダー１３０ 発泡剤導入路１４０ 発泡成形体１５０ マンドレル１６０ 切断部材１７０ 巻き取りローラ
100 Extrusion
Claims (4)
第１段目の重合において、実質的に水素の非存在下でプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとを重合させて、前記プロピレン系重合体（ａ１）を、最終的に得られるプロピレン系重合体組成物の全体〔前記プロピレン系重合体（ａ１）と前記プロピレン系重合体（ａ２）との合計量〕の２０～５０質量％製造し、
次に、第２段目以降の重合において、前記プロピレン系重合体（ａ２）を、最終的に得られるプロピレン系重合体組成物の全体の５０～８０質量％製造するようにプロピレン、若しくはプロピレンと炭素数２～８のα－オレフィンとの重合を行い、かつ最終的に得られるプロピレン系重合体組成物のＭＦＲが０．０１～５ｇ／１０分となるようにプロピレンの重合を行うことを特徴とする、プロピレン系重合体組成物の製造方法。 (a) A solid catalyst component containing magnesium, titanium, and halogen as essential components obtained by contacting a carrier, a titanium compound, and di-n-butyl phthalate, (b) an organoaluminum compound, and (c) in the presence of a polymerization catalyst formed from at least one organosilicon compound selected from the group consisting of dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, diethylaminotriethoxysilane, diisopropyldimethoxysilane, and cyclohexylisobutyldimethoxysilane; Polymerize propylene by multistage polymerization to obtain 20 to 50% by mass of a propylene polymer (a1) having an intrinsic viscosity [η] of 10 to 12 dl/g measured in a tetralin solvent at 135°C. , and 50 to 80% by mass of a propylene polymer (a2) having an intrinsic viscosity [η] of 0.5 to 3 dl/g as measured in tetralin at 135°C. ) and the propylene polymer (a2) are 100% by mass. ], the peak molecular weight ML on the low molecular weight side of the molecular weight distribution curve measured by gel permeation chromatography (GPC) is 50,000 or less, and the number of FE [film thickness 50 μm formed with a 25 mmΦ T-die film forming machine] A method for producing a propylene polymer composition in which the number of FEs measured using an FE counter converted into the number per unit area (3000 cm 2 ) is 100 or less for the film,
In the first stage polymerization, propylene or propylene and an α-olefin having 2 to 8 carbon atoms are polymerized in substantially the absence of hydrogen to finally produce the propylene polymer (a1). Producing 20 to 50% by mass of the entirety of the resulting propylene polymer composition [ total amount of the propylene polymer (a1) and the propylene polymer (a2)],
Next, in the second and subsequent stages of polymerization, the propylene polymer (a2) is mixed with propylene or propylene so as to produce 50 to 80% by mass of the entire propylene polymer composition finally obtained. It is characterized by polymerizing with an α-olefin having 2 to 8 carbon atoms, and polymerizing propylene so that the MFR of the finally obtained propylene polymer composition is 0.01 to 5 g/10 minutes. A method for producing a propylene polymer composition .
（ｉ）２３０℃、２．１６ｋｇ荷重で測定されるＭＦＲが、０．０１～５ｇ／１０分の範囲にある。 (i) MFR measured at 230° C. and 2.16 kg load is in the range of 0.01 to 5 g/10 min.
（ｉｉ）２３０℃で測定される溶融張力（ＭＴ）が、５～３０ｇの範囲にある。 (ii) Melt tension (MT) measured at 230° C. is in the range of 5 to 30 g.
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