JP2004323754A - Cross-linked polyolefin resin foam - Google Patents
Cross-linked polyolefin resin foam Download PDFInfo
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- JP2004323754A JP2004323754A JP2003122751A JP2003122751A JP2004323754A JP 2004323754 A JP2004323754 A JP 2004323754A JP 2003122751 A JP2003122751 A JP 2003122751A JP 2003122751 A JP2003122751 A JP 2003122751A JP 2004323754 A JP2004323754 A JP 2004323754A
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- resin foam
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- polyolefin resin
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- 229920005672 polyolefin resin Polymers 0.000 title claims abstract description 62
- 239000006260 foam Substances 0.000 title claims abstract description 50
- 229920001400 block copolymer Polymers 0.000 claims abstract description 28
- 229920000573 polyethylene Polymers 0.000 claims abstract description 14
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 8
- 239000011342 resin composition Substances 0.000 claims abstract description 6
- 229920005678 polyethylene based resin Polymers 0.000 claims description 10
- 229920005673 polypropylene based resin Polymers 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 4
- 229920005989 resin Polymers 0.000 abstract description 18
- 239000011347 resin Substances 0.000 abstract description 18
- -1 polypropylene Polymers 0.000 abstract description 15
- 150000001993 dienes Chemical class 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 13
- 239000004743 Polypropylene Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 7
- 229920013716 polyethylene resin Polymers 0.000 abstract description 7
- 229920001155 polypropylene Polymers 0.000 abstract description 7
- 239000004088 foaming agent Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 230000005865 ionizing radiation Effects 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 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
- 239000000178 monomer Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920000092 linear low density polyethylene Polymers 0.000 description 3
- 239000004707 linear low-density polyethylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920005606 polypropylene copolymer Polymers 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- ROLAGNYPWIVYTG-UHFFFAOYSA-N 1,2-bis(4-methoxyphenyl)ethanamine;hydrochloride Chemical compound Cl.C1=CC(OC)=CC=C1CC(N)C1=CC=C(OC)C=C1 ROLAGNYPWIVYTG-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- RRWFUWRLNIZICP-UHFFFAOYSA-N 1-bromo-2-phenoxybenzene Chemical compound BrC1=CC=CC=C1OC1=CC=CC=C1 RRWFUWRLNIZICP-UHFFFAOYSA-N 0.000 description 1
- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 description 1
- YJVIKVWFGPLAFS-UHFFFAOYSA-N 9-(2-methylprop-2-enoyloxy)nonyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCOC(=O)C(C)=C YJVIKVWFGPLAFS-UHFFFAOYSA-N 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- KJQMOGOKAYDMOR-UHFFFAOYSA-N CC(=C)C=C.CC(=C)C=C Chemical compound CC(=C)C=C.CC(=C)C=C KJQMOGOKAYDMOR-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 229920005674 ethylene-propylene random copolymer Polymers 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 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
- 229920001179 medium density polyethylene Polymers 0.000 description 1
- 239000004701 medium-density polyethylene Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、耐熱性、機械的強度及び柔軟性に優れた架橋ポリオレフィン系樹脂発泡体に関する。
【０００２】
【従来の技術】
従来から、架橋ポリオレフィン系樹脂発泡体は、優れた柔軟性及び耐熱性を有していることから、各種断熱材や雑貨として広く用いられており、最近では車両用内装材としても用いられている。
【０００３】
そして、架橋ポリオレフィン系樹脂発泡体を車両用内装材として用いるにあたっては、真空成形やスタンピング成形などの汎用の成形方法を用いて成形されるが、近年、車両の内装が複雑化してきている。
【０００４】
従って、架橋ポリオレフィン系樹脂発泡体を汎用の成形方法を用いて所望形状に成形するにあたり、架橋ポリオレフィン系樹脂発泡体は、大きく延伸或いは圧縮され、その結果、架橋ポリオレフィン系樹脂発泡体に破れや皺が発生するといった問題点が発生していた。
【０００５】
そこで、架橋ポリオレフィン系樹脂発泡体の耐熱性及び機械的強度を改善するために、特許文献１には、ポリプロピレン系樹脂と直鎖状ポリエチレンとからなるポリオレフィン系樹脂に、両端のブロック相がスチレン重合体で中央のブロック相がポリイソプレンを水素添加したエチレン−プロピレン共重合体を添加したものを発泡させてなる架橋ポリオレフィン系樹脂発泡体が提案されている。
【０００６】
しかしながら、上記架橋ポリオレフィン系樹脂発泡体は、その気泡にばらつきが大きくて不均質であると共に耐熱性及び機械的強度の点においても不充分なものであった。
【０００７】
【特許文献１】
特開平５−９３２４号公報
【０００８】
【発明が解決しようとする課題】
本発明は、耐熱性、機械的強度及び柔軟性に優れており、外観性に優れた所望形状の成形品を得ることができる架橋ポリオレフィン系樹脂発泡体を提供する。
【０００９】
【課題を解決するための手段】
本発明の架橋ポリオレフィン系樹脂発泡体は、ポリプロピレン系樹脂４０〜８０重量％及びポリエチレン系樹脂２０〜６０重量％からなるポリオレフィン系樹脂１００重量部と、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるブロック共重合体の水素添加物１〜２０重量部とからなる樹脂組成物を架橋発泡させてなることを特徴とする。
【００１０】
上記架橋ポリオレフィン系樹脂発泡体を構成するポリオレフィン系樹脂は、ポリプロピレン系樹脂とポリエチレン系樹脂とからなるが、上記ポリプロピレン系樹脂としては、従来から発泡体に用いられているものであれば、特に限定されず、例えば、ホモポリプロピレン、プロピレンを５０重量％以上含有するプロピレンとプロピレンと共重合可能なモノマーとの共重合体などが挙げられ、単独で用いられても二種類以上が併用されてもよい。なお、プロピレンと重合性モノマーとの共重合体は、ブロック共重合体又はランダム共重合体の何れであってもよいが、ランダム共重合体が好ましい。
【００１１】
又、プロピレンと共重合可能なモノマーとしては、例えば、エチレン、１−ブテン、１−ペンテン、１−ヘキセン、４−メチル−１−ペンテン、１−ヘプテン、１−オクテンなどのα−オレフィンが挙げられ、エチレンが好ましい。プロピレンと共重合可能なモノマーは、単独で用いられても二種類以上が併用されてもよい。
【００１２】
そして、上記架橋ポリオレフィン系樹脂発泡体を構成するポリエチレン系樹脂としては、高密度ポリエチレン、中密度ポリエチレン、低密度ポリエチレン、超低密度ポリエチレン、直鎖状低密度ポリエチレンなどが挙げられ、高密度ポリエチレン、直鎖状低密度ポリエチレンが好ましい。なお、ポリエチレン系樹脂は、単独で用いられても二種類以上が併用されてもよい。
【００１３】
又、ポリオレフィン系樹脂中におけるポリプロピレン系樹脂の含有量は、少ないと、架橋ポリオレフィン系樹脂発泡体の耐熱性及び機械的強度が低下する一方、多いと、架橋ポリオレフィン系樹脂発泡体の柔軟性が低下するので、４０〜８０重量％に限定され、５０〜７０重量％が好ましい。同様に、ポリオレフィン系樹脂中におけるポリエチレン系樹脂の含有量は、２０〜６０重量％に限定され、３０〜５０重量％が好ましい。
【００１４】
更に、上記ポリオレフィン系樹脂には、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるブロック共重合体の水素添加物（以下、「ブロック共重合体水素添加物」という）が添加され、上記ブロック共重合体の水素添加物としては、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるのが好ましい。なお、上記ブロック共重合体は、Ａ−Ｂ−Ａ型の所謂、サンドイッチ型ブロック共重合体である（Ａはエチレン重合体ブロックであり、Ｂは共役ジエン系重合体ブロックである）。
【００１５】
上記ブロック共重合体水素添加物のエチレン重合体ブロック中のエチレン成分の含有量は、少ないと、ブロック共重合体水素添加物のポリエチレン系樹脂との相溶性が低下するので、７０重量％以上が好ましく、８０重量％以上が好ましい。
【００１６】
上記ブロック共重合体水素添加物の共役ジエン系重合体ブロックとしては、一種類の共役ジエン化合物の単独重合体ブロック、又は、二種類以上の共役ジエン化合物同士の共重合体ブロックが挙げられるが、一種類の共役ジエン化合物の単独重合体ブロックが好ましい。
【００１７】
上記ブロック共重合体水素添加物中の共役ジエン系重合体ブロックを構成する共役ジエン化合物としては、例えば、１，３−ブタジエン、イソプレン（２−メチル−１，３−ブタジエン）、１，３−ペンタジエン、２，３−ジメチル−１，３−ブタジエンなどが挙げられ、ブロック共重合体水素添加物がポリプロピレン系樹脂に対する相溶性に優れていることから、１，３−ブタジエンとイソプレンが好ましく、１，３−ブタジエンがより好ましい。
【００１８】
更に、上記ブロック共重合体水素添加物中における共役ジエン系重合体ブロックの含有量は、少ないと、ポリプロピレン系樹脂との相溶性が低下することがある一方、多いと、ポリエチレン系樹脂との相溶性が低下することがあるので、２０〜８０重量％が好ましく、５０〜８０重量％がより好ましい。
【００１９】
なお、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるブロック共重合体の水素添加物としては、ジェイエスアール社から商品名「ダイナロン６２００Ｐ」で市販されている。
【００２０】
そして、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるブロック共重合体の水素添加物の添加量は、少ないと、ブロック共重合体水素添加物を添加した効果が発現せず、又、多いと、架橋ポリオレフィン系樹脂発泡体の引張強さ及び耐熱性が却って低下するので、ポリオレフィン系樹脂１００重量部に対して１〜２０重量部に限定され、３〜１０重量部が好ましい。
【００２１】
このように、本発明では、上記のような特定の分子構造を有するブロック共重合体水素添加物を添加することによって、得られる架橋ポリオレフィン系樹脂発泡体の耐熱性、機械的強度及び柔軟性を向上させている。この架橋ポリオレフィン系樹脂発泡体の耐熱性、機械的強度及び柔軟性の向上の原因は明確には解明されていないものの以下のことが考えられる。
【００２２】
即ち、上述したブロック共重合体水素添加物は、両端のブロック部がエチレン重合体ブロックから形成されている一方、中央のブロック部が共役ジエン系重合体ブロックの水素添加物から形成されている。
【００２３】
そして、両端のブロック部は、エチレン重合体に起因してポリエチレン系樹脂との相溶性に優れていると共に、中央のブロック部は、共役ジエン系重合体の水素添加物に起因してポリプロピレン系樹脂との相溶性に優れている。
【００２４】
従って、上記ブロック共重合体水素添加物は、互いに相溶性が低いポリプロピレン系樹脂とポリエチレン系樹脂との間の相溶化剤として作用し、ポリプロピレン系樹脂とポリエチレン系樹脂とを互いに相分離させることなく均一に混合させることができる。
【００２５】
その結果、架橋ポリオレフィン系樹脂発泡体は、ポリプロピレン系樹脂に起因した優れた耐熱性及び機械的強度と、ポリエチレン系樹脂に起因した優れた柔軟性を安定的に且つ効果的に発揮しており、よって、耐熱性、機械的強度及び柔軟性の全てにおいて優れたものとなっており、汎用の成形方法により成形した場合にあっても、破れたり皺を生じたりすることはなく、複雑にして美麗な成形品を確実に得ることができるものである。
【００２６】
更に、上述のように、ポリプロピレン系樹脂とポリエチレン系樹脂とは上記ブロック共重合体水素添加物を介して均一に混合されていることから、架橋ポリオレフィン系樹脂発泡体は、その製造時における発泡工程において全体的に略均一に発泡してなり、その気泡形態が全体に亘って均一なものとなっており、均質なものとなっている。
【００２７】
又、本発明の架橋ポリオレフィン系樹脂発泡体には、架橋ポリオレフィン系樹脂発泡体の物性を損なわない範囲内において、炭酸カルシウム、タルク、クレー、酸化マグネシウムなどの気泡形成剤；２，６−ジ−ｔ−ブチル−ｐ−クレゾールなどのフェノール系、リン系、アミン系、ジラウリルチオプロピオネートなどのイオウ系などの酸化防止剤；メチルベンゾトリアゾールなどの金属害防止剤；ヘキサブロモビフェニルエーテル、デカブロモジフェニルエーテルなどのハロゲン化難燃剤、ポリリン酸アンモニウム、トリメチルフォスフェートなどのリン系難燃剤などの難燃剤の他、充填剤、帯電防止剤、安定剤、顔料などが添加されてもよい。
【００２８】
次に、上記架橋ポリオレフィン系樹脂発泡体の製造方法について説明する。先ず、上記ポリプロピレン系樹脂及びポリエチレン系樹脂からなるポリオレフィン系樹脂、ブロック共重合体水素添加物及び熱分解型発泡剤、必要に応じて架橋助剤及びその他の添加剤を添加してなる発泡性樹脂組成物を汎用の混練装置に供給して熱分解型発泡剤の分解温度未満の温度にて溶融、混練して所望形状の発泡性樹脂成形品に成形する。
【００２９】
なお、上記混練装置としては、例えば、単軸押出機、二軸押出機などの押出機、バンバリーミキサー、ロールなどの汎用混練装置などが挙げられ、押出機が好ましい。
【００３０】
ここで、上記熱分解型発泡剤としては、従来から発泡体の製造に用いられているものであれば、特に限定されず、例えば、アゾジカルボンアミド、ベンゼンスルホニルヒドラジド、ジニトロソペンタメチレンテトラミン、トルエンスルホニルヒドラジド、４，４−オキシビス（ベンゼンスルホニルヒドラジド）などが挙げられ、これらは単独で用いられても二種類以上が併用されてもよい。
【００３１】
そして、上記熱分解型発泡剤の添加量は、少ないと、発泡性樹脂成形品が発泡しないことがある一方、多いと、架橋ポリオレフィン系樹脂発泡体の気泡が破裂することがあるので、ポリオレフィン系樹脂１００重量部に対して１〜５０重量部が好ましく、４〜２５重量部がより好ましい。
【００３２】
更に、上記架橋助剤としては、従来から発泡体の製造に用いられているものであれば、特に限定されず、例えば、ジビニルベンゼン、トリメチロールプロパントリメタクリレート、１，９−ノナンジオールジメタクリレート、１，１０−デカンジオールジメタクリレート、トリメリット酸トリアリルエステル、トリアリルイソシアヌレート、エチルビニルベンゼン、ネオペンチルグリコールジメタクリレート、１，２，４−ベンゼントリカルボン酸トリアリルエステル、１，６−ヘキサンジオールジメタクリレート、ラウリルメタクリレート、ステアリルメタクリレート、フタル酸ジアリル、テレフタル酸ジアリル、イソフタル酸ジアリルなどが挙げられ、これらは単独で用いられても二種類以上が併用されてもよい。
【００３３】
そして、上記架橋助剤の添加量は、少ないと、発泡性樹脂組成物が発泡時に必要な架橋度、即ち、剪断粘度を得ることができないことがある一方、多いと、発泡性樹脂組成物に付与する架橋度の制御が困難となることがあるので、ポリオレフィン系樹脂１００重量部に対して０．１〜１０重量部が好ましく、０．２〜８重量部がより好ましく、０．３〜６重量部が特に好ましく、０．５〜５重量部が最も好ましい。
【００３４】
次に、上記発泡性樹脂成形品に電離性放射線を照射して架橋構造を付与する。この際、上述した架橋助剤を発泡性樹脂組成物に添加することによって、発泡性樹脂成形品に照射する電離性放射線量を低減して、電離性放射線の照射に伴うポリオレフィン系樹脂分子の切断、劣化を防止することができる。
【００３５】
なお、上記電離性放射線としては、特に限定されず、例えば、α線、β線、γ線、電子線などを挙げることができ、電子線が好ましい。又、発泡性樹脂成形品に対する電離性放射線の照射量は、少ないと、発泡性樹脂成形品の発泡に必要な剪断粘度を付与することができないことがある一方、多いと、発泡性樹脂成形品の剪断粘度が高くなりすぎて発泡性が低下し、発泡倍率の高い架橋ポリオレフィン系樹脂発泡体を得ることができなくなると共に架橋ポリオレフィン系樹脂発泡体の外観性も低下することがあるので、０．１〜１０Ｍｒａｄが好ましく、０．２〜５Ｍｒａｄがより好ましく、０．５〜３Ｍｒａｄが特に好ましい。
【００３６】
そして、上記のようにして架橋された発泡性樹脂成形品を熱分解型発泡剤の分解温度以上に加熱し発泡させて架橋ポリオレフィン系樹脂発泡体を得ることができる。
【００３７】
【実施例】
（実施例１〜４、比較例１〜５）
表１に示した所定量のエチレン−プロピレンランダム共重合体（エチレン成分：２重量％、メルトインデックス：０．５ｇ／１０分、密度：０．９１ｇ／ｃｍ３ ）、ホモポリプロピレン（メルトインデックス＝０．４ｇ／１０分、密度０．９１ｇ／ｃｍ３ ）、直鎖状低密度ポリエチレン（メルトインデックス＝２．１ｇ／１０分、密度：０．９２ｇ／ｃｍ３ ）、高密度ポリエチレン（メルトインデックス＝３．０ｇ／１０分、密度０．９６ｇ／ｃｃ）、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部がエチレン−ブチレン共重合体ブロックであるブロック共重合体水素添加物（ジェイエスアール社製 商品名「ダイナロン６２００Ｐ」）、ジビニルベンゼン３重量部、アゾジカルボンアミド１３重量部、２，６−ジ−ｔ−ブチル−ｐ−クレゾール０．３重量部、ジラウリルチオプロピオネート０．３重量部及びメチルベンゾトリアゾール０．５重量部を単軸押出機に供給して樹脂温度１８５℃にて溶融混練して厚さ１ｍｍの発泡性ポリオレフィン系樹脂シートを得た。
【００３８】
得られた発泡性ポリオレフィン系樹脂シートの両面に加速電圧７００ｋＶで電子線を１．５Ｍｒａｄ照射して発泡性ポリオレフィン系樹脂シートを架橋させた後、この発泡性ポリオレフィン系樹脂シートを２５０℃に加熱して発泡させて架橋ポリオレフィン系樹脂発泡体を得た。
【００３９】
得られた架橋ポリオレフィン系樹脂発泡体のゲル分率、見掛け密度、２３℃における破断点伸度及び引張強さ、１７５℃における破断点伸度及び引張強さを下記に示した要領で測定し、その結果を表２に示した。
【００４０】
（ゲル分率）
架橋ポリオレフィン系樹脂発泡体をＡｇ秤量し、これを１２０℃のキシレン中に２４時間浸漬して不溶解分を２００メッシュの金網で濾過し、金網上の残渣を真空乾燥して乾燥残渣の重量を測定し（Ｂｇ）、下記式により算出した。
ゲル分率（重量％）＝（Ｂ／Ａ）×１００
【００４１】
（見掛け密度）
架橋ポリオレフィン系樹脂発泡体の見掛け密度をＪＩＳ Ｋ７２２２に準拠して測定した。
【００４２】
（破断点伸度）
架橋ポリオレフィン系樹脂発泡体の破断点伸度は、設定温度を変更した以外は、ＪＩＳ Ｋ６７６７（Ａ法）に準拠して測定された伸びをいい、具体的には、架橋ポリオレフィン系樹脂発泡体を所定温度に調整されたオーブン内に放置し、架橋ポリオレフィン系樹脂発泡体の表面温度をサーモラベルにより測定して、２３℃での破断点伸度を測定する場合には、架橋ポリオレフィン系樹脂発泡体の表面温度が２３℃となった時に、１７５℃での破断点伸度を測定する場合には、架橋ポリオレフィン系樹脂発泡体の表面温度が１７５℃となった時に測定した。
【００４３】
（引張強さ）
架橋ポリオレフィン系樹脂発泡体の引張強さは、設定温度を変更した以外はＪＩＳ Ｋ６７６７（Ａ法）に準拠して測定された引張強さをいい、具体的には、架橋ポリオレフィン系樹脂発泡体を所定温度に調整されたオーブン内に放置し、架橋ポリオレフィン系樹脂発泡体の表面温度をサーモラベルにより測定して、２３℃での引張強さを測定する場合には、架橋ポリオレフィン系樹脂発泡体の表面温度が２３℃となった時に、１７５℃での引張強さを測定する場合には、架橋ポリオレフィン系樹脂発泡体の表面温度が１７５℃となった時に測定した。
【００４４】
【表１】
【表２】
【発明の効果】
本発明の架橋ポリオレフィン系樹脂発泡体は、ポリプロピレン系樹脂４０〜８０重量％及びポリエチレン系樹脂２０〜６０重量％からなるポリオレフィン系樹脂１００重量部と、両端のブロック部がエチレン重合体ブロックで且つ中央のブロック部が共役ジエン系重合体ブロックであるブロック共重合体の水素添加物１〜２０重量部とからなる樹脂組成物を架橋発泡させてなることを特徴とするので、ポリプロピレン系樹脂とポリエチレン系樹脂とを特定分子構造を有するブロック共重合体の水素添加物の作用によって均一に相溶させ、ポリプロピレン系樹脂とポリエチレン系樹脂の双方の優れた作用を効果的に発揮させることによって、優れた耐熱性、機械的強度及び柔軟性を有しており、汎用の成形方法によって複雑にして美麗な成形品を確実に得ることができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a crosslinked polyolefin-based resin foam excellent in heat resistance, mechanical strength, and flexibility.
[0002]
[Prior art]
BACKGROUND ART Conventionally, crosslinked polyolefin-based resin foams have been widely used as various heat insulating materials and miscellaneous goods since they have excellent flexibility and heat resistance, and are also recently used as interior materials for vehicles. .
[0003]
When a crosslinked polyolefin-based resin foam is used as an interior material for a vehicle, it is molded using a general-purpose molding method such as vacuum molding or stamping molding, but in recent years, the interior of the vehicle has become complicated.
[0004]
Therefore, in molding the crosslinked polyolefin resin foam into a desired shape using a general-purpose molding method, the crosslinked polyolefin resin foam is greatly stretched or compressed, and as a result, the crosslinked polyolefin resin foam is torn or wrinkled. Has occurred.
[0005]
In order to improve the heat resistance and mechanical strength of a crosslinked polyolefin resin foam, Patent Document 1 discloses that a block phase at both ends is added to a polyolefin resin composed of a polypropylene resin and a linear polyethylene. There has been proposed a crosslinked polyolefin-based resin foam obtained by foaming a mixture obtained by adding an ethylene-propylene copolymer obtained by hydrogenation of polyisoprene and having a central block phase.
[0006]
However, the above-mentioned crosslinked polyolefin-based resin foam has a large variation in cells and is inhomogeneous, and also has insufficient heat resistance and mechanical strength.
[0007]
[Patent Document 1]
JP-A-5-9324
[Problems to be solved by the invention]
The present invention provides a crosslinked polyolefin-based resin foam that is excellent in heat resistance, mechanical strength, and flexibility, and that can obtain a molded article having a desired shape and excellent appearance.
[0009]
[Means for Solving the Problems]
The crosslinked polyolefin-based resin foam of the present invention comprises a polyolefin-based resin composed of 40 to 80% by weight of a polypropylene-based resin and 20 to 60% by weight of a polyethylene-based resin, and an ethylene polymer block at both end blocks and a center. Is characterized in that a resin composition composed of 1 to 20 parts by weight of a hydrogenated product of a block copolymer in which the block portion is a conjugated diene polymer block is crosslinked and foamed.
[0010]
The polyolefin resin constituting the crosslinked polyolefin resin foam is composed of a polypropylene resin and a polyethylene resin, but the polypropylene resin is not particularly limited as long as it has been conventionally used for a foam. Examples thereof include, for example, homopolypropylene, a copolymer of propylene containing 50% by weight or more of propylene and a monomer copolymerizable with propylene, and the like, and may be used alone or in combination of two or more. . In addition, the copolymer of propylene and the polymerizable monomer may be either a block copolymer or a random copolymer, but is preferably a random copolymer.
[0011]
Examples of the monomer copolymerizable with propylene include α-olefins such as ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene and 1-octene. And ethylene is preferred. The monomers copolymerizable with propylene may be used alone or in combination of two or more.
[0012]
And, as the polyethylene resin constituting the crosslinked polyolefin resin foam, high-density polyethylene, medium-density polyethylene, low-density polyethylene, ultra-low-density polyethylene, linear low-density polyethylene, and the like, and high-density polyethylene, Linear low density polyethylene is preferred. The polyethylene resin may be used alone or in combination of two or more.
[0013]
In addition, when the content of the polypropylene resin in the polyolefin resin is small, the heat resistance and mechanical strength of the crosslinked polyolefin resin foam are reduced, while when the content is large, the flexibility of the crosslinked polyolefin resin foam is reduced. Therefore, the amount is limited to 40 to 80% by weight, and preferably 50 to 70% by weight. Similarly, the content of the polyethylene resin in the polyolefin resin is limited to 20 to 60% by weight, and preferably 30 to 50% by weight.
[0014]
Further, the above polyolefin-based resin includes a hydrogenated product of a block copolymer (hereinafter, referred to as “block copolymer hydrogen”) in which both end block portions are ethylene polymer blocks and a central block portion is a conjugated diene polymer block. As the hydrogenated product of the block copolymer, it is preferable that the block portions at both ends are ethylene polymer blocks and the central block portion is a conjugated diene-based polymer block. The block copolymer is a so-called sandwich type block copolymer of ABA type (A is an ethylene polymer block, and B is a conjugated diene-based polymer block).
[0015]
If the content of the ethylene component in the ethylene polymer block of the hydrogenated block copolymer is small, the compatibility of the hydrogenated block copolymer with the polyethylene resin is reduced. It is preferably at least 80% by weight.
[0016]
Examples of the conjugated diene-based polymer block of the hydrogenated block copolymer include a homopolymer block of one type of conjugated diene compound, or a copolymer block of two or more types of conjugated diene compounds, Homopolymer blocks of one type of conjugated diene compound are preferred.
[0017]
Examples of the conjugated diene compound constituting the conjugated diene-based polymer block in the hydrogenated block copolymer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene) and 1,3-butadiene. Examples thereof include pentadiene and 2,3-dimethyl-1,3-butadiene, and 1,3-butadiene and isoprene are preferred because hydrogenated block copolymers have excellent compatibility with polypropylene resins. , 3-butadiene is more preferred.
[0018]
Further, if the content of the conjugated diene-based polymer block in the hydrogenated block copolymer is small, the compatibility with the polypropylene-based resin may be reduced. On the other hand, if the content is large, the compatibility with the polyethylene-based resin may be reduced. Since solubility may be reduced, 20 to 80% by weight is preferable, and 50 to 80% by weight is more preferable.
[0019]
As a hydrogenated product of a block copolymer having an ethylene polymer block at both ends and a conjugated diene-based polymer block at the center, it is commercially available from JSR Co. under the trade name “Dynalon 6200P”. ing.
[0020]
When the amount of the hydrogenated product of the block copolymer in which the block portions at both ends are ethylene polymer blocks and the central block portion is a conjugated diene-based polymer block is small, the hydrogenated product of the block copolymer is reduced. The effect of the addition is not exhibited, and if too large, the tensile strength and heat resistance of the crosslinked polyolefin-based resin foam are rather reduced, so the amount is limited to 1 to 20 parts by weight with respect to 100 parts by weight of the polyolefin-based resin, 3 to 10 parts by weight are preferred.
[0021]
Thus, in the present invention, by adding a hydrogenated block copolymer having the specific molecular structure as described above, the heat resistance, mechanical strength and flexibility of the obtained crosslinked polyolefin resin foam are improved. Have improved. Although the cause of the improvement in heat resistance, mechanical strength, and flexibility of the crosslinked polyolefin resin foam has not been clearly elucidated, the following may be considered.
[0022]
That is, in the above-described hydrogenated block copolymer, the block portions at both ends are formed from an ethylene polymer block, while the central block portion is formed from a hydrogenated product of a conjugated diene-based polymer block.
[0023]
The block portions at both ends are excellent in compatibility with the polyethylene resin due to the ethylene polymer, and the central block portion is the polypropylene resin due to the hydrogenated product of the conjugated diene polymer. Excellent compatibility with
[0024]
Accordingly, the hydrogenated block copolymer acts as a compatibilizer between the polypropylene-based resin and the polyethylene-based resin having low compatibility with each other, without causing phase separation between the polypropylene-based resin and the polyethylene-based resin. It can be mixed uniformly.
[0025]
As a result, the crosslinked polyolefin-based resin foam exhibits excellent heat resistance and mechanical strength due to the polypropylene-based resin and excellent flexibility due to the polyethylene-based resin stably and effectively. Therefore, it is excellent in all of heat resistance, mechanical strength and flexibility. Even when molded by a general-purpose molding method, it does not break or wrinkle, it is complicated and beautiful. A reliable molded product can be obtained reliably.
[0026]
Further, as described above, since the polypropylene-based resin and the polyethylene-based resin are uniformly mixed via the above-described block copolymer hydrogenated product, the crosslinked polyolefin-based resin foam is subjected to a foaming process during its production. , The foam is substantially uniformly foamed as a whole, and the bubble form is uniform over the whole.
[0027]
The crosslinked polyolefin-based resin foam of the present invention also includes a foaming agent such as calcium carbonate, talc, clay, and magnesium oxide within a range that does not impair the physical properties of the crosslinked polyolefin-based resin foam; Antioxidants such as phenol-based such as t-butyl-p-cresol, phosphorus-based, amine-based and sulfur-based such as dilaurylthiopropionate; metal harm inhibitor such as methylbenzotriazole; hexabromobiphenyl ether, deca In addition to halogenated flame retardants such as bromodiphenyl ether, and flame retardants such as phosphorus-based flame retardants such as ammonium polyphosphate and trimethyl phosphate, fillers, antistatic agents, stabilizers, pigments, and the like may be added.
[0028]
Next, a method for producing the crosslinked polyolefin resin foam will be described. First, a polyolefin-based resin composed of the above-mentioned polypropylene-based resin and polyethylene-based resin, a hydrogenated block copolymer and a pyrolytic foaming agent, and a foamable resin obtained by adding a crosslinking assistant and other additives as necessary. The composition is supplied to a general-purpose kneading device, melted and kneaded at a temperature lower than the decomposition temperature of the pyrolytic foaming agent, and molded into a foamable resin molded product having a desired shape.
[0029]
Examples of the kneading apparatus include extruders such as a single-screw extruder and a twin-screw extruder, and general-purpose kneading apparatuses such as a Banbury mixer and a roll, and an extruder is preferable.
[0030]
Here, the thermal decomposition type foaming agent is not particularly limited as long as it has been conventionally used for producing a foam, and examples thereof include azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, and toluene. Examples thereof include sulfonyl hydrazide and 4,4-oxybis (benzenesulfonyl hydrazide), and these may be used alone or in combination of two or more.
[0031]
If the amount of the pyrolytic foaming agent is too small, the foamable resin molded article may not foam, while if it is too large, the cells of the crosslinked polyolefin resin foam may burst, so that the polyolefin-based foaming agent may be ruptured. The amount is preferably 1 to 50 parts by weight, more preferably 4 to 25 parts by weight, based on 100 parts by weight of the resin.
[0032]
Further, the crosslinking aid is not particularly limited as long as it has been conventionally used in the production of a foam, and for example, divinylbenzene, trimethylolpropane trimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, triallylic acid triallyl ester, triallyl isocyanurate, ethylvinylbenzene, neopentyl glycol dimethacrylate, 1,2,4-benzenetricarboxylic acid triallyl ester, 1,6-hexanediol Examples thereof include dimethacrylate, lauryl methacrylate, stearyl methacrylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate. These may be used alone or in combination of two or more.
[0033]
When the amount of the crosslinking aid added is small, the foamable resin composition may not be able to obtain a degree of crosslinking required during foaming, that is, may not be able to obtain a shear viscosity. Since it may be difficult to control the degree of crosslinking to be applied, the amount is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 8 parts by weight, and more preferably 0.3 to 6 parts by weight based on 100 parts by weight of the polyolefin resin. Part by weight is particularly preferred, and 0.5 to 5 parts by weight is most preferred.
[0034]
Next, the foamable resin molded article is irradiated with ionizing radiation to give a crosslinked structure. At this time, by adding the above-mentioned crosslinking aid to the foamable resin composition, the amount of ionizing radiation applied to the foamable resin molded article is reduced, and the polyolefin resin molecules are cut off by the irradiation of the ionizing radiation. , Deterioration can be prevented.
[0035]
In addition, it does not specifically limit as said ionizing radiation, For example, (alpha) ray, (beta) ray, (gamma) ray, an electron beam etc. can be mentioned, and an electron beam is preferable. Further, when the irradiation amount of the ionizing radiation to the foamable resin molded product is small, it may not be possible to impart the shear viscosity necessary for foaming the foamable resin molded product. Is too high, the foaming property is reduced, the crosslinked polyolefin resin foam having a high expansion ratio cannot be obtained, and the appearance of the crosslinked polyolefin resin foam may also be reduced. 1 to 10 Mrad is preferable, 0.2 to 5 Mrad is more preferable, and 0.5 to 3 Mrad is particularly preferable.
[0036]
Then, the foamable resin molded product crosslinked as described above is heated to a temperature equal to or higher than the decomposition temperature of the thermal decomposition type foaming agent and foamed to obtain a crosslinked polyolefin resin foam.
[0037]
【Example】
(Examples 1 to 4, Comparative Examples 1 to 5)
A predetermined amount of ethylene-propylene random copolymer (ethylene component: 2% by weight, melt index: 0.5 g / 10 min, density: 0.91 g / cm 3 ), homopolypropylene (melt index = 0) shown in Table 1 0.4 g / 10 min, density 0.91 g / cm 3 ), linear low density polyethylene (melt index = 2.1 g / 10 min, density: 0.92 g / cm 3 ), high density polyethylene (melt index = 3) 0.0g / 10 min, density 0.96 g / cc), a block copolymer hydrogenated product in which both end blocks are ethylene polymer blocks and the center block is an ethylene-butylene copolymer block (JSR Co., Ltd.) Manufactured by Dynalon 6200P), 3 parts by weight of divinylbenzene, 13 parts by weight of azodicarbonamide, 2,6-di- 0.3 parts by weight of t-butyl-p-cresol, 0.3 parts by weight of dilaurylthiopropionate and 0.5 parts by weight of methylbenzotriazole are supplied to a single screw extruder and melt-kneaded at a resin temperature of 185 ° C. Thus, a foamable polyolefin-based resin sheet having a thickness of 1 mm was obtained.
[0038]
After irradiating 1.5 Mrad of an electron beam at an accelerating voltage of 700 kV to both sides of the obtained expandable polyolefin resin sheet to crosslink the expandable polyolefin resin sheet, the expandable polyolefin resin sheet is heated to 250 ° C. To obtain a crosslinked polyolefin resin foam.
[0039]
The gel fraction, apparent density, elongation at break and tensile strength at 23 ° C. of the obtained crosslinked polyolefin-based resin foam were measured in the manner shown below at 175 ° C. The results are shown in Table 2.
[0040]
(Gel fraction)
The crosslinked polyolefin-based resin foam was weighed with Ag, immersed in xylene at 120 ° C. for 24 hours, and the insoluble matter was filtered through a 200-mesh wire gauze. It was measured (Bg) and calculated by the following equation.
Gel fraction (% by weight) = (B / A) × 100
[0041]
(Apparent density)
The apparent density of the crosslinked polyolefin resin foam was measured according to JIS K7222.
[0042]
(Elongation at break)
The elongation at break of a crosslinked polyolefin resin foam refers to elongation measured in accordance with JIS K6767 (Method A) except that the set temperature is changed. When left in an oven adjusted to a predetermined temperature, the surface temperature of the crosslinked polyolefin resin foam is measured by a thermo label, and when the elongation at break at 23 ° C. is measured, the crosslinked polyolefin resin foam is used. In the case where the elongation at break at 175 ° C. was measured when the surface temperature became 23 ° C., it was measured when the surface temperature of the crosslinked polyolefin-based resin foam reached 175 ° C.
[0043]
(Tensile strength)
The tensile strength of the crosslinked polyolefin resin foam refers to the tensile strength measured in accordance with JIS K6767 (Method A) except that the set temperature is changed. When left in an oven adjusted to a predetermined temperature, the surface temperature of the crosslinked polyolefin resin foam is measured by a thermo label, and when the tensile strength at 23 ° C. is measured, the crosslinked polyolefin resin foam is When measuring the tensile strength at 175 ° C. when the surface temperature was 23 ° C., it was measured when the surface temperature of the crosslinked polyolefin-based resin foam was 175 ° C.
[0044]
[Table 1]
[Table 2]
【The invention's effect】
The crosslinked polyolefin-based resin foam of the present invention comprises a polyolefin-based resin composed of 40 to 80% by weight of a polypropylene-based resin and 20 to 60% by weight of a polyethylene-based resin, and an ethylene polymer block at both end blocks and a center. Is obtained by crosslinking and foaming a resin composition comprising 1 to 20 parts by weight of a hydrogenated product of a block copolymer which is a conjugated diene-based polymer block. Excellent compatibility with resins by the action of hydrogenated block copolymers having a specific molecular structure, and by effectively exerting the excellent actions of both polypropylene-based and polyethylene-based resins, excellent heat resistance Complicated and beautiful molded product with generality, mechanical strength and flexibility It is possible to reliably obtain.
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