JP2021172748A - Polyethylene-based extrusion foam - Google Patents
Polyethylene-based extrusion foam Download PDFInfo
- Publication number
- JP2021172748A JP2021172748A JP2020078363A JP2020078363A JP2021172748A JP 2021172748 A JP2021172748 A JP 2021172748A JP 2020078363 A JP2020078363 A JP 2020078363A JP 2020078363 A JP2020078363 A JP 2020078363A JP 2021172748 A JP2021172748 A JP 2021172748A
- Authority
- JP
- Japan
- Prior art keywords
- polyethylene
- foam
- resin
- temperature
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006260 foam Substances 0.000 title claims abstract description 169
- -1 Polyethylene Polymers 0.000 title claims abstract description 71
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 44
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 40
- 238000001125 extrusion Methods 0.000 title abstract description 21
- 229920005678 polyethylene based resin Polymers 0.000 claims abstract description 50
- 238000005259 measurement Methods 0.000 claims abstract description 38
- 238000007711 solidification Methods 0.000 claims abstract description 25
- 230000008023 solidification Effects 0.000 claims abstract description 25
- 229920005989 resin Polymers 0.000 claims description 80
- 239000011347 resin Substances 0.000 claims description 80
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 46
- 239000005977 Ethylene Substances 0.000 claims description 46
- 238000005187 foaming Methods 0.000 claims description 29
- 229920001684 low density polyethylene Polymers 0.000 claims description 20
- 239000004702 low-density polyethylene Substances 0.000 claims description 18
- 239000004711 α-olefin Substances 0.000 claims description 7
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 description 37
- 239000004088 foaming agent Substances 0.000 description 32
- 239000002667 nucleating agent Substances 0.000 description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 27
- 239000002994 raw material Substances 0.000 description 26
- 150000003839 salts Chemical class 0.000 description 26
- 239000000203 mixture Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000000463 material Substances 0.000 description 16
- 150000007524 organic acids Chemical class 0.000 description 16
- 229920001577 copolymer Polymers 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000008901 benefit Effects 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000011342 resin composition Substances 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 11
- 235000006708 antioxidants Nutrition 0.000 description 11
- 238000004132 cross linking Methods 0.000 description 11
- 238000000465 moulding Methods 0.000 description 10
- 229920013716 polyethylene resin Polymers 0.000 description 10
- 230000003078 antioxidant effect Effects 0.000 description 9
- 235000014113 dietary fatty acids Nutrition 0.000 description 9
- 239000000194 fatty acid Substances 0.000 description 9
- 229930195729 fatty acid Natural products 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000000155 melt Substances 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 8
- 238000005482 strain hardening Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 238000010899 nucleation Methods 0.000 description 7
- 239000012860 organic pigment Substances 0.000 description 7
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 239000004594 Masterbatch (MB) Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 239000003086 colorant Substances 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920005672 polyolefin resin Polymers 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 150000001451 organic peroxides Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 150000002642 lithium compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 239000007870 radical polymerization initiator Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- DMBUODUULYCPAK-UHFFFAOYSA-N 1,3-bis(docosanoyloxy)propan-2-yl docosanoate Chemical compound CCCCCCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCCCCCC DMBUODUULYCPAK-UHFFFAOYSA-N 0.000 description 2
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 2
- DXCHWXWXYPEZKM-UHFFFAOYSA-N 2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(O)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O DXCHWXWXYPEZKM-UHFFFAOYSA-N 0.000 description 2
- QTWKINKGAHTPFJ-UHFFFAOYSA-N 2-(butan-2-yldisulfanyl)butane Chemical compound CCC(C)SSC(C)CC QTWKINKGAHTPFJ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- CETBSQOFQKLHHZ-UHFFFAOYSA-N Diethyl disulfide Chemical compound CCSSCC CETBSQOFQKLHHZ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 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
- 229920001400 block copolymer Polymers 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012933 diacyl peroxide Substances 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- ALVPFGSHPUPROW-UHFFFAOYSA-N dipropyl disulfide Chemical compound CCCSSCCC ALVPFGSHPUPROW-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N glycerol group Chemical group OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 2
- 239000002524 monosodium citrate Substances 0.000 description 2
- 235000018342 monosodium citrate Nutrition 0.000 description 2
- 230000004899 motility Effects 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920005673 polypropylene based resin Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- VHOCUJPBKOZGJD-UHFFFAOYSA-N triacontanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VHOCUJPBKOZGJD-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- KDGNCLDCOVTOCS-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy propan-2-yl carbonate Chemical compound CC(C)OC(=O)OOC(C)(C)C KDGNCLDCOVTOCS-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VCMZIKKVYXGKCI-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butyl-6-methylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)C(C)(C)C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C)C(C)(C)C)C(C)(C)C VCMZIKKVYXGKCI-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- UJNVTDGCOKFBKM-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)hexane Chemical compound CCCCCC(OOC(C)(C)C)OOC(C)(C)C UJNVTDGCOKFBKM-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- LOMJGCFEVIUZMW-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-(2-ethylhexoxy)-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(OCC(CC)CCCC)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C LOMJGCFEVIUZMW-UHFFFAOYSA-N 0.000 description 1
- MYMKXVFDVQUQLG-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-fluoro-5-methyl-5h-benzo[d][1,3,2]benzodioxaphosphocine Chemical compound CC1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(F)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C MYMKXVFDVQUQLG-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- GAYUSSOCODCSNF-UHFFFAOYSA-N 1-(dodecyldisulfanyl)dodecane Chemical compound CCCCCCCCCCCCSSCCCCCCCCCCCC GAYUSSOCODCSNF-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- ZIMCZOLRXKPXLN-UHFFFAOYSA-N 2,2,4-trimethyl-4-(2,4,4-trimethylpentan-2-yldisulfanyl)pentane Chemical compound CC(C)(C)CC(C)(C)SSC(C)(C)CC(C)(C)C ZIMCZOLRXKPXLN-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- LXWZXEJDKYWBOW-UHFFFAOYSA-N 2,4-ditert-butyl-6-[(3,5-ditert-butyl-2-hydroxyphenyl)methyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O LXWZXEJDKYWBOW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BKCNDTDWDGQHSD-UHFFFAOYSA-N 2-(tert-butyldisulfanyl)-2-methylpropane Chemical compound CC(C)(C)SSC(C)(C)C BKCNDTDWDGQHSD-UHFFFAOYSA-N 0.000 description 1
- XKBHBVFIWWDGQX-UHFFFAOYSA-N 2-bromo-3,3,4,4,5,5,5-heptafluoropent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(Br)=C XKBHBVFIWWDGQX-UHFFFAOYSA-N 0.000 description 1
- OGTZMPFMCIZSIB-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-yldisulfanyl)butane Chemical compound CCC(C)(C)SSC(C)(C)CC OGTZMPFMCIZSIB-UHFFFAOYSA-N 0.000 description 1
- DRDBBZHENIKVRG-UHFFFAOYSA-N 2-n-hexadecylpropane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCNC(C)CN DRDBBZHENIKVRG-UHFFFAOYSA-N 0.000 description 1
- KFXTTZQGCNRYEN-UHFFFAOYSA-N 2-n-octadecylpropane-1,2-diamine Chemical compound CCCCCCCCCCCCCCCCCCNC(C)CN KFXTTZQGCNRYEN-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 description 1
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- CUDSBWGCGSUXDB-UHFFFAOYSA-N Dibutyl disulfide Chemical compound CCCCSSCCCC CUDSBWGCGSUXDB-UHFFFAOYSA-N 0.000 description 1
- ODHAQPXNQDBHSH-UHFFFAOYSA-N Dicyclohexyl disulfide Chemical compound C1CCCCC1SSC1CCCCC1 ODHAQPXNQDBHSH-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
- 241000360590 Erythrites Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 235000021353 Lignoceric acid Nutrition 0.000 description 1
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-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
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite 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
- 238000005299 abrasion Methods 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012753 anti-shrinkage agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- LEDIWWJKWAMGLD-UHFFFAOYSA-N bis(2-methylundecan-2-yl) disulfide Chemical compound CCCCCCCCCC(C)(C)SSC(C)(C)CCCCCCCCC LEDIWWJKWAMGLD-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940105990 diglycerin Drugs 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- PPSZHCXTGRHULJ-UHFFFAOYSA-N dioxazine Chemical compound O1ON=CC=C1 PPSZHCXTGRHULJ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- VPNOHCYAOXWMAR-UHFFFAOYSA-N docosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCCCN VPNOHCYAOXWMAR-UHFFFAOYSA-N 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical class CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical class C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZUNGGJHBMLMRFJ-UHFFFAOYSA-O ethoxy-hydroxy-oxophosphanium Chemical compound CCO[P+](O)=O ZUNGGJHBMLMRFJ-UHFFFAOYSA-O 0.000 description 1
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 1
- WUDNUHPRLBTKOJ-UHFFFAOYSA-N ethyl isocyanate Chemical compound CCN=C=O WUDNUHPRLBTKOJ-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000013538 functional additive Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical class NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- BUHXFUSLEBPCEB-UHFFFAOYSA-N icosan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCCCN BUHXFUSLEBPCEB-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910001872 inorganic gas Inorganic materials 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000006178 methyl benzyl group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YIADEKZPUNJEJT-UHFFFAOYSA-N n-ethyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNCC YIADEKZPUNJEJT-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical class CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical class CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004091 panning Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- JIYXDFNAPHIAFH-UHFFFAOYSA-N tert-butyl 3-tert-butylperoxycarbonylbenzoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC(C(=O)OC(C)(C)C)=C1 JIYXDFNAPHIAFH-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 229920001862 ultra low molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
本発明は、ポリエチレン系押出発泡体に関する。 The present invention relates to a polyethylene-based extruded foam.
ポリエチレン系樹脂発泡体は、柔軟性および耐磨耗性に比較的優れていることから、車両の内装材、工業用断熱材、スポーツ用品、緩衝材（例えば梱包用緩衝材）として広く使用されている。 Polyethylene resin foam is widely used as a vehicle interior material, industrial heat insulating material, sports equipment, and cushioning material (for example, packing cushioning material) because it has relatively excellent flexibility and abrasion resistance. There is.
近年、柔らかい感触を有するなどの理由から、気泡径が微細なポリエチレン系樹脂押出発泡体が求められている。 In recent years, a polyethylene-based resin extruded foam having a fine bubble diameter has been required for reasons such as having a soft feel.
例えば、特許文献１では、樹脂物性の指標の一つとしてひずみ硬化性に着目し、密度９３０〜９６０ｋｇ／ｍ３、メルトフローレート（１９０℃、２．１６ｋｇ荷重）が０．１〜２０ｇ／１０分、伸長粘度測定におけるひずみ硬化度２．０〜３０であるポリエチレン系樹脂組成物を用いた無架橋押出発泡シートが提案されている。
For example,
本発明の目的は、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ないポリエチレン系押出発泡体を提供することである。 An object of the present invention is to provide a polyethylene-based extruded foam having a small average cell diameter, a high closed cell ratio, and few nests.
本発明者らは、前記課題を解決するため鋭意検討した結果、押出発泡の成形時における押出物が固化する段階付近での樹脂物性を制御することで発泡体の諸特性に寄与できる点を見出し、固化温度近傍における樹脂の伸長粘度特性を制御することで、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ない、ポリエチレン系押出発泡体を提供できることに成功し、本発明を完成させるに至った。 As a result of diligent studies to solve the above problems, the present inventors have found that it is possible to contribute to various properties of the foam by controlling the resin physical properties near the stage where the extrusion is solidified during the molding of the extrusion foam. By controlling the extensional viscosity characteristics of the resin in the vicinity of the solidification temperature, we succeeded in providing a polyethylene-based extruded foam having a small average cell diameter, a high closed cell ratio, and few nests, and completed the present invention. It came to.
すなわち、本発明の一実施形態は、以下の構成を含むものである。
［１］ 伸長粘度測定における次の（ａ）および（ｂ）を満たすポリエチレン系樹脂を含有するポリエチレン系押出発泡体；
（ａ）固化温度＋１℃における伸長ひずみ０．５での伸長粘度が２．０Ｅ＋６Ｐａ・ｓ以上である、
（ｂ）伸長ひずみ０．５での伸長粘度が４．０Ｅ＋５Ｐａ・ｓ以上となる温度から、固化温度＋１℃までの温度範囲が４℃以上、９℃以下である。
［２］ 前記ポリエチレン系樹脂が分岐状低密度ポリエチレンを含有する、前記［１］に記載のポリエチレン系押出発泡体。
［３］ 前記分岐状低密度ポリエチレンが、樹脂密度が９１０〜９３５ｋｇ／ｍ３であり、かつ、ＭＦＲが０．１〜１０ｇ／１０ｍｉｎである、前記［２］に記載のポリエチレン系押出発泡体。
［４］ 前記ポリエチレン系樹脂が、さらに、樹脂密度が８７０〜９２０ｋｇ／ｍ３であり、かつ、ＭＦＲが０．５〜２０ｇ／１０ｍｉｎであるエチレン／α−オレフィン共重合体を含有する、前記［２］または［３］に記載のポリエチレン系押出発泡体。
［５］ 前記ポリエチレン系樹脂が、有機過酸化物からなる構成単位を含む、前記［１］〜［４］のいずれか一項に記載のポリエチレン系押出発泡体。
［６］ 前記ポリエチレン系押出発泡体の厚みが１０〜１６０ｍｍである、前記［１］〜［５］５のいずれか一項に記載のポリエチレン系押出発泡体。
［７］ 前記ポリエチレン系押出発泡体の発泡倍率が４〜３５倍である、前記［１］〜［６］のいずれか一項に記載のポリエチレン系樹脂押出発泡体。
［８］ 前記前記ポリエチレン系押出発泡体が板状である、前記［１］〜［７］のいずれか一項に記載のポリエチレン系樹脂押出発泡体。
That is, one embodiment of the present invention includes the following configurations.
[1] A polyethylene-based extruded foam containing a polyethylene-based resin that satisfies the following (a) and (b) in the extensional viscosity measurement;
(A) The extensional viscosity at an extensional strain of 0.5 at a solidification temperature of + 1 ° C. is 2.0E + 6Pa · s or more.
(B) The temperature range from the temperature at which the extensional viscosity at an extension strain of 0.5 is 4.0 E + 5 Pa · s or more to the solidification temperature + 1 ° C. is 4 ° C. or more and 9 ° C. or less.
[2] The polyethylene-based extruded foam according to the above [1], wherein the polyethylene-based resin contains branched low-density polyethylene.
[3] The polyethylene-based extruded foam according to the above [2], wherein the branched low-density polyethylene has a resin density of 910 to 935 kg / m3 and an MFR of 0.1 to 10 g / 10 min.
[4] The polyethylene-based resin further contains an ethylene / α-olefin copolymer having a resin density of 870 to 920 kg / m3 and an MFR of 0.5 to 20 g / 10 min. ] Or [3]. The polyethylene-based extruded foam.
[5] The polyethylene-based extruded foam according to any one of the above [1] to [4], wherein the polyethylene-based resin contains a structural unit composed of an organic peroxide.
[6] The polyethylene-based extruded foam according to any one of [1] to [5] 5, wherein the polyethylene-based extruded foam has a thickness of 10 to 160 mm.
[7] The polyethylene-based resin extruded foam according to any one of the above [1] to [6], wherein the polyethylene-based extruded foam has a foaming ratio of 4 to 35 times.
[8] The polyethylene-based resin extruded foam according to any one of the above [1] to [7], wherein the polyethylene-based extruded foam is plate-shaped.
本発明によれば、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ない、ポリエチレン系押出発泡体を提供できる、という効果を奏する。 According to the present invention, it is possible to provide a polyethylene-based extruded foam having a small average cell diameter, a high closed cell ratio, and few nests.
本発明の一実施形態について以下に説明するが、本発明はこれに限定されるものではない。本発明は、以下に説明する各構成に限定されるものではなく、請求の範囲に示した範囲で種々の変更が可能である。また、異なる実施形態または実施例にそれぞれ開示された技術的手段を適宜組み合わせて得られる実施形態または実施例についても、本発明の技術的範囲に含まれる。更に、各実施形態にそれぞれ開示された技術的手段を組み合わせることにより、新しい技術的特徴を形成することができる。なお、本明細書中に記載された学術文献および特許文献の全てが、本明細書中において参考文献として援用される。 An embodiment of the present invention will be described below, but the present invention is not limited thereto. The present invention is not limited to the configurations described below, and various modifications can be made within the scope of the claims. The technical scope of the present invention also includes embodiments or examples obtained by appropriately combining the technical means disclosed in the different embodiments or examples. Furthermore, new technical features can be formed by combining the technical means disclosed in each embodiment. In addition, all the academic documents and patent documents described in the present specification are incorporated as references in the present specification.
本明細書において特記しない限り、数値範囲を表す「Ａ〜Ｂ」は、「Ａ以上（Ａを含みかつＡより大きい）Ｂ以下（Ｂを含みかつＢより小さい）」を意図する。 Unless otherwise specified in the present specification, "A to B" representing a numerical range is intended to be "A or more (including A and larger than A) and B or less (including B and smaller than B)".
本明細書において特記しない限り、構成単位として、Ｘ１単量体に由来する構成単位と、Ｘ２単量体に由来する構成単位と、・・・およびＸｎ単量体（ｎは２以上の整数）に由来する構成単位とを含む共重合体を、Ｘ１／Ｘ２／・・・／Ｘｎ共重合体とも称する。Ｘ１／Ｘ２／・・・／Ｘｎ共重合体としては、明示されている場合を除き、重合様式は特に限定されず、ランダム共重合体であってもよく、ブロック共重合体であってもよく、グラフト共重合体であってもよい。また、Ｘ単量体に由来する構成単位を「Ｘ単位」と称する場合もある。 Unless otherwise specified in the present specification, the structural units include a structural unit derived from an X1 monomer, a structural unit derived from an X2 monomer, ..., And an Xn monomer (n is an integer of 2 or more). A copolymer containing a structural unit derived from the above is also referred to as an X1 / X2 / ... / Xn copolymer. Unless otherwise specified, the X1 / X2 / ... / Xn copolymer is not particularly limited in the polymerization mode, and may be a random copolymer or a block copolymer. , It may be a graft copolymer. Further, the structural unit derived from the X monomer may be referred to as "X unit".
〔本発明の技術的思想〕
本発明者らが鋭意検討した結果、上述した特許文献１に記載の技術には、以下に示すような改善の余地または問題点があることを見出した。
[Technical Idea of the Present Invention]
As a result of diligent studies by the present inventors, it has been found that the technique described in
押出発泡においては、発泡時の樹脂粘度のコントロールが非常に重要であることは分かっているが、具体的にどの樹脂物性をどのようにコントロールすれば良いのかは分かっていないという問題がある。 In extrusion foaming, it is known that control of the resin viscosity at the time of foaming is very important, but there is a problem that it is not known specifically which resin physical characteristics should be controlled and how.
特許文献１では、均一な気泡膜と独立した気泡を保持した発泡体を得るためにひずみ硬化度の大きなポリエチレン系樹脂組成物を用いることが提案されている。
しかし、特許文献１に記載の技術のように、ひずみ硬化性に着目し、大きなひずみ硬化度を有する樹脂を検討したところ、高い溶融張力を有し、また大きなスウェル比を示し、ひずみ硬化度以外の押出発泡に適すると言われている溶融特性も有しているものであっても、得られる発泡体が独立気泡率に劣る傾向が見られ、さらに、押出機内で樹脂溶融物の温度を樹脂が結晶化する温度ぎりぎりまで降温させた場合に、樹脂溶融物中の一部の樹脂が結晶化し、得られる発泡体に当該結晶化部を核として巨大気泡（巣）が発生するという問題があった。中でも、厚みのある板状発泡体を得ようとする場合、小さい平均気泡径、および、高い独立気泡率、かつ少ない巣を達成することが困難であることが分った。そのため、押出発泡に適すると言われていた樹脂の溶融特性であっても、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ないポリエチレン系押出発泡体を提供するには改良の余地があり、特に、厚さが大きい板状の発泡体を製造するためには、用いるポリエチレン系樹脂の溶融特性を精密に制御する必要がある。
However, when a resin having a large strain curability was examined by paying attention to the strain curability as in the technique described in
一般的に、発泡性には伸長粘度測定時のひずみ硬化度が重要であると言われているが、従来のひずみ硬化度は樹脂が完全に溶融している温度で測定されている。一方、実際の押出発泡においては、ダイスから吐出される樹脂は、固化寸前にまで冷却された樹脂であり、大気圧下に開放された後には、さらに樹脂温度は下がり、気泡膜が固化し安定化する温度まで低下する。従来のひずみ硬化度では、この固化近傍の樹脂特性を示すことができるものではなかった。溶融張力、及びスウェル比についても同様である。従来の測定温度と固化近傍の温度との差が樹脂特性に与える影響としては、次のように考えらえる。従来の伸長粘度測定の温度域で伸長変形が発生した場合には、高分子鎖の枝部分の絡み合いは緩和時間が短いため、ひずみ硬化性を示すような絡み合いとして作用しない。一方、固化近傍の温度においては、高分子の運動性が大きく低下するため、緩和しない絡み合いとして作用し始める。つまり、従来の測定温度では、こういった温度低下による高分子の運動性の変化について評価できない。 Generally, it is said that the degree of strain hardening at the time of measuring the extensional viscosity is important for foamability, but the conventional degree of strain hardening is measured at a temperature at which the resin is completely melted. On the other hand, in actual extrusion foaming, the resin discharged from the die is a resin that has been cooled to just before solidification, and after being released under atmospheric pressure, the resin temperature further drops and the bubble film solidifies and stabilizes. It drops to the temperature at which it becomes plastic. The conventional strain hardening degree could not show the resin characteristics in the vicinity of this solidification. The same applies to the melt tension and the swell ratio. The effect of the difference between the conventional measurement temperature and the temperature near solidification on the resin characteristics can be considered as follows. When elongational deformation occurs in the temperature range of the conventional extensional viscosity measurement, the entanglement of the branch portion of the polymer chain does not act as an entanglement showing strain curability because the relaxation time is short. On the other hand, at a temperature near solidification, the motility of the polymer is greatly reduced, so that it begins to act as an unrelaxed entanglement. That is, the conventional measurement temperature cannot evaluate the change in the motility of the polymer due to such a decrease in temperature.
また、実際の押出発泡を鑑みた場合には、押出された発泡体の中心部と、大気と接するスキン部では、圧力のバランスが異なることが言える。発泡体の中心部においては、同じ内圧を有する気泡同士が隣接して存在するため、気泡の全方位に対して圧力バランスが等しくなるが、スキン部においては、気泡内圧よりも低い大気圧と接する気泡膜が存在することとなり、局所的に圧力バランスが保たれない箇所が存在する。このような圧力バランスが保たれない箇所においては、局所的な応力がかかり易くなり、気泡膜に局所的に大きな伸長変形が発生して破泡しやすくなる。局所的に大きな伸長変形を引き起こさないためには、一般的に重要と言われている変形終期のひずみ硬化度よりも、変形初期から伸長粘度が上昇していくことが重要であると考える。変形初期から伸長粘度が上昇していけば、局所的な変形が発生する状況となった場合でも、変形初期から変形した箇所の粘度が上昇するため、局所的な変形が効果的に抑制され均一な膜となり易く、気泡膜の破泡を抑制できる。 Further, when considering the actual extruded foaming, it can be said that the pressure balance is different between the central portion of the extruded foam and the skin portion in contact with the atmosphere. In the central part of the foam, bubbles having the same internal pressure are adjacent to each other, so that the pressure balance is equal in all directions of the bubbles, but in the skin part, the bubbles come into contact with the atmospheric pressure lower than the internal pressure of the bubbles. The bubble film is present, and there are places where the pressure balance cannot be maintained locally. In such a place where the pressure balance is not maintained, local stress is likely to be applied, and large elongation deformation is locally generated in the bubble film, so that bubbles are likely to break. In order not to cause large elongational deformation locally, it is important that the extensional viscosity increases from the initial stage of deformation rather than the strain hardening degree at the final stage of deformation, which is generally said to be important. If the extensional viscosity increases from the initial stage of deformation, even if local deformation occurs, the viscosity of the deformed part increases from the initial stage of deformation, so that local deformation is effectively suppressed and uniform. It is easy to form a flexible film and can suppress the bubble rupture of the bubble film.
さらに、気泡径が小さなもの、つまり気泡核点が多く、核点への発泡剤の流入が速い場合には、発泡速度が速くなり、より局所的な変形が起こりやすくなるため、変形初期の伸長粘度特性が重要であると考えられる。 Furthermore, when the bubble diameter is small, that is, when there are many bubble core points and the foaming agent flows into the core points quickly, the foaming rate becomes high and more local deformation is likely to occur, so that the elongation at the initial stage of deformation is achieved. Viscosity properties are considered important.
以上のことから、特許文献１に記載のような従来のひずみ硬化度の制御では、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ないポリエチレン系押出発泡体を得るには不十分であると考える。
From the above, the conventional control of strain hardening degree as described in
本発明者らは、用いる樹脂の固化近傍での伸長粘度特性を精密に制御することにより、課題であった高い独立気泡率に加えて、小さい平均気泡径および巣が少ないことを達成し得るポリエチレン系押出発泡体を提供できることを独自に見出し、本発明を完成させるに至った。 By precisely controlling the extensional viscosity characteristics of the resin used in the vicinity of solidification, the present inventors can achieve a small average cell diameter and a small number of nests in addition to the high closed cell ratio, which has been a problem. We have independently found that we can provide a system-based extruded foam, and have completed the present invention.
〔ポリエチレン系樹脂〕
本発明の一実施形態に係るポリエチレン系発泡体は、伸長粘度測定における次の（ａ）および（ｂ）を満たすポリエチレン系樹脂を含有することを特徴とする；
（ａ）固化温度＋１℃における伸長ひずみ０．５での伸長粘度が２．０Ｅ＋６Ｐａ・ｓ以上である、
（ｂ）伸長ひずみ０．５での伸長粘度が４．０Ｅ＋５Ｐａ・ｓ以上となる温度から、固化温度＋１℃までの温度範囲が４℃以上、９℃以下である。
[Polyethylene resin]
The polyethylene-based foam according to the embodiment of the present invention is characterized by containing a polyethylene-based resin that satisfies the following (a) and (b) in the extensional viscosity measurement;
(A) The extensional viscosity at an extensional strain of 0.5 at a solidification temperature of + 1 ° C. is 2.0E + 6Pa · s or more.
(B) The temperature range from the temperature at which the extensional viscosity at an extension strain of 0.5 is 4.0 E + 5 Pa · s or more to the solidification temperature + 1 ° C. is 4 ° C. or more and 9 ° C. or less.
「ポリエチレン系樹脂板状発泡体」を「発泡体」と称する場合もある。「本発明の一実施形態に係るポリエチレン系樹脂板状発泡体」を、「本発泡体」と称する場合もある。 The "polyethylene resin plate-like foam" may be referred to as a "foam". The "polyethylene resin plate-like foam according to one embodiment of the present invention" may be referred to as the "present foam".
本発泡体は、前記構成を有するため、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ない。 Since this foam has the above-mentioned structure, the average cell diameter is small, the closed cell ratio is high, and the number of nests is small.
上述したとおり、押出発泡において、発泡させる時の樹脂温度は、樹脂が結晶固化するぎりぎりの温度であることから、固化寸前での伸長粘度特性を知ることが重要である。また、平均気泡径が小さく、発泡速度が速いものについては、変形初期の伸長粘度の大きさが重要である。さらに、固化寸前においても気泡膜が容易に破断せずに伸びる特性も重要となる。 As described above, in extrusion foaming, the resin temperature at the time of foaming is the temperature at which the resin crystallizes and solidifies, so it is important to know the extensional viscosity characteristics on the verge of solidification. Further, for those having a small average cell diameter and a high foaming rate, the magnitude of the extensional viscosity at the initial stage of deformation is important. Further, the property that the bubble film is stretched without being easily broken even on the verge of solidification is also important.
これらの観点から伸長粘度特性を整理した結果、ポリエチレン系樹脂が、（ａ）固化温度＋１℃における伸長ひずみ０．５での伸長粘度が２．０Ｅ＋６Ｐａ・s以上であり、（ｂ）伸長ひずみ０．５での伸長粘度の値が４．０Ｅ＋５Ｐａ・ｓ以上となる温度から固化温度＋１℃までの温度範囲（以下、単に「伸長粘度が急上昇する温度範囲」と称することがある。）が４℃以上、９℃以下である場合に、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ないポリエチレン系押出発泡体を得ることができることを、本発明者らは独自に見出した。 As a result of arranging the extensional viscosity characteristics from these viewpoints, the polyethylene-based resin has (a) an extensional viscosity of 2.0E + 6Pa · s or more at an extensional strain of 0.5 at a solidification temperature of + 1 ° C., and (b) an extensional strain of 0. The temperature range from the temperature at which the extensional viscosity value at .5 is 4.0 E + 5 Pa · s or more to the solidification temperature + 1 ° C. (hereinafter, may be simply referred to as “the temperature range in which the extensional viscosity rapidly increases”) is 4 ° C. As described above, the present inventors have independently found that a polyethylene-based extruded foam having a small average cell diameter, a high closed cell ratio, and few nests can be obtained when the temperature is 9 ° C. or lower.
本発明のポリエチレン系樹脂は、伸長粘度の測定において、固化温度＋１℃で伸長ひずみ０．５における伸長粘度が２．０Ｅ＋６Ｐａ・s以上であり、好ましくは２．３Ｅ＋６Ｐａ・s以上であり、より好ましくは２．５Ｅ＋６Ｐａ・s以上である。伸長ひずみ０．５における伸長粘度が２．０Ｅ＋６Ｐａ・s以上であることにより、平均気泡径が小さい場合においても高い独立気泡率の発泡体が得られ易い。また、本発明のポリエチレン系樹脂は、固化温度＋１℃での伸長ひずみ０．５における伸長粘度が、好ましくは１．０Ｅ＋７Ｐａ・s以下であり、より好ましくは８．０Ｅ＋６Ｐａ・s以下であり、さらに好ましくは６．０Ｅ＋６Ｐａ・s以下である。伸長ひずみ０．５における伸長粘度が１．０Ｅ＋７Ｐａ・s以下であることにより、均一な気泡構造の発泡体が得られ易い。 In the measurement of the extensional viscosity, the polyethylene-based resin of the present invention has an extensional viscosity of 2.0E + 6Pa · s or more, preferably 2.3E + 6Pa · s or more, more preferably 2.3E + 6Pa · s or more at a solidification temperature of + 1 ° C. and an extensional strain of 0.5. Is 2.5E + 6Pa · s or more. Since the extensional viscosity at an extensional strain of 0.5 is 2.0E + 6Pa · s or more, a foam having a high closed cell ratio can be easily obtained even when the average cell diameter is small. Further, the polyethylene-based resin of the present invention has an extensional viscosity at an extensional strain of 0.5 at a solidification temperature of + 1 ° C., preferably 1.0E + 7Pa · s or less, more preferably 8.0E + 6Pa · s or less, and further. It is preferably 6.0E + 6Pa · s or less. When the extensional viscosity at an extensional strain of 0.5 is 1.0E + 7Pa · s or less, a foam having a uniform bubble structure can be easily obtained.
また、伸長ひずみ０．５での伸長粘度が４．０Ｅ＋５Ｐａ・ｓ以上となる温度から、固化温度＋１℃までの温度範囲がが４℃以上、９℃以下であり、好ましくは４℃以上、８℃以下である。上記構成であることにより、板状発泡体とした時においても独立気泡率の高い発泡体が得られ易く、巣の発生もない発泡体が得られ易い。 Further, the temperature range from the temperature at which the extensional viscosity at an extension strain of 0.5 is 4.0 E + 5 Pa · s or more to the solidification temperature + 1 ° C. is 4 ° C. or higher and 9 ° C. or lower, preferably 4 ° C. or higher and 8 ° C. It is below ° C. With the above configuration, it is easy to obtain a foam having a high closed cell ratio even when it is made into a plate-shaped foam, and it is easy to obtain a foam without nesting.
すなわち、ポリエチレン系樹脂の発泡性の指標として、固化温度近傍の伸長粘度測定から得られる上記要件（ａ）および（ｂ）に着目することが有効であることを、本発明者らは独自に見出した。上記要件（ａ）および（ｂ）を満たすポリエチレン系樹脂は、平均気泡径が小さい場合においても幅広い温度域で発泡の状態が良好となるため、独立気泡率が高く、かつ巣が少ないポリエチレン系樹脂板状発泡体を得ることが可能となる。ここで、上記要件（ａ）および（ｂ）の測定方法は後述する。 That is, the present inventors have independently found that it is effective to pay attention to the above requirements (a) and (b) obtained from the measurement of the extensional viscosity near the solidification temperature as an index of the foamability of the polyethylene resin. rice field. The polyethylene-based resin that satisfies the above requirements (a) and (b) has a high closed cell ratio and few nests because the foaming state is good in a wide temperature range even when the average cell diameter is small. It becomes possible to obtain a plate-shaped foam. Here, the measurement methods of the above requirements (a) and (b) will be described later.
本発泡体において、ポリエチレン系樹脂は上記（ａ）および（ｂ）を満たすものであれば、特に限定されず、例えば、エチレン成分単位が５０モル％以上の樹脂が挙げられ、高密度ポリエチレン、分岐状低密度ポリエチレン、直鎖状低密度ポリエチレン、超低密度ポリエチレン、エチレン−酢酸ビニル共重合体、エチレン−プロピレン共重合体、エチレン−プロピレン−ブテン−１共重合体、エチレン−ブテン−１共重合体、エチレン−ヘキセン−１共重合体、エチレン−４−メチルペンテン−１共重合体、エチレン−オクテン−１共重合体等が例示される。これらは一種のみであってもよいし、２種以上を組み合わせてもよい。 In the present foam, the polyethylene-based resin is not particularly limited as long as it satisfies the above (a) and (b), and examples thereof include resins having an ethylene component unit of 50 mol% or more, high-density polyethylene, and branched. Low density polyethylene, linear low density polyethylene, ultra low density polyethylene, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, ethylene-butene-1 copolymer Examples thereof include coalescence, ethylene-hexene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-octene-1 copolymer and the like. These may be only one kind, or two or more kinds may be combined.
（分岐状低密度ポリエチレン）
本発泡体において、ポリエチレン系樹脂は、押出発泡性の観点から、長鎖分岐を有する分岐状低密度ポリエチレン（以下、「エチレン系重合体（Ａ）」と称することがある。）を含有することが好ましい。一般的に、分岐状低密度ポリエチレンは、「ＬＤＰＥ」と称される場合もある。
(Branched low density polyethylene)
In the present foam, the polyethylene-based resin contains branched low-density polyethylene having long-chain branches (hereinafter, may be referred to as "ethylene-based polymer (A)") from the viewpoint of extrusion foamability. Is preferable. Generally, branched low density polyethylene is sometimes referred to as "LDPE".
エチレン系重合体Ａとしては、構成単位として、全構成単位１００モル％中、エチレンに由来する構成単位を５０モル％以上有する、公知の分岐状低密度ポリエチレンを使用できる。エチレン系重合体Ａは、エチレンと共重合可能な他の単量体に由来する構成単位を有していてもよい。エチレン系重合体Ａは、エチレンの単独重合体であってもよく、エチレンとエチレン以外の単量体との共重合体であってもよい。 As the ethylene-based polymer A, a known branched low-density polyethylene having 50 mol% or more of ethylene-derived structural units out of 100 mol% of all structural units can be used as the structural unit. The ethylene-based polymer A may have a structural unit derived from another monomer copolymerizable with ethylene. The ethylene-based polymer A may be a homopolymer of ethylene or a copolymer of ethylene and a monomer other than ethylene.
エチレン系重合体Ａの密度は、９１０ｋｇ／ｍ３〜９３５ｋｇ／ｍ３であることが好ましく、９１１ｋｇ／ｍ３〜９３３ｋｇ／ｍ３であることがより好ましく、９１３ｋｇ／ｍ３〜９２８ｋｇ／ｍ３であることが更に好ましく、９１４ｋｇ／ｍ３〜９２５ｋｇ／ｍ３であることが尚更に好ましく、９１５ｋｇ／ｍ３〜９２３ｋｇ／ｍ３であることが特に好ましい。当該構成によると、製造過程における樹脂溶融物の発泡性と得られる発泡体の耐熱性とのバランスが優れるという利点を有する。 The density of ethylene polymer A is preferably 910kg / m 3 ~935kg / m 3 , more preferably from 911kg / m3~933kg / m3, still to be 913kg / m3~928kg / m3 Preferably, it is 914 kg / m3 to 925 kg / m3, more preferably 915 kg / m3 to 923 kg / m3. According to this configuration, there is an advantage that the balance between the foamability of the resin melt in the manufacturing process and the heat resistance of the obtained foam is excellent.
エチレン系重合体ＡのＭＦＲは特に限定されないが、０．１ｇ／１０分〜１０．０ｇ／１０分が好ましく、０．３ｇ／１０分〜８．０ｇ／１０分がより好ましく、０．３ｇ／１０分〜５．０ｇ／１０分が更に好ましく、０．５ｇ／１０分〜６．０ｇ／１０分が尚更に好ましく、０．８ｇ／１０分〜５．０ｇ／１０分がことさらに好ましく、１．０ｇ／１０分〜４．０ｇ／１０分が特に好ましい。当該構成によると、製造過程における樹脂溶融物は、高い伸長粘度を達成し易く、かつ押出機内での過度なせん断発熱を防止できる。その結果、本発泡体の製造において、押出発泡に適した条件設定が容易となる傾向がある。 The MFR of the ethylene-based polymer A is not particularly limited, but is preferably 0.1 g / 10 minutes to 10.0 g / 10 minutes, more preferably 0.3 g / 10 minutes to 8.0 g / 10 minutes, and 0.3 g / 10 minutes. 10 minutes to 5.0 g / 10 minutes is even more preferable, 0.5 g / 10 minutes to 6.0 g / 10 minutes is even more preferable, and 0.8 g / 10 minutes to 5.0 g / 10 minutes is even more preferable. 0.0 g / 10 minutes to 4.0 g / 10 minutes is particularly preferable. According to this configuration, the resin melt in the manufacturing process can easily achieve high extensional viscosity and can prevent excessive shear heat generation in the extruder. As a result, in the production of the present foam, it tends to be easy to set conditions suitable for extrusion foaming.
なお、本明細書において、エチレン系重合体ＡのＭＦＲは、ＪＩＳ Ｋ−７２１０に準じて、１９０℃、かつ２．１６ｋｇ荷重にて測定を行って得られる値である。 In this specification, the MFR of the ethylene-based polymer A is a value obtained by measuring at 190 ° C. and a load of 2.16 kg according to JIS K-7210.
本発泡体におけるポリエチレン系樹脂１００重量％において、エチレン系重合体Ａを５１〜１００重量％含むことが好ましく、５５〜９５重量％含むことがより好ましく、６０〜９２重量％含むことが更に好ましく、６５〜９０重量％含むことが尚更に好ましく、６８〜８８重量％含むことが殊更に好ましく、７０〜８６重量％含むことが特に好ましい。製造過程における樹脂溶融物が発泡性に優れ易い、という利点を有する。 In 100% by weight of the polyethylene-based resin in the present foam, it is preferable to contain 51 to 100% by weight of the ethylene-based polymer A, more preferably 55 to 95% by weight, further preferably 60 to 92% by weight. It is even more preferably contained in an amount of 65 to 90% by weight, particularly preferably contained in an amount of 68 to 88% by weight, and particularly preferably contained in an amount of 70 to 86% by weight. It has the advantage that the resin melt in the manufacturing process tends to have excellent foamability.
エチレン系重合体Ａとしては、構成単位の組成が同一である１種の重合体を単独で使用してもよく、構成単位の組成が異なる２種以上の重合体を組み合わせて使用してもよい。エチレン系重合体Ａとしては、異なる密度を有する２種以上の重合体を組み合わせて使用してもよく、例えば、異なる密度を有する２種以上の分岐状低密度ポリエチレンを組み合わせて使用してもよい。異なる融点を有する２種以上の分岐状低密度ポリエチレンを組み合わせて使用してもよい。また、異なるＭＦＲを有する２種以上の分岐状低密度ポリエチレンを組み合わせて使用してもよい。 As the ethylene-based polymer A, one kind of polymer having the same composition of the constituent units may be used alone, or two or more kinds of polymers having different constituent units may be used in combination. .. As the ethylene-based polymer A, two or more kinds of polymers having different densities may be used in combination, and for example, two or more kinds of branched low-density polyethylenes having different densities may be used in combination. .. Two or more kinds of branched low density polyethylene having different melting points may be used in combination. Further, two or more kinds of branched low-density polyethylenes having different MFRs may be used in combination.
（エチレン系重合体Ｂ）
本発泡体におけるポリエチレン系樹脂は、エチレン系重合体Ａを含む実施形態の一つとして、エチレン／α−オレフィン共重合体（以下、「エチレン系重合体Ｂ」と称することがある。）を併用することが好ましい。発泡体を所望の独立気泡率および平均気泡径に調整しやすく、巣の発生を低減し易くなる。エチレン系重合体Ｂとしては、構成単位として、エチレンに由来する構成単位が５０モル％以上、およびα−オレフィンに由来する構成単位が５０モル％以下である限り、その他の構成は特に限定されない。エチレン系重合体Ｂは、エチレンと共重合可能な他の単量体に由来する構成単位を有していてもよい。
(Ethylene polymer B)
The polyethylene-based resin in the present foam is used in combination with an ethylene / α-olefin copolymer (hereinafter, may be referred to as “ethylene-based polymer B”) as one of the embodiments containing the ethylene-based polymer A. It is preferable to do so. It is easy to adjust the foam to the desired closed cell ratio and average cell diameter, and it is easy to reduce the generation of nests. The composition of the ethylene-based polymer B is not particularly limited as long as the composition unit derived from ethylene is 50 mol% or more and the composition unit derived from α-olefin is 50 mol% or less. The ethylene-based polymer B may have a structural unit derived from another monomer copolymerizable with ethylene.
本発泡体におけるポリエチレン系樹脂１００重量％において、エチレン系重合体Ｂを０〜４０重量％含むことが好ましく、５〜４５重量％含むことがより好ましく、８〜４０重量％含むことが更に好ましく、１０〜３５重量％含むことが尚更に好ましく、１２〜３２重量％含むことが殊更に好ましく、１４〜３０重量％含むことが特に好ましい。製造過程における樹脂溶融物が発泡性に優れ易い、という利点を有する。 The polyethylene-based polymer B is preferably contained in an amount of 0 to 40% by weight, more preferably 5 to 45% by weight, still more preferably 8 to 40% by weight, based on 100% by weight of the polyethylene-based resin in the present foam. It is even more preferably contained in an amount of 10 to 35% by weight, particularly preferably contained in an amount of 12 to 32% by weight, and particularly preferably contained in an amount of 14 to 30% by weight. It has the advantage that the resin melt in the manufacturing process tends to have excellent foamability.
本発泡体において、ポリエチレン系樹脂が、エチレン系重合体Ａ、または、エチレン系重合体Ａおよびエチレン系重合体Ｂを含有する場合、ポリエチレン系樹脂１００重量％において、エチレン系重合体Ａ、または、エチレン系重合体Ａおよびエチレン系重合体Ｂが５５〜１００重量％含むことが好ましく、６０〜１００重量％含むことがより好ましく、６５〜１００重量％含むことが更に好ましく、７０〜１００重量％含むことが尚更に好ましく、７５〜１００重量％含むことが殊更に好ましく、８０〜１００重量％含むことが特に好ましい。なお、ポリエチレン系樹脂が上記要件（ａ）および（ｂ）を満たす限り、エチレン系重合体Ａおよびエチレン系重合体Ｂ以外のエチレン系重合体を含んでもよい。上述したエチレン系重合体以外のエチレン系重合体としては、高密度ポリエチレン、エチレン／酢酸ビニル共重合体、スチレン改質ポリエチレン系重合体、塩素化ポリエチレンなどが挙げられる。 In the present foam, when the polyethylene-based resin contains the ethylene-based polymer A or the ethylene-based polymer A and the ethylene-based polymer B, the ethylene-based polymer A or the ethylene-based polymer A or 100% by weight of the polyethylene-based resin is used. The ethylene-based polymer A and the ethylene-based polymer B are preferably contained in an amount of 55 to 100% by weight, more preferably 60 to 100% by weight, still more preferably 65 to 100% by weight, and containing 70 to 100% by weight. Even more preferably, it is particularly preferably contained in an amount of 75 to 100% by weight, and particularly preferably 80 to 100% by weight. As long as the polyethylene-based resin satisfies the above requirements (a) and (b), an ethylene-based polymer other than the ethylene-based polymer A and the ethylene-based polymer B may be contained. Examples of ethylene-based polymers other than the above-mentioned ethylene-based polymers include high-density polyethylene, ethylene / vinyl acetate copolymers, styrene-modified polyethylene-based polymers, and chlorinated polyethylene.
（その他の樹脂）
本発泡体は、上述したポリエチレン系樹脂以外に、その他の樹脂を含んでいてもよい。その他の樹脂としては、（ａ）上述したポリエチレン系樹脂以外のポリオレフィン系樹脂、および（ｂ）ポリオレフィン系樹脂以外の合成樹脂などが挙げられる。本明細書において、上述したポリエチレン系樹脂とその他の樹脂とを合わせて「原料樹脂」と称する場合もある。
(Other resins)
The present foam may contain other resins in addition to the polyethylene-based resin described above. Examples of other resins include (a) polyolefin resins other than the above-mentioned polyethylene resins, and (b) synthetic resins other than polyolefin resins. In the present specification, the polyethylene-based resin described above and other resins may be collectively referred to as a "raw material resin".
上述したポリエチレン系樹脂以外のポリオレフィン系樹脂としては、ポリプロピレン系樹脂などが挙げられる。ポリプロピレン系樹脂としては、ポリプロピレン単独重合体、ポリプロピレン／エチレンブロック共重合体、ポリプロピレン／エチレンランダム共重合体、プロピレン／α−オレフィン共重合体、プロピレン／１−ブテン共重合体、エチレン／１−ブテン／プロピレン共重合体、プロピレン／塩素化ビニル共重合体、プロピレン／無水マレイン酸共重合体、高い溶融張力を有する長鎖分岐ポリプロピレン、イソプレン変性ポリプロピレン、超高分子量成分を含むポリプロピレンなどが挙げられる。 Examples of the polyolefin-based resin other than the polyethylene-based resin described above include polypropylene-based resins. Examples of polypropylene-based resins include polypropylene homopolymers, polypropylene / ethylene block copolymers, polypropylene / ethylene random copolymers, propylene / α-olefin copolymers, propylene / 1-butene copolymers, and ethylene / 1-butene. Examples thereof include / propylene copolymer, propylene / vinyl chlorinated copolymer, propylene / maleic anhydride copolymer, long-chain branched polypropylene having high melt tension, isoprene-modified polypropylene, and polypropylene containing an ultra-high molecular weight component.
ポリオレフィン系樹脂以外の合成樹脂としては、例えば、（ａ）酢酸ビニル系樹脂、ポリエステル樹脂、アクリル樹脂、アクリル酸エステル樹脂、スチレン系樹脂、ポリアミド樹脂、ポリカーボネート樹脂、ポリ塩化ビニル樹脂等の熱可塑性樹脂、（ｂ）ポリアミド／ポリオール共重合体等のポリアミド系エラストマー、および（ｃ）ポリ塩化ビニル系エラストマー、ポリブタジエン系エラストマー、エチレン／プロピレンゴム、エチレン／プロピレン／ブタジエンゴム等の熱可塑性エラストマー、等が挙げられる。 Examples of synthetic resins other than polyolefin resins include (a) thermoplastic resins such as vinyl acetate resin, polyester resin, acrylic resin, acrylic acid ester resin, styrene resin, polyamide resin, polycarbonate resin, and polyvinyl chloride resin. , (B) Polyamide-based elastomers such as polyamide / polyol copolymers, and (c) Polyvinyl chloride-based elastomers, polybutadiene-based elastomers, ethylene / propylene rubbers, thermoplastic elastomers such as ethylene / propylene / butadiene rubbers, and the like. Be done.
原料樹脂は、原料樹脂１００重量％中、上述したポリエチレン系樹脂を５０重量％以上含むことが好ましく、６０重量％以上含むことがより好ましく、７０重量％以上含むことがより好ましく、７５重量％以上含むことがより好ましく、８０重量％以上含むことがより好ましく、８５重量％以上含むことがさらに好ましい。当該構成によると、溶融物が発泡性に優れ、かつ得られる発泡体は柔軟性を有するため緩衝材として好適に使用可能である。 The raw material resin preferably contains 50% by weight or more of the above-mentioned polyethylene-based resin, more preferably 60% by weight or more, more preferably 70% by weight or more, and 75% by weight or more, based on 100% by weight of the raw material resin. It is more preferably contained, more preferably 80% by weight or more, and further preferably 85% by weight or more. According to this structure, the melt has excellent foamability, and the obtained foam has flexibility, so that it can be suitably used as a cushioning material.
原料樹脂が複数種の樹脂を含んでいる場合、発泡体を解析することによって、原料樹脂に含まれる樹脂の種類および含有比率を特定することができる場合もある。また、発泡体を再度樹脂の状態に戻し、伸長粘度特性を評価することも可能である。 When the raw material resin contains a plurality of types of resins, it may be possible to identify the type and content ratio of the resin contained in the raw material resin by analyzing the foam. It is also possible to return the foam to the resin state again and evaluate the extensional viscosity characteristics.
（その他添加剤）
本発泡体は、必要に応じて、気泡核形成剤、気泡核形成補助剤、耐候剤、酸化防止剤、収縮防止剤、結晶造核剤、熱安定剤、帯電防止剤、導電性付与剤、難燃剤等の機能性添加剤、滑剤、無機充填剤、着色剤（例えば顔料）などのその他添加剤をさらに含んでいてもよい。
(Other additives)
This foam can be used as a bubble nucleating agent, a bubble nucleating auxiliary agent, a weather resistant agent, an antioxidant, an antioxidant, a crystal nucleating agent, a heat stabilizer, an antistatic agent, a conductivity-imparting agent, and the like. It may further contain functional additives such as flame retardants, lubricants, inorganic fillers, and other additives such as colorants (eg pigments).
（気泡核形成剤）
気泡核形成剤としては、熱分解型発泡剤、有機酸（塩）および無機物（例えばタルクなど）などが挙げられる。本明細書において、「有機酸（塩）」とは「有機酸および／または有機酸塩」を意味する。気泡核形成剤は、熱分解型発泡剤および／または有機酸（塩）を含むことが好ましい。気泡核形成剤が熱分解型発泡剤および／または有機酸（塩）を含む場合、気泡核形成剤が熱分解型発泡剤および／または有機酸（塩）を含まず無機物（例えばタルクなど）のみを含む場合と比較して、得られる発泡体の気泡径をより容易に小さくすることができる。気泡核形成剤は、熱分解型発泡剤および有機酸（塩）を含むことがより好ましく、熱分解型発泡剤と有機酸（塩）との混合物からなることがさらに好ましい。
(Bubble nucleating agent)
Examples of the bubble nucleating agent include a pyrolytic foaming agent, an organic acid (salt) and an inorganic substance (for example, talc). As used herein, the term "organic acid (salt)" means "organic acid and / or organic acid salt". The bubble nucleating agent preferably contains a pyrolytic foaming agent and / or an organic acid (salt). If the bubble nucleating agent contains a pyrolysis foaming agent and / or an organic acid (salt), the bubble nucleating agent does not contain a pyrolysis foaming agent and / or an organic acid (salt) and is only an inorganic substance (eg, talc). The bubble diameter of the obtained foam can be made smaller more easily than in the case of containing. The bubble nucleating agent more preferably contains a pyrolysis-type foaming agent and an organic acid (salt), and further preferably consists of a mixture of a pyrolysis-type foaming agent and an organic acid (salt).
熱分解型発泡剤としては、例えば、ＡＤＣＡ（アゾジカルボンアミド）、ＤＰＴ（Ｎ，Ｎ’−ジニトロペンタメチレンテトラミン）、ＯＢＳＨ（４，４’−オキシビスベンゼンスルホニルヒドラジド）、炭酸水素塩、炭酸塩等が挙げられる。熱分解型発泡剤としては、炭酸水素塩、炭酸塩、または炭酸水素塩と炭酸塩との混合物、が好ましい。炭酸水素塩としては、例えば、炭酸水素ナトリウムが挙げられる。 Examples of the pyrolytic foaming agent include ADCA (azodicarbonamide), DPT (N, N'-dinitropentamethylenetetramine), OBSH (4,4'-oxybisbenzenesulfonyl hydrazide), bicarbonate, and carbonate. And so on. As the pyrolytic foaming agent, a hydrogen carbonate, a carbonate, or a mixture of a hydrogen carbonate and a carbonate is preferable. Examples of the hydrogen carbonate include sodium hydrogen carbonate.
有機酸（塩）としては、シュウ酸（塩）、乳酸（塩）、コハク酸（塩）、リンゴ酸（塩）、クエン酸（塩）などが挙げられる。気泡径の微細化効果が高いことから、有機酸（塩）としては、クエン酸（塩）が好ましい。クエン酸（塩）としては、クエン酸、クエン酸モノナトリウム、クエン酸トリナトリウム、クエン酸水素ナトリウム、クエン酸カリウム等が挙げられる。 Examples of the organic acid (salt) include oxalic acid (salt), lactic acid (salt), succinic acid (salt), malic acid (salt), citric acid (salt) and the like. Citric acid (salt) is preferable as the organic acid (salt) because the effect of refining the bubble diameter is high. Examples of citric acid (salt) include citric acid, monosodium citrate, trisodium citrate, sodium hydrogen citrate, potassium citrate and the like.
気泡核形成剤としては、取り扱いが容易であり、かつ気泡核の生成効果が高いことから、炭酸水素塩とクエン酸（塩）との混合物、炭酸塩とクエン酸（塩）との混合物、および炭酸水素塩および炭酸塩とクエン酸（塩）との混合物からなる群より選択される１種以上の混合物が好ましく、炭酸水素塩とクエン酸塩との混合物がより好ましく、炭酸水素ナトリウムとクエン酸モノナトリウムとの混合物が特に好ましい。 As a bubble nucleating agent, since it is easy to handle and has a high effect of forming bubble nuclei, a mixture of bicarbonate and citric acid (salt), a mixture of carbonate and citric acid (salt), and One or more mixtures selected from the group consisting of bicarbonates and mixtures of carbonates and citric acid (salts) are preferred, mixtures of bicarbonate and citrate are more preferred, sodium hydrogen carbonate and citric acid. A mixture with monosodium is particularly preferred.
気泡核形成剤における熱分解型発泡剤と有機酸（塩）との含有比率は、熱分解型発泡剤および有機酸（塩）の総量を１００重量％とすると、熱分解型発泡剤が１０重量％〜９０重量％および有機酸（塩）が９０重量％〜１０重量％が好ましく、熱分解型発泡剤が２０重量％〜８５重量％および有機酸（塩）が８０重量％〜１５重量％がより好ましく、熱分解型発泡剤が３０重量％〜８０重量％および有機酸（塩）が７０重量％〜２０重量％が更に好ましい。当該構成によると、少量の気泡核形成剤によって、効率良く造核効果が得られ易い、という利点を有する。 The content ratio of the heat-decomposable foaming agent and the organic acid (salt) in the bubble nucleating agent is 10% by weight, assuming that the total amount of the heat-decomposing foaming agent and the organic acid (salt) is 100% by weight. % To 90% by weight and organic acid (salt) are preferably 90% to 10% by weight, the heat-decomposable foaming agent is 20% to 85% by weight, and the organic acid (salt) is 80% to 15% by weight. More preferably, the heat-decomposable foaming agent is 30% by weight to 80% by weight, and the organic acid (salt) is more preferably 70% by weight to 20% by weight. According to this configuration, there is an advantage that a nucleation effect can be easily obtained efficiently with a small amount of bubble nucleating agent.
本発泡体の製造において、気泡核形成剤の使用量を多くするほど、得られる発泡体の気泡径は小さくなる傾向にある。ただし、発泡体の製造において、気泡核形成剤の使用量を多くするほど、製造コストが上昇し、気泡核形成剤の分解物による異物発生のリスクが高まる場合がある。よって、本発泡体の製造における気泡核形成剤の使用量は、ポリエチレン系樹脂１００重量部に対して、０．０３重量部〜１．５０重量部が好ましく、０．０８重量部〜１．２０重量部がより好ましく、０．１０重量部〜１．００重量部が更に好ましい。 In the production of the present foam, the larger the amount of the bubble nucleating agent used, the smaller the bubble diameter of the obtained foam tends to be. However, in the production of foam, the larger the amount of the bubble nucleating agent used, the higher the production cost, and the risk of foreign matter generation due to the decomposition products of the bubble nucleating agent may increase. Therefore, the amount of the bubble nucleating agent used in the production of the present foam is preferably 0.03 parts by weight to 1.50 parts by weight, and 0.08 parts by weight to 1.20 parts by weight, based on 100 parts by weight of the polyethylene resin. The parts by weight are more preferable, and 0.10 parts by weight to 1.00 parts by weight are further preferable.
本発泡体の製造において、気泡核形成剤としては、粉体状の気泡核形成剤を直接使用しても良く、原料樹脂との混合性およびハンドリング性を考慮した気泡核形成剤のマスターバッチを使用しても良い。気泡核形成剤のマスターバッチとしては、市販品を使用することもでき、例えば、永和化成工業製ポリスレンＥＥ２７５Ｆ、大日精化工業製ファインセルマスター ＳＳＣ ＰＯ２１７Ｋ等が挙げられる。 In the production of the present foam, a powdery bubble nucleating agent may be directly used as the bubble nucleating agent, and a masterbatch of the bubble nucleating agent in consideration of mixability with the raw material resin and handleability may be used. You may use it. As the masterbatch of the bubble nucleation agent, a commercially available product can also be used, and examples thereof include Polyslen EE275F manufactured by Eiwa Kasei Kogyo and Finecell Master SSC PO217K manufactured by Dainichiseika Kogyo.
本発泡体の製造において、気泡核形成剤の効果を促進する目的で、気泡核形成補助剤を使用することが可能である。前記気泡核形成補助剤としては、タルク、シリカ、炭酸カルシウム、ゼオライト、亜鉛華、リチウム化合物などが挙げられる。リチウム化合物としては、例えば、酢酸リチウム、シュウ酸リチウム、クエン酸リチウム、炭酸リチウム、ほう酸リチウム、ステアリン酸リチウム等が挙げられる。気泡核形成補助剤は、前記気泡核形成剤との併用において気泡径を微細化する効果が高いとの理由から、リチウム化合物を含むことが好ましく、炭酸リチウムを含むことがより好ましい。本発泡体の製造において、気泡核形成補助剤としては、粉体状の気泡核形成補助剤を直接使用しても良く、原料樹脂との混合性を考慮した気泡核形成補助剤のマスターバッチを使用しても良い。 In the production of the present foam, it is possible to use a bubble nucleation aid for the purpose of promoting the effect of the bubble nucleating agent. Examples of the bubble nucleation aid include talc, silica, calcium carbonate, zeolite, zinc oxide, and lithium compounds. Examples of the lithium compound include lithium acetate, lithium oxalate, lithium citrate, lithium carbonate, lithium borate, lithium stearate and the like. The bubble nucleation aid preferably contains a lithium compound, and more preferably lithium carbonate, because it has a high effect of reducing the bubble diameter when used in combination with the bubble nucleation agent. In the production of this foam, a powdery bubble nucleation aid may be directly used as the bubble nucleation aid, and a masterbatch of the bubble nucleation aid in consideration of mixing with the raw material resin is used. You may use it.
（耐候剤）
耐候剤としては、ポリエチレン系押出発泡体に通常使用される耐候剤を使用することができる。耐候剤としては、例えば、ヒンダードアミン系光安定剤（「ＨＡＬＳ」と称する場合もある。）、紫外線吸収剤（「ＵＶＡ」と称する場合もある。）、カーボンブラックなどの紫外線遮蔽剤、有機ニッケル化合物などの消光剤、などが挙げられる。
(Weather resistant)
As the weathering agent, a weathering agent usually used for polyethylene-based extruded foam can be used. Examples of the weather resistant agent include a hindered amine-based light stabilizer (sometimes referred to as "HALS"), an ultraviolet absorber (sometimes referred to as "UVA"), an ultraviolet shielding agent such as carbon black, and an organic nickel compound. Quenching agents such as, etc.
ＨＡＬＳとしては、入手可能な市販品として、ＢＡＳＦ製のＴｉｎｕｖｉｎ６２２ＳＦ、ＴｉｎｕｖｉｎＰＡ１２３、ＴｉｎｕｖｉｎＰＡ１４４、Ｔｉｎｕｖｉｎ７７０ＤＦ、Ｕｖｉｎｕｌ４０５０ＦＦ、Ｃｈｉｍａｓｓｏｒｂ９４４ＦＤＬ、Ｃｈｉｍａｓｓｏｒｂ２０２０ＦＤＬなど、およびＡＤＥＫＡ製のＬＡ−５２、ＬＡ−８１、ＬＡ−４０ＭＰなどが挙げられる。 Examples of HALS include BASF's Tinuvin622SF, TinuvinPA123, TinuvinPA144, Tinuvin770DF, Uvinul4050FF, Chimassorb944FDL, Chimassorb2020FDL, Chimassorb2020FDL, and ADEKA's LAM-52.
ＵＶＡとしては、例えば、トリアジン系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、ベンゾエート系紫外線吸収剤、シアノアクリレート系紫外線吸収剤などが挙げられる。 Examples of UVA include triazine-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, benzoate-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers.
ＨＡＬＳおよびＵＶＡなどの耐候剤は液体、粉末状、顆粒状、ペレット状等の形態で用いられ得る。耐候剤は、樹脂、樹脂添加剤等の成分にあらかじめ耐候剤を高濃度に配合した組成物（いわゆるマスターバッチ）として用いることもできる。 Weatherproofing agents such as HALS and UVA can be used in the form of liquids, powders, granules, pellets and the like. The weathering agent can also be used as a composition (so-called masterbatch) in which the weathering agent is previously mixed in a high concentration with components such as a resin and a resin additive.
（酸化防止剤）
本発泡体の製造では、酸化防止剤を含んでも良い。当該構成によると、加工熱安定性に優れる、という利点を有する。酸化防止剤としては、例えば、フェノール系酸化防止剤、リン系酸化防止剤、イオウ系酸化防止剤などが挙げられる。これら酸化防止剤は、１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。
(Antioxidant)
In the production of the present foam, an antioxidant may be included. According to this configuration, there is an advantage that the processing thermal stability is excellent. Examples of the antioxidant include a phenol-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant. These antioxidants may be used alone or in combination of two or more.
フェノール系酸化防止剤としては、例えば、２，６−ジ−ｔ−ブチル−４−メチルフェノール、テトラキス［メチレン−３（３’，５’−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］メタン、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、３，９−ビス［２−｛３−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ｝−１，１−ジメチルエチル］−２，４，８，１０−テトラオキサスピロ[５・５]ウンデカン、１，３，５−トリス２[３（３，５−ジ−ｔ−ブチル− ４−ヒドロキシフェニル）プロピオニルオキシ]エチルイソシアネート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、１，３，５−トリス（４−ｔ−ブチル−３−ヒドロキシ−２，６−ジメチルベンジル）イソシアヌレート、ペンタエリスリトールテトラキス[３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート]、トリエチレングリコール−Ｎ−ビス−３−（３−t−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート、１，６−ヘキサンジオールビス[３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート]、２，２−チオビス−ジエチレンビス[３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート]、２，２’−メチレン−ビス−（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４−エチル−６−ｔ−ブチルフェノール）、２，２’−メチレン−ビス−（４，６−ジ−ｔ−ブチルフェノール）、２，２’−エチリデン−ビス−（４，６−ジ−ｔ−ブチルフェノール）、２，２’−ブチリデン−ビス−（４−メチル−６−ｔ−ブチルフェノール）、４，４’−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、２−ｔ−ブチル−６−（３−ｔ−ブチル−２−ヒドロキシ−５−メチルベンジル）−４−メチルフェニルアクリレート、２，４−ジ−ｔ−アミル−６−（１−（３，５−ジ−ｔ−アミル−２−ヒドロキシフェニル）エチル）フェニルアクリレート、トコフェロール類等が挙げられる。２，２’−エチリデン−ビス−（４，６−ジ−ｔ−ブチルフェノール）としては、ケミプロ化成株式会社製の「ケミノックス１１２９」など、市販品を用いることもできる。 Examples of the phenolic antioxidant include 2,6-di-t-butyl-4-methylphenol and tetrakis [methylene-3 (3', 5'-di-t-butyl-4-hydroxyphenyl) propionate]. Methane, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) ) Propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,3,5-tris2 [3 (3,5-di-t-) Butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris (3, 5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol-N-bis-3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate, 1,6 -Hexanediol bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thiobis-diethylenebis [3- (3,5-di-t-butyl-4-) Hydroxyphenyl) propionate], 2,2'-methylene-bis- (4-methyl-6-t-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-t-butylphenol), 2, 2'-methylene-bis- (4,6-di-t-butylphenol), 2,2'-ethylidene-bis- (4,6-di-t-butylphenol), 2,2'-butylidene-bis- (4,6-di-t-butylphenol) 4-Methyl-6-t-butylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-) Methylbenzyl) -4-methylphenyl acrylate, 2,4-di-t-amyl-6- (1- (3,5-di-t-amyl-2-hydroxyphenyl) ethyl) phenyl acrylate, tocopherols, etc. Can be mentioned. As the 2,2'-ethylidene-bis- (4,6-di-t-butylphenol), a commercially available product such as "Cheminox 1129" manufactured by Chemipro Kasei Co., Ltd. can also be used.
リン系酸化防止剤としては、例えば、トリス（ノニルフェニル）ホスファイト、トリス(２，４−ジ−t−ブチルフェニル)ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス(２，４−ジ−t−ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(２，４−ジ−t−ブチル−６−メチルフェニル)ペンタエリスリトールジホスファイト、ビス(２，６−ジ−t−ブチル−４−メチルフェニル)ペンタエリスリトールジホスファイト、ビス(２，４− ジクミルフェニル)ペンタエリスリトールジホスファイト、テトラキス(２，４−ジ−t−ブチルフェニル)−４，４'−ジフェニレンジホスホナイト、２，２'−メチレンビス(４，６−ジ−t− ブチルフェニル)２−エチルヘキシルホスファイト、２，２'−エチリデンビス(４，６−ジ−t−ブチルフェニル)フルオロホスファイト、ビス(２，４−ジ−t−ブチル−６−メチルフェニル)エチルホスファイト、２−(２，４，６−トリ−t−ブチルフェニル)−５−エチル−５−ブチル−１，３，２−オキサホスホリナン、２，２'，２''−ニトリロ［トリエチル−トリス(３，３' ５，５'−テトラ−t−ブチル−１，１'−ビフェニル−２，２'−ジイル)ホスファイト、２，４，８，１０−テトラ−ｔ−ブチル−６−[３−（３−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）プロポキシ]ジベンゾ［ｄ，ｆ］［１，３，２］ジオキサホスフェピン等が挙げられる。 Examples of phosphorus-based antioxidants include tris (nonylphenyl) phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearylpentaerythritol diphosphite, and bis (2,4-di-). t-Butylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) ) Pentaerythritol diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4,4'-diphenylenediphosphonite, 2, 2'-Methylenebis (4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, 2,2'-ethylidenebis (4,6-di-t-butylphenyl) fluorophosphite, bis (2,4) -Di-t-butyl-6-methylphenyl) ethylphosphite, 2- (2,4,6-tri-t-butylphenyl) -5-ethyl-5-butyl-1,3,2-oxaphosphorinane , 2,2', 2''-Nitrilo [triethyl-tris (3,3'5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 2, 4,8,10-Tetra-t-butyl-6- [3- (3-methyl-4-hydroxy-5-t-butylphenyl) propoxy] dibenzo [d, f] [1,3,2] dioxa Hosfepine and the like can be mentioned.
イオウ系酸化防止剤としては、例えば、ジメチルジスルフィド、ジエチルジスルフィド、ジ−ｎ−プロピルジスルフィド、ジ−ｎ−ブチルジスルフィド、ジ−ｓｅｃ−ブチルジスルフィド、ジ−ｔ−ブチルジスルフィド、ジ−ｔ−アミルジスルフィド、ジシクロヘキシルジスルフィド、ジ−ｔ−オクチルジスルフィド、ジ−ｎ−ドデシルジスルフィド、ジ−ｔ−ドデシルジスルフィドなどが挙げられる。 Examples of the sulfur-based antioxidant include dimethyl disulfide, diethyl disulfide, di-n-propyl disulfide, di-n-butyl disulfide, di-sec-butyl disulfide, di-t-butyl disulfide, and di-t-amyl disulfide. , Dicyclohexyl disulfide, di-t-octyl disulfide, di-n-dodecyl disulfide, di-t-dodecyl disulfide and the like.
収縮防止剤としては、脂肪酸エステル、脂肪族アミン、脂肪酸アミドなどの従来周知のものが使用できる。前記脂肪酸エステルとしては、炭素数８〜３０の脂肪酸と水酸基を３〜７個有する多価アルコールとのエステルが好ましい。炭素数８〜３０の脂肪酸としては、ラウリン酸、オレイン酸、ステアリン酸、ベヘン酸、リグノセリン酸、セロチン酸、ヘプタコ酸、モンタン酸、メリシン酸、ラクセル酸などが挙げられる。水酸基を３〜７個有する多価アルコールとしては、グリセリン、ジグリセリン、トリグリセリン、エリトリットアラビット、キシリマアット、マンニット、ソルビット、ソルビタンなどが挙げられる。 As the shrinkage inhibitor, conventionally known agents such as fatty acid esters, aliphatic amines, and fatty acid amides can be used. As the fatty acid ester, an ester of a fatty acid having 8 to 30 carbon atoms and a polyhydric alcohol having 3 to 7 hydroxyl groups is preferable. Examples of fatty acids having 8 to 30 carbon atoms include lauric acid, oleic acid, stearic acid, behenic acid, lignoceric acid, cerotic acid, heptacoic acid, montanic acid, melissic acid, and laxelic acid. Examples of the polyhydric alcohol having 3 to 7 hydroxyl groups include glycerin, diglycerin, triglycerin, erythrit arabit, xylimaat, mannitol, sorbit, and sorbitan.
脂肪族アミンとしては、ドデシルアミン、テトラデシルアミン、ヘキサデシルアミン、オクタデシルアミン、エイコシルアミン、ドコシルアミン、Ｎ−メチルオクタデシルアミン、Ｎ−エチルオクタデシルアミン、ヘキサデシルプロピレンジアミン、オクタデシルプロピレンジアミンなどが挙げられる。 Examples of the aliphatic amine include dodecylamine, tetradecylamine, hexadecylamine, octadecylamine, eicosylamine, docosylamine, N-methyloctadecylamine, N-ethyloctadecylamine, hexadecylpropylenediamine, octadecylpropylenediamine and the like. ..
脂肪酸アミドとしては、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド、ラウリン酸ビスアミド、などが挙げられる。これらの収縮防止剤は一種のみを使用してもよいし、２種以上を組み合わせて使用してもよい。 Examples of fatty acid amides include stearic acid amides, oleic acid amides, erucic acid amides, methylene bisstearic acid amides, ethylene bisstearic acid amides, and lauric acid bisamides. These shrinkage inhibitors may be used alone or in combination of two or more.
これらの収縮防止剤の中でも、発泡性や発泡体諸物性への影響が少なく収縮防止効果が大きいとの観点から、脂肪酸エステルが好ましい。脂肪酸エステル化合物の中でも、完全エステル化物よりは部分エステル化物、特にモノエステル化物がより顕著な収縮防止効果が得られるため好ましい。脂肪酸エステルの中でも、ステアリン酸モノグリセライド、ベヘン酸モノグリセライド、またはステアリン酸モノグリセライドとベヘン酸モノグリセライドとの混合物が更に好ましく、特に、ステアリン酸モノグリセライド（グリセリンモノステアレート）が好ましい。 Among these shrinkage inhibitors, fatty acid esters are preferable from the viewpoint of having little influence on foamability and various physical properties of the foam and having a large shrinkage prevention effect. Among the fatty acid ester compounds, a partial esterified product, particularly a mono esterified product, is preferable to a complete esterified product because a more remarkable shrinkage-preventing effect can be obtained. Among the fatty acid esters, stearic acid monoglyceride, behenic acid monoglyceride, or a mixture of stearic acid monoglyceride and behenic acid monoglyceride is more preferable, and stearic acid monoglyceride (glycerin monostearate) is particularly preferable.
（発泡剤）
発泡剤としては、押出発泡で使用される一般的に使用される発泡剤であれば特に問わず、例えば、（ａ）（ａ−１）プロパン、ノルマルブタン、イソブタン、ノルマルペンタン、イソペンタン、ヘキサン等の脂肪族炭化水素類；（ａ−２）シクロペンタン、シクロブタン等の脂環式炭化水素類；（ａ−３）ジメチルエーテル、ジエチルエーテル、メチルエチルエーテル等のエーテル類；（ａ−４）メタノール、エタノール等のアルコール類；（ａ−５）空気、窒素、炭酸ガス等の無機ガス；並びに（ａ−６）水、などの物理系発泡剤、並びに、（ｂ）重炭酸ナトリウム、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などの熱分解型発泡剤を含む化学系発泡剤、等が挙げられる。発泡剤としては、これらのうちでも、所望の発泡倍率、所望の独立気泡率、および所望の平均気泡径が得られやすいことから物理系発泡剤が好ましく、脂肪族炭化水素類がより好ましく、特にノルマルブタンおよび／またはイソブタンが好ましい。
(Foaming agent)
The foaming agent is not particularly limited as long as it is a generally used foaming agent used in extrusion foaming, and examples thereof include (a) and (a-1) propane, normal butane, isobutane, normal pentane, isopentane, and hexane. (A-2) Alicyclic hydrocarbons such as cyclopentane and cyclobutane; (a-3) Ethers such as dimethyl ether, diethyl ether and methyl ethyl ether; (a-4) Methanol, Alcohols such as ethanol; (a-5) Inorganic gases such as air, nitrogen, carbon dioxide; and physical foaming agents such as (a-6) water, and (b) Sodium bicarbonate, azodicarboxylic amide, Examples thereof include chemical foaming agents containing a heat-decomposable foaming agent such as dinitrosopentamethylenetetramine. Among these, as the foaming agent, a physical foaming agent is preferable, and an aliphatic hydrocarbon is more preferable, and particularly, because a desired foaming ratio, a desired closed cell ratio, and a desired average cell diameter can be easily obtained. Normal butane and / or isobutane are preferred.
上述した発泡剤は１種を単独で使用してもよく、２種類以上を組み合わせて使用してもよい。 The above-mentioned foaming agent may be used alone or in combination of two or more.
発泡剤の使用量は、特に限定されない。発泡剤の使用量は、発泡剤の種類および目標とする発泡体の発泡倍率に応じて、適宜調整すればよい。使用する発泡剤の合計使用量は、原料樹脂１００重量部に対して、０．５重量部〜２０．０重量部が好ましく、１．０重量部〜１５．０重量部がより好ましい。 The amount of the foaming agent used is not particularly limited. The amount of the foaming agent used may be appropriately adjusted according to the type of the foaming agent and the target foaming ratio of the foam. The total amount of the foaming agent used is preferably 0.5 parts by weight to 20.0 parts by weight, more preferably 1.0 parts by weight to 15.0 parts by weight, based on 100 parts by weight of the raw material resin.
本発泡体において、着色剤（顔料）の使用に特に制限はない。着色剤を使用せずにナチュラル色の発泡体を得てもよく、青、赤、黒など着色剤を使用して所望の色の発泡体を得てもよい。着色剤としては、例えば、ペリレン系有機顔料、アゾ系有機顔料、キナクリドン系有機顔料、フタロシアニン系有機顔料、スレン系有機顔料、ジオキサジン系有機顔料、イソインドリン系有機顔料、カーボンブラックなどが挙げられる。 There are no particular restrictions on the use of colorants (pigments) in this foam. A natural-colored foam may be obtained without using a colorant, or a foam of a desired color may be obtained by using a colorant such as blue, red, or black. Examples of the colorant include perylene-based organic pigments, azo-based organic pigments, quinacridone-based organic pigments, phthalocyanine-based organic pigments, slene-based organic pigments, dioxazine-based organic pigments, isoindoline-based organic pigments, carbon black and the like.
本発泡体は架橋したものであってもよく、無架橋であってもよい。本発泡体の架橋度（ゲル分率）は、小さいほど好ましく、例えば、５重量％以下であることが好ましく、４重量％以下であることがより好ましく、３重量％以下であることがより好ましく、２重量％以下であることがより好ましく、２重量％未満であることがさらに好ましく、１重量％以下であることがよりさらに好ましい。本発泡体の架橋度（ゲル分率）は好ましくは微架橋であり、実質的に無架橋であることが好ましく、具体的には０．５重量％未満であることが好ましい。当該構成によると、得られた発泡体は良好な熱接着性を有するため、緩衝材としての加工適性が高く、また加熱溶融によって元の樹脂組成物に戻して再利用することが可能となり、その結果、リサイクルが容易であるという利点も有する。 The present foam may be crosslinked or may not be crosslinked. The degree of cross-linking (gel fraction) of the present foam is preferably as small as possible, for example, preferably 5% by weight or less, more preferably 4% by weight or less, and even more preferably 3% by weight or less. It is more preferably 2% by weight or less, further preferably less than 2% by weight, and even more preferably 1% by weight or less. The degree of cross-linking (gel fraction) of the present foam is preferably micro-cross-linked, preferably substantially non-cross-linked, and specifically less than 0.5% by weight. According to this structure, the obtained foam has good thermal adhesiveness, so that it is highly suitable for processing as a cushioning material, and can be returned to the original resin composition by heat melting and reused. As a result, it also has the advantage of being easy to recycle.
本発泡体のポリエチレン系樹脂は、架橋処理は公知の架橋方法であれば、特に問われず、電子線照射処理や、シラングラフト化による水架橋処理や、加熱処理や、有機過酸化物などの架橋剤による架橋処理などが例示されるが、架橋度を制御しやすい観点から、架橋剤によって架橋処理されているものが好適である。つまり、ポリエチレン系樹脂は有機過酸化物などの架橋剤を含むものであってもよい。 The polyethylene-based resin of this foam is not particularly limited as long as the cross-linking treatment is a known cross-linking method, such as electron beam irradiation treatment, water cross-linking treatment by silane grafting, heat treatment, and cross-linking of organic peroxides. Examples thereof include cross-linking treatment with an agent, but from the viewpoint of easy control of the degree of cross-linking, those subjected to cross-linking treatment with a cross-linking agent are preferable. That is, the polyethylene-based resin may contain a cross-linking agent such as an organic peroxide.
架橋剤としては、一般に過酸化物、アゾ化合物などのラジカル重合開始剤が挙げられるが、ポリエチレン系樹脂からの水素引き抜き能を有するものが好ましく、一般にケトンパーオキサイド、パーオキシケタール、ハイドロパーオキサイド、ジアルキルパーオキサイド、ジアシルパーオキサイド、パーオキシジカーボネート、パーオキシエステルなどの有機過酸化物が挙げられる。これらのうち、特に水素引き抜き能が高いものが好ましく、例えば１，１−ビス（ｔ−ブチルパーオキシ）３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、ｎ−ブチル４，４−ビス（ｔ−ブチルパーオキシ）バレレート、２，２−ビス（ｔ−ブチルパーオキシ）ブタンなどのパーオキシケタール、ジクミルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン、α，α’−ビス（ｔ−ブチルパーオキシ−ｍ−イソプロピル）ベンゼン、ｔ−ブチルクミルパーオキサイド、ジ−ｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）−３−ヘキシンなどのジアルキルパーオキサイド、ベンゾイルパーオキサイドなどのジアシルパーオキサイド、ｔ−ブチルパーオキシオクテート、ｔ−ブチルパーオキシイソブチレート、ｔ−ブチルパーオキシラウレート、ｔ−ブチルパーオキシ３，５，５−トリメチルヘキサノエート、ｔ−ブチルパーオキシイソプロピルカーボネート、２，５−ジメチル−２，５−ジ（ベンゾイルパーオキシ）ヘキサン、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジ−ｔ−ブチルパーオキシイソフタレートなどのパーオキシエステルなどが挙げられる。これらは、単独で用いてもよく、２種以上を組み合わせて用いてもよい。 Examples of the cross-linking agent include radical polymerization initiators such as peroxides and azo compounds, but those having the ability to extract hydrogen from polyethylene-based resins are generally preferable, and generally ketone peroxides, peroxyketals, hydroperoxides, etc. Examples thereof include organic peroxides such as dialkyl peroxides, diacyl peroxides, peroxydicarbonates and peroxyesters. Of these, those having a particularly high hydrogen abstraction ability are preferable, for example, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, and the like. n-Butyl 4,4-bis (t-butylperoxy) valerate, peroxyketal such as 2,2-bis (t-butylperoxy) butane, dicumyl peroxide, 2,5-dimethyl-2,5 -Di (t-butylperoxy) hexane, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl Dialkyl peroxides such as −2,5-di (t-butylperoxy) -3-hexine, diacyl peroxides such as benzoyl peroxide, t-butylperoxyoctate, t-butylperoxyisobutyrate, t -Butyl peroxylaurate, t-butylperoxy 3,5,5-trimethylhexanoate, t-butylperoxyisopropyl carbonate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, t Examples thereof include peroxyesters such as -butylperoxyacetate, t-butylperoxybenzoate, and di-t-butylperoxyisophthalate. These may be used alone or in combination of two or more.
架橋剤の添加量としては、ポリエチレン系樹脂１００重量部に対して、０．００１重量部以上１重量部以下が好ましく、０．００３重量部以上０．５重量部以下がさらに好ましい。ラジカル重合開始剤の添加量が０．００１重量部未満では架橋反応の効果が得られにくい場合があり、また、１重量部を超える添加量では、過度な架橋反応が起きてしまい、押出発泡に適さない高粘度となってしまう虞がある。 The amount of the cross-linking agent added is preferably 0.001 part by weight or more and 1 part by weight or less, and more preferably 0.003 part by weight or more and 0.5 part by weight or less with respect to 100 parts by weight of the polyethylene resin. If the amount of the radical polymerization initiator added is less than 0.001 part by weight, the effect of the cross-linking reaction may be difficult to obtain, and if the amount of the radical polymerization initiator added exceeds 1 part by weight, an excessive cross-linking reaction occurs, resulting in extrusion foaming. There is a risk of unsuitable high viscosity.
ポリエチレン系樹脂は、予め架橋処理されたポリエチレン系樹脂であってもよいし、発泡体の押出成形における溶融混練・溶融押出時にポリエチレン系樹脂が架橋剤によって架橋処理されたものであってもよい。 The polyethylene-based resin may be a polyethylene-based resin that has been cross-linked in advance, or may be a polyethylene-based resin that has been cross-linked with a cross-linking agent during melt-kneading / melt extrusion in extrusion molding of a foam.
本発泡体の発泡倍率は、特に限定されず、製品の重量および／または要求される物性によって適宜選択され得る。本発泡体の発泡倍率は、４倍〜３５倍が好ましく、５倍〜３３倍がより好ましく、５．５倍〜３０倍がさらに好ましく、６倍〜２８倍が特に好ましい。当該構成によると、得られる発泡体は、軽量性、製品のグリップ性および緩衝性等のバランスに優れるという利点を有する。また、当該構成によると、発泡体の主要な用途の一つである緩衝材にするための発泡体の加工性が良好となる。その結果、得られる発泡体を加工して緩衝材とし、軽量部品から重量部品まで幅広い搬送品の緩衝材として使用することが可能となる。本明細書において、発泡体の発泡倍率は、後述する実施例に記載の測定方法により得られた値である。 The expansion ratio of the present foam is not particularly limited and may be appropriately selected depending on the weight of the product and / or the required physical characteristics. The foaming ratio of the present foam is preferably 4 to 35 times, more preferably 5 to 33 times, further preferably 5.5 to 30 times, and particularly preferably 6 to 28 times. According to this configuration, the obtained foam has an advantage that it has an excellent balance of lightness, grip of the product, cushioning property and the like. Further, according to the structure, the processability of the foam for making it into a cushioning material, which is one of the main uses of the foam, is improved. As a result, the obtained foam can be processed into a cushioning material, which can be used as a cushioning material for a wide range of transported products from lightweight parts to heavy parts. In the present specification, the foaming ratio of the foam is a value obtained by the measuring method described in Examples described later.
本発泡体は、微細な平均気泡径および高い独立気泡率を両立することができる。本発泡体の平均気泡径は、１００μｍ〜６００μｍが好ましく、１５０μｍ〜５００μｍがより好ましく、１８０μｍ〜５００μｍがさらに好ましく、２００μｍ〜４００μｍが特に好ましい。当該構成によると、得られる発泡体を所望の独立気泡率および発泡倍率に調整し易い、および、得られる発泡体が、発泡体の主要な用途である緩衝材用途において、製品保護に優れる、という利点を有する。本明細書において、発泡体の平均気泡径は、後述する実施例に記載の測定方法により得られた値である。 This foam can achieve both a fine average cell diameter and a high closed cell ratio. The average cell diameter of the foam is preferably 100 μm to 600 μm, more preferably 150 μm to 500 μm, further preferably 180 μm to 500 μm, and particularly preferably 200 μm to 400 μm. According to this configuration, it is easy to adjust the obtained foam to a desired closed cell ratio and foaming ratio, and the obtained foam is excellent in product protection in the cushioning material application, which is the main application of the foam. Has advantages. In the present specification, the average cell diameter of the foam is a value obtained by the measuring method described in Examples described later.
本発泡体の独立気泡率は、６６％より大きいことが好ましく、７０％以上がより好ましく、７５％以上がより好ましく、８０％以上がより好ましく、８３％以上がより好ましく、８５％以上がより好ましく、８８％以上がより好ましく、９０％以上がより好ましい。当該構成によると、得られる発泡体の、緩衝材としての緩衝性能、繰り返し使用性能、および打ち抜き加工時の寸法回復性、が良好となるという利点を有する。 The closed cell ratio of the present foam is preferably larger than 66%, more preferably 70% or more, more preferably 75% or more, more preferably 80% or more, more preferably 83% or more, and more preferably 85% or more. Preferably, 88% or more is more preferable, and 90% or more is more preferable. According to this configuration, the obtained foam has the advantages of good cushioning performance as a cushioning material, repetitive use performance, and dimensional recovery during punching.
本発泡体の厚さは、特に限定されない。本発泡体の厚さは、１０ｍｍ以上であることが好ましく、１０ｍｍ〜１６０ｍｍがより好ましく、２０ｍｍ〜１６０ｍｍがより好ましく、２０ｍｍ〜１３０ｍｍがより好ましく、３０ｍｍ〜１００ｍｍがさらに好ましく、４０ｍｍ〜７０ｍｍが特に好ましい。当該構成によると、（ａ）さまざまな緩衝材形状への発泡体の加工が可能となる利点、およびシートの積層体ではなく一枚物で（すなわち、発泡体１つで）緩衝材として使用できるため、緩衝材として均質なものが得られ易いという利点を有する。ダイスの開口部の厚さや、成形ダイのサイズや、成形機における発泡体を挟みこむ寸法や、発泡体の引取速度などを適宜調節することにより、得られる発泡体の厚さを調節できる。 The thickness of the foam is not particularly limited. The thickness of the foam is preferably 10 mm or more, more preferably 10 mm to 160 mm, more preferably 20 mm to 160 mm, more preferably 20 mm to 130 mm, further preferably 30 mm to 100 mm, and particularly preferably 40 mm to 70 mm. .. According to this configuration, (a) the advantage of being able to process the foam into various cushioning material shapes, and the fact that it can be used as a cushioning material as a single piece (that is, with one foam) instead of a laminated sheet. Therefore, it has an advantage that a homogeneous material can be easily obtained as a cushioning material. The thickness of the obtained foam can be adjusted by appropriately adjusting the thickness of the opening of the die, the size of the molding die, the size of sandwiching the foam in the molding machine, the pick-up speed of the foam, and the like.
本発明の一実施形態に係るポリエチレン系押出発泡体は、一般的な押出発泡により製造することができる。 The polyethylene-based extruded foam according to one embodiment of the present invention can be produced by general extrusion foaming.
本発泡体の形状は特に限定されず、平板状および丸棒状などが挙げられる。本発泡体は、ポリエチレン系平板状押出発泡体、換言すればポリエチレン系押出発泡板であることが好ましい。本発泡体は、厚さ１０ｍｍ以上の板状発泡体であることが好ましい。当該構成によると、切削、打抜き等の加工により各種緩衝材に容易に適用可能であるという利点を有する。 The shape of the foam is not particularly limited, and examples thereof include a flat plate shape and a round bar shape. The present foam is preferably a polyethylene-based flat extruded foam, in other words, a polyethylene-based extruded foam plate. The present foam is preferably a plate-shaped foam having a thickness of 10 mm or more. According to this configuration, there is an advantage that it can be easily applied to various cushioning materials by processing such as cutting and punching.
本発泡体の製造方法としては、ポリエチレン系樹脂押出発泡体が得られる限り、いかなる方法を用いてもよい。本発泡体の製造方法では、二軸押出機と単軸押出機とを連結したタンデム押出機装置を使用してもよい。本発泡体の製造方法の具体的な例としては、次の（１）〜（６）の操作を順に行う方法が挙げられる：（１）ポリオレフィン系樹脂などの原料樹脂および必要に応じて、気泡核形成剤、収縮防止剤などのその他添加剤を、各々所定量準備し、準備した全ての原料を第１押出機（一段目の押出機、二軸）に供給する；（２）供給された原料を混錬に適した温度で溶融混錬する；（３）得られた溶融混練物（樹脂組成物）に対して、第１押出機の途中から、発泡剤を圧入する；（４）得られた樹脂組成物を所望の吐出量に調整し、第１押出機から、連結された第２押出機（二段目の押出機、単軸）に吐出する；（５）次いで第２押出機において、吐出された樹脂組成物の温度が発泡に適した温度となるように調整（例えば冷却）する；（６）発泡に適した温度に調整された樹脂組成物を、第２押出機の先端に取り付けたダイから、押出機内よりも低圧の領域に押出して、樹脂組成物を発泡させる。 As a method for producing the present foam, any method may be used as long as a polyethylene-based resin extruded foam can be obtained. In the method for producing the foam, a tandem extruder device in which a twin-screw extruder and a single-screw extruder are connected may be used. Specific examples of the method for producing the foam include the following operations (1) to (6) in order: (1) Raw material resin such as polyolefin resin and, if necessary, air bubbles. A predetermined amount of each other additive such as a nucleating agent and a shrinkage inhibitor was prepared, and all the prepared raw materials were supplied to the first extruder (first-stage extruder, twin-screw); (2) supplied. The raw materials are melt-kneaded at a temperature suitable for kneading; (3) a foaming agent is press-fitted into the obtained melt-kneaded product (resin composition) from the middle of the first extruder; (4) Obtained. The resulting resin composition is adjusted to a desired discharge rate and discharged from the first extruder to the connected second extruder (second stage extruder, single shaft); (5) then the second extruder. In, the temperature of the discharged resin composition is adjusted (for example, cooled) so as to be a temperature suitable for foaming; (6) The resin composition adjusted to a temperature suitable for foaming is brought into the tip of the second extruder. The resin composition is foamed by extruding the resin composition from the die attached to the die to a region having a lower pressure than the inside of the extruder.
前記（１）において、準備した全ての原料を第１押出機に供給する操作について、具体的に説明する。準備した全ての原料は、各々の原料を別々のフィーダーから第１押出機に供給してもよいし、原料の一部または全てを一緒に第１押出機に供給してもよい。準備した各々の原料を別々のフィーダーから第１押出機に供給する場合、各々の原料を第１押出機に同時に供給してもよいし、任意の時宜で供給してもよい。準備した原料の一部または全てを一緒に第１押出機に供給する場合、準備した原料の一部または全てを予め混合して混合物とし、当該混合物を第１押出機に供給してもよい。 In the above (1), the operation of supplying all the prepared raw materials to the first extruder will be specifically described. For all the prepared raw materials, each raw material may be supplied to the first extruder from a separate feeder, or a part or all of the raw materials may be supplied to the first extruder together. When each of the prepared raw materials is supplied to the first extruder from a separate feeder, each raw material may be supplied to the first extruder at the same time, or may be supplied at any time. When a part or all of the prepared raw materials are supplied to the first extruder together, a part or all of the prepared raw materials may be mixed in advance to form a mixture, and the mixture may be supplied to the first extruder.
なお、前記混錬に適した温度とは、原料樹脂が確実に溶融し、溶融した原料樹脂と必要に応じて添加される添加剤、及び発泡剤との混錬が好適に実施される温度であれば良く、特に限定されない。本発明の一実施形態において、前記混錬に適した温度とは、原料樹脂（例えばポリエチレン系樹脂）の融点以上の温度が好ましい。本発明の一実施形態において気泡核形成剤を使用する場合、前記混錬に適した温度は、使用する気泡核形成剤の効果が効率的に発揮される温度が好ましい。気泡核形成剤が分解型発泡剤を含む場合、気泡核形成剤の効果が効率的に発揮される温度とは、分解型発泡剤の分解が十分に進行し所望の造核作用が得られる温度である。例えば、気泡核形成剤として炭酸水素ナトリウムとクエン酸モノナトリウムとの混合物を使用する場合は、前記混錬に適した温度は、気泡核形成剤の効果が効率的に発揮される温度である１８０℃〜２４０℃が好ましい。 The temperature suitable for the kneading is a temperature at which the raw material resin is surely melted and the melted raw material resin is preferably kneaded with an additive added as needed and a foaming agent. It is sufficient, and there is no particular limitation. In one embodiment of the present invention, the temperature suitable for the kneading is preferably a temperature equal to or higher than the melting point of the raw material resin (for example, polyethylene-based resin). When the bubble nucleating agent is used in one embodiment of the present invention, the temperature suitable for the kneading is preferably a temperature at which the effect of the bubble nucleating agent used is efficiently exhibited. When the bubble nucleating agent contains a decomposing foaming agent, the temperature at which the effect of the bubble nucleating agent is efficiently exhibited is the temperature at which the decomposition of the decomposing foaming agent proceeds sufficiently and the desired nucleation action is obtained. Is. For example, when a mixture of sodium hydrogen carbonate and monosodium citrate is used as the bubble nucleating agent, the temperature suitable for the kneading is a temperature at which the effect of the bubble nucleating agent is efficiently exhibited 180. ° C to 240 ° C is preferable.
前記発泡に適した温度は、特に限定されない。前記発泡に適した温度は、一般的にはダイスから押出される樹脂組成物の温度が主原料となるポリエチレン系樹脂の融点に対して、マイナス１０℃からプラス２０℃の範囲内が好ましい。樹脂組成物の温度は、二段目の押出機で調整可能であるが、必要に応じて樹脂温度の均一化および樹脂温度調整を目的としてクーリングミキサーを用いてもよい。 The temperature suitable for foaming is not particularly limited. The temperature suitable for foaming is generally preferably in the range of -10 ° C to + 20 ° C with respect to the melting point of the polyethylene-based resin whose main raw material is the temperature of the resin composition extruded from the die. The temperature of the resin composition can be adjusted by the second-stage extruder, but if necessary, a cooling mixer may be used for the purpose of homogenizing the resin temperature and adjusting the resin temperature.
目的とする発泡体の形状に応じて、二段目の押出機の先端に取り付けるダイを選択することにより、平板状発泡体、丸棒状発泡体などの各種形状の押出発泡体を製造することができる。なお、樹脂組成物の押出条件、押出された発泡体の引取り条件、および押出された発泡体の冷却条件などは、適宜設定すればよい。本発泡体は、平板状発泡体であることが好ましく、換言すれば発泡板であることが好ましい。 By selecting a die to be attached to the tip of the second-stage extruder according to the shape of the desired foam, it is possible to manufacture extruded foams of various shapes such as flat foams and round bar foams. can. The extruding conditions of the resin composition, the taking-back conditions of the extruded foam, the cooling conditions of the extruded foam, and the like may be appropriately set. The present foam is preferably a flat foam, in other words, a foam plate.
押出機内よりも低圧の前記領域は、大気圧下の領域であることが好ましい。換言すれば、押出機内部は、大気圧よりも高圧であることが好ましい。 The region having a lower pressure than that in the extruder is preferably a region under atmospheric pressure. In other words, the inside of the extruder is preferably higher than atmospheric pressure.
以下、実施例および比較例を挙げて本発明の一実施形態を更に詳細に説明する。本発明は以下の実施例に限定されるものではない。 Hereinafter, an embodiment of the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.
実施例および比較例において、各種の評価方法に用いられた試験法および判定基準は次の通りである。 The test methods and criteria used for the various evaluation methods in the examples and comparative examples are as follows.
＜伸長粘度＞
測定装置はアントンパール社製のＭＣＲ１０２、およびユニバーサル伸長測定システム（ＵＸＦ）を用いた。サンプルには、各ポリエチレン系樹脂をプレス成型して２５ｍｍ×１０ｍｍ、厚み０．８５ｍｍのシートを作成して用いた。装置のオーブンを１２０℃に加熱しておき、温度が安定していることを確認して、１０秒以内にサンプルを治具にセットしオーブンを閉じた。結晶部分も完全に溶融させるため、１２０℃設定で５分間静置した。その後、オーブンの設定温度を測定温度に変更して、１５分間静置し、測定温度で安定したことを確認してから、０．２／ｓのひずみ速度で伸長粘度測定を行った。各温度での伸長粘度の測定はｎ＝３で行い、平均値をその温度での伸長粘度の値とした。要件（ａ）、（ｂ）を満たすかどうか判断できる温度範囲において、測定温度を１℃単位で設定して、測定温度毎に上記作業で測定を行った。
<Extensional viscosity>
As the measuring device, MCR102 manufactured by Anton Pearl Co., Ltd. and a universal elongation measuring system (UXF) were used. For the sample, each polyethylene-based resin was press-molded to prepare a sheet having a thickness of 25 mm × 10 mm and a thickness of 0.85 mm, which was used. The oven of the device was heated to 120 ° C., and after confirming that the temperature was stable, the sample was set on the jig within 10 seconds and the oven was closed. In order to completely melt the crystal part, it was allowed to stand at 120 ° C. for 5 minutes. Then, the set temperature of the oven was changed to the measurement temperature, and the mixture was allowed to stand for 15 minutes to confirm that it was stable at the measurement temperature, and then the extensional viscosity was measured at a strain rate of 0.2 / s. The extensional viscosity at each temperature was measured at n = 3, and the average value was taken as the value of the extensional viscosity at that temperature. In the temperature range in which it can be determined whether or not the requirements (a) and (b) are satisfied, the measurement temperature is set in units of 1 ° C., and the measurement is performed for each measurement temperature by the above operation.
測定条件として、オーブン内の加熱に用いられるエアーの流量は１４００Ｎｌ／ｈとした。また、温度の応答性が鋭敏である被覆付熱電対線を用いてサンプルセット部近傍の実温度を測定することで、オーブンの設定温度を１２０℃から測定温度に降温した際に、オーブン内の実温度が安定化する前に低温側にオーバーシュートしていないことを確認した。測定時に装置のトルクが３０ｍＮ・ｍとなり、ひずみ速度０．２／Ｓで変形できなくなった測定温度、もしくは伸長ひずみが０．５未満で破断してしまう温度を、その樹脂の固化温度とした。 As a measurement condition, the flow rate of air used for heating in the oven was 1400 Nl / h. In addition, by measuring the actual temperature near the sample set using a coated thermocouple wire that is sensitive to temperature, when the set temperature of the oven is lowered from 120 ° C to the measured temperature, the temperature inside the oven is reduced. It was confirmed that there was no overshoot to the low temperature side before the actual temperature stabilized. The solidification temperature of the resin was defined as the measurement temperature at which the torque of the device became 30 mN · m at the time of measurement and could not be deformed at a strain rate of 0.2 / S, or the temperature at which the elongation strain was broken at less than 0.5.
＜メルトフローレート（ＭＦＲ）＞
ＭＦＲはＪＩＳ Ｋ ７２１０−１（２０１４）に準拠して測定した。具体的には、メルトインデクサーＳ−０１（東洋精機製作所製）を用い、１９０℃、一定荷重（２．１６ｋｇ）下にて、ダイから単位時間に押し出される樹脂量（ｇ）を測定した。得られた樹脂量（ｇ）を１０分間に押し出される樹脂量（ｇ）に換算した値を算出した。
<Melt flow rate (MFR)>
MFR was measured according to JIS K 7210-1 (2014). Specifically, a melt indexer S-01 (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the amount of resin (g) extruded from the die in a unit time under a constant load (2.16 kg) at 190 ° C. A value obtained by converting the obtained resin amount (g) into the resin amount (g) extruded in 10 minutes was calculated.
なお、前記単位時間とは、メルトフローレートが０．５ｇ／１０分を超え１．０ｇ／１０分以下の場合は１２０秒間、１．０ｇ／１０分を超え３．５ｇ／１０分以下の場合は、６０秒間、３．５ｇ／１０分を超え１０ｇ／１０分以下の場合は３０秒間、１０ｇ／１０分を超え２５ｇ／１０分以下の場合は１０秒間、２５ｇ／１０分を超え１００ｇ／１０分以下の場合は５秒間、１００ｇ／１０分を超える場合は３秒間とした。 The unit time is 120 seconds when the melt flow rate is more than 0.5 g / 10 minutes and 1.0 g / 10 minutes or less, and is when the melt flow rate is more than 1.0 g / 10 minutes and 3.5 g / 10 minutes or less. Is 60 seconds, more than 3.5 g / 10 minutes and less than 10 g / 10 minutes for 30 seconds, more than 10 g / 10 minutes and more than 25 g / 10 minutes for 10 seconds, more than 25 g / 10 minutes and more than 100 g / 10 When it was less than a minute, it was set to 5 seconds, and when it exceeded 100 g / 10 minutes, it was set to 3 seconds.
ダイから単位時間に押し出される樹脂量を樹脂１ユニットとした。ＭＦＲの測定では、樹脂３ユニットを採取し、各々のユニットに対して、１０分間に押し出される樹脂量（ｇ）に換算した値を算出し、その平均値を各樹脂のＭＦＲとした。一回の測定で３ユニットの樹脂量を採取できない場合は、３ユニット採取できるまで測定を継続するものとした。ある単位時間で測定した際のメルトフローレートが対応する範囲に無かった場合は、そのメルトフローレートに応じた単位時間で再度測定するものとした。 The amount of resin extruded from the die per unit time was defined as one resin unit. In the measurement of MFR, 3 resin units were collected, a value converted into the amount of resin (g) extruded in 10 minutes was calculated for each unit, and the average value was taken as the MFR of each resin. If it was not possible to collect 3 units of resin in one measurement, the measurement was continued until 3 units could be collected. If the melt flow rate when measured in a certain unit time was not within the corresponding range, the measurement was performed again in a unit time corresponding to the melt flow rate.
＜ひずみ硬化度＞
測定装置はアントンパール社製のＭＣＲ１０２、およびユニバーサル伸長測定システム（ＵＸＦ）を用いた。試験片はプレス成型して２５ｍｍ×１０ｍｍ、厚み０．８５ｍｍのシートを作成して用いた。測定温度は１２０℃、ひずみ速度は０．５／ｓで得られた伸長粘度測定結果を、横軸に時間（秒）、縦軸に伸長粘度（Ｐａ・ｓ）を両対数グラフでプロットし、その両対数グラフ上で伸長粘度の立ち上がり（ひずみ硬化性を示す）を起こす直前の粘度を直線で近似し、伸長粘度の最大値を求め、その粘度の最大値を伸長粘度が最大となる時間までの近似直線上の粘度で割ったものを、ひずみ硬化度とした。
<Strain hardening degree>
As the measuring device, MCR102 manufactured by Anton Pearl Co., Ltd. and a universal elongation measuring system (UXF) were used. The test piece was press-molded to prepare a sheet having a size of 25 mm × 10 mm and a thickness of 0.85 mm, which was used. The extensional viscosity measurement results obtained at a measurement temperature of 120 ° C. and a strain rate of 0.5 / s are plotted on a double logarithmic graph with time (seconds) on the horizontal axis and extensional viscosity (Pa · s) on the vertical axis. On both logarithmic graphs, the viscosity immediately before the rise of the extensional viscosity (indicating strain curability) is approximated by a straight line, the maximum value of the extensional viscosity is obtained, and the maximum value of the viscosity is set to the time when the extensional viscosity becomes maximum. Divided by the viscosity on the approximate straight line of the above was taken as the strain hardening degree.
＜独立気泡率＞
実施例および比較例で得られた各発泡体から、長さ３０ｍｍ、幅２０ｍｍ、厚み２０ｍｍの試験片を３つ切り出した。当該試験片を用い、ＡＳＴＭ Ｄ２８５６に記載の方法に準拠し、エアピクノメータ（東京サイエンス株式会社製空気比較式比重計モデル１０００）を用いて、試験片の体積Ｖｃ（ｃｍ３）測定した。次に測定後の同じ試験片をエタノールの入ったメスシリンダー内の、エタノール中に沈めた。メスシリンダーの液面（エタノール面）上昇分から見かけ上の体積Ｖａ（ｃｍ３）を求めた。このような見かけ上の体積
の測定方法を、水没法と称する場合もある。下記式に従って独立気泡率（％）を求めた。
独立気泡率（％）＝（Ｖｃ／Ｖａ）×１００
なお、測定は、１つの発泡体あたり、３つの試験片について実施し、その平均値を発泡
体の独立気泡率とした。
<Closed cell ratio>
From each of the foams obtained in Examples and Comparative Examples, three test pieces having a length of 30 mm, a width of 20 mm, and a thickness of 20 mm were cut out. Using the test piece, the volume Vc (cm3) of the test piece was measured using an air pycnometer (air comparative hydrometer model 1000 manufactured by Tokyo Science Co., Ltd.) in accordance with the method described in ASTM D2856. The same test piece after the measurement was then submerged in ethanol in a graduated cylinder containing ethanol. The apparent volume Va (cm3) was determined from the amount of increase in the liquid level (ethanol level) of the measuring cylinder. Such a method of measuring the apparent volume may be referred to as a submersion method. The closed cell ratio (%) was determined according to the following formula.
Closed cell ratio (%) = (Vc / Va) x 100
The measurement was carried out for three test pieces per foam, and the average value was taken as the closed cell ratio of the foam.
＜発泡体密度＞
前記独立気泡率の測定で用いた試験片の重量Ｗ（ｋｇ）と前記水没法により求めた体積
Ｖａ（ｍ３）とを用いて、発泡体密度を下記式により求めた。
発泡体密度（ｋｇ／ｍ３）＝Ｗ／Ｖａ
なお、測定は、１つの発泡体あたり、３つの試験片について実施し、その平均値を発泡
体の密度とした。
<Foam density>
The foam density was determined by the following formula using the weight W (kg) of the test piece used in the measurement of the closed cell ratio and the volume Va (m 3) determined by the submersion method.
Foam density (kg / m 3 ) = W / Va
The measurement was carried out for three test pieces per foam, and the average value was taken as the density of the foam.
＜発泡倍率＞
実施例および比較例で使用した、原料樹脂の樹脂密度をＪＩＳ Ｋ ７１１２に準じて測定した。前記発泡体密度（ｋｇ／ｍ３）と樹脂密度（ｋｇ／ｍ３）とを用いて、発泡倍率を下記式により求めた。
発泡倍率（倍）＝樹脂密度／発泡体密度
<Foam magnification>
The resin density of the raw material resin used in Examples and Comparative Examples was measured according to JIS K 7112. Using the foam density (kg / m3) and the resin density (kg / m3), the foaming ratio was calculated by the following formula.
Foaming magnification (times) = resin density / foam density
＜平均気泡径＞
発泡体サイズの測定で作成した３つのサンプルＡの各々から、下記に示す各測定点（５箇所）について、各辺が５〜１０ｍｍの立方体（サンプルＢとする。）を切り出した。サンプルＢを、上述した面ａ、ｂおよびｃの各々と平行な面に沿って、両刃カミソリ［フェザー製、ハイステンレス両刃］を用いて、気泡膜（セル膜）が破壊されないように充分注意して切断した。得られた切断面（３面）をマイクロスコープ［キーエンス社製、ＶＨＸ−９００］を用いて観察し、各々の切断面の画像を得た。得られた各画像において、長さ４０００μｍの線分を引き、該線分が通る気泡数ｎを測定し、下記式により気泡径を算出した。
気泡径（μｍ）＝４０００／ｎ
３つのサンプルＡの各測定点（５箇所）について得られたサンプルＢ（１５個）の３つの切断面の各々の画像から得られた気泡径の相加平均値を平均気泡径（μｍ）とした。すなわち、４５面（３面×５箇所×３つのサンプルＡ）の気泡径の相加平均値を平均気泡径（μｍ）とした。
<Average cell diameter>
From each of the three samples A prepared by measuring the foam size, a cube (referred to as sample B) having a side of 5 to 10 mm was cut out at each measurement point (5 points) shown below. Use a double-edged razor [Feather, high stainless double-edged] along the plane parallel to each of the above-mentioned surfaces a, b, and c, and take sufficient care not to destroy the bubble film (cell film). And disconnected. The obtained cut surfaces (three surfaces) were observed using a microscope [VHX-900, manufactured by KEYENCE CORPORATION], and images of each cut surface were obtained. In each of the obtained images, a line segment having a length of 4000 μm was drawn, the number of bubbles n through which the line segment passed was measured, and the bubble diameter was calculated by the following formula.
Bubble diameter (μm) = 4000 / n
The arithmetic mean value of the bubble diameters obtained from the images of the three cut surfaces of the sample B (15 pieces) obtained for each measurement point (5 points) of the three samples A is defined as the average bubble diameter (μm). bottom. That is, the arithmetic mean value of the bubble diameters of 45 faces (3 faces x 5 locations x 3 samples A) was defined as the average bubble diameter (μm).
測定点を、サンプルＡに対して説明する。下記に示すように、１つのサンプルＡに対して５か所測定した：
（ａ）サンプルＡの面ｂにおける、幅方向および厚さ方向の中央部（１箇所、「測定点Ａ」とする）；
（ｂ）サンプルＡの面ｂにおける、厚さ方向の中央部の、測定点Ａと幅方向端部との中央部（幅方向両端部につき、２箇所）；
（ｃ）サンプルＡの面ｂにおける、幅方向の中央部の、測定点Ａと厚さ方向端部との中央部（厚さ方向両端部につき、２箇所）。
The measurement points will be described for Sample A. As shown below, 5 points were measured for one sample A:
(A) Central portion in the width direction and the thickness direction on the surface b of the sample A (one point, referred to as "measurement point A");
(B) The central portion of the surface b of the sample A in the thickness direction, the central portion between the measurement point A and the end portion in the width direction (two locations at both ends in the width direction);
(C) The central portion of the surface b of the sample A in the width direction between the measurement point A and the end portion in the thickness direction (two locations at both ends in the thickness direction).
＜巣（空洞）の評価＞
実施例および比較例で得られた発泡体を面ｂに沿って切断し、押出方向の長さが１２０ｍｍのサンプルＣを３つ作製した。サンプルＣを面ｂに沿ってパン切りスライサーにて切断し、押出方向の長さが１５ｍｍのサンプルＤを作製した。サンプルＣ１つあたり７つ、または６つのサンプルＤを作製し、合計２０個のサンプルＤを作製した。２０個のサンプルＤについて、パン切りスライサーにて切断して得られた切断面を観察し、空洞の有無を調べた。発見された空洞１つ１つについて、長径と短径とを測定し、長径と短径との平均値を当該空洞の平均径とした。この時、異なるサンプルＤであるが同切断面である面については、重複して測定を行っていない。得られた平均径を用いて下記基準により点数をつけた。空洞の数は、２０個のサンプルＤの断面の合計値である。
<Evaluation of nest (cavity)>
The foams obtained in Examples and Comparative Examples were cut along the surface b to prepare three samples C having a length in the extrusion direction of 120 mm. Sample C was cut along the surface b with a panning slicer to prepare Sample D having a length of 15 mm in the extrusion direction. Seven or six sample Ds were prepared for each sample C, and a total of 20 sample Ds were prepared. The cut surface obtained by cutting 20 samples D with a pan-cutting slicer was observed, and the presence or absence of cavities was examined. The major axis and the minor axis were measured for each of the discovered cavities, and the average value of the major axis and the minor axis was taken as the average diameter of the cavity. At this time, the surfaces of different samples D but having the same cut surface were not measured in duplicate. Using the obtained average diameter, points were given according to the following criteria. The number of cavities is the total value of the cross sections of 20 samples D.
５点・・・平均径１ｍｍ以上の空洞が無い
４点・・・平均径１ｍｍ以上２ｍｍ未満の空洞があり、平均径２ｍｍ以上５ｍｍ未満の空洞がない
３点・・・平均径２ｍｍ以上５ｍｍ未満の空洞が１個以上３個以下あり、平均径５ｍｍ以上の空洞がない
２点・・・平均径２ｍｍ以上５ｍｍ未満の空洞が４個以上あり、平均径５ｍｍ以上の空洞がない
１点・・・平均径５ｍｍ以上の空洞がある
サンプルＣの採取から点数付けまでの一連の評価を発泡体の異なる任意の３箇所についておこない、３箇所の合計点が１０点以上を合格とした（５点×３箇所＝１５点満点）。
5 points: No cavities with an average diameter of 1 mm or more 4 points: There are cavities with an average diameter of 1 mm or more and less than 2 mm, and there are no cavities with an average diameter of 2 mm or more and less than 5 mm 3 points: Average diameter of 2 mm or more and less than 5 mm There are 1 or more and 3 or less cavities, and there are no cavities with an average diameter of 5 mm or more.・ A series of evaluations from sampling of sample C with cavities with an average diameter of 5 mm or more to scoring were performed for any three locations with different foams, and the total score of the three locations was 10 points or more (5 points x). 3 places = 15 points out of 100).
以下の実施例および比較例において用いた原料は、次の通りである。 The raw materials used in the following examples and comparative examples are as follows.
＜ポリエチレン系樹脂＞
以下に示すエチレン系重合体Ａおよびエチレン系重合体Ｂを、表１および２に示す配合量で混合し、ポリエチレン系樹脂とした。
（エチレン系重合体Ａ）
Ａ−１：分岐状低密度ポリエチレン「Ｃ４７０」（宇部丸善ポリエチレン製、ＭＦＲ２．０ｇ／１０分、密度９１８ｋｇ／ｍ３）
Ａ−２：分岐状低密度ポリエチレン「Ｃ４１０」（宇部丸善ポリエチレン製、ＭＦＲ３．５ｇ／１０分、密度９１８ｋｇ／ｍ３）
Ａ−３：分岐状低密度ポリエチレン「Ｇ２０１」（住友化学製、ＭＦＲ２．０ｇ／１０分、密度９１９ｋｇ／ｍ３）
Ａ−４：分岐状低密度ポリエチレン「ＬＦ４４１ＭＤ１」（日本ポリエチレン製、ＭＦＲ２．０ｇ／１０分、密度９２４ｋｇ／ｍ３）
Ａ−５：分岐状低密度ポリエチレンを含む微架橋樹脂
<Polyethylene resin>
The ethylene-based polymer A and the ethylene-based polymer B shown below were mixed in the blending amounts shown in Tables 1 and 2 to obtain a polyethylene-based resin.
(Ethylene polymer A)
A-1: Branched low-density polyethylene "C470" (made of Ube-Maruzen polyethylene, MFR 2.0 g / 10 minutes, density 918 kg / m3)
A-2: Branched low-density polyethylene "C410" (made of Ube-Maruzen polyethylene, MFR 3.5 g / 10 minutes, density 918 kg / m3)
A-3: Branched low-density polyethylene "G201" (manufactured by Sumitomo Chemical, MFR 2.0 g / 10 minutes, density 919 kg / m3)
A-4: Branched low-density polyethylene "LF441MD1" (made by Japan Polyethylene, MFR 2.0 g / 10 minutes, density 924 kg / m3)
A-5: Microcrosslinked resin containing branched low density polyethylene
ここで、分岐状的密度ポリエチレンを含む微架橋樹脂は、次のようにして調製した。分岐状低密度ポリエチレン「Ｃ４１０」とエチレン／α−オレフィンコポリマー「０５４０Ｆ」を７５：２５となるようにブレンドし、上記ポリエチレン系樹脂１００重量部に対して、２，５−ジメチル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサンをシリカで希釈した過酸化物である日油製のパーヘキサ２５Ｂ−４０を０．０４４重量部となるように添加し、均一に混合したものを、２１０℃に設定した二軸押出機を用いて押出加工を行うことで、分岐状低密度ポリエチレンを含む微架橋樹脂を得た。（エチレン系重合体Ｂ）
Ｂ−１：線状低密度ポリエチレン「０５４０Ｆ」（宇部丸善ポリエチレン製、ＭＦＲ４．０ｇ／１０分、密度９０４ｋｇ／ｍ３）
Ｂ−２：エチレン／α−オレフィンコポリマー「Ａ−２００９０Ｓ」（三井化学株式会社製、ＭＦＲ１８ｇ／１０分、密度８９３ｋｇ／ｍ３）
Here, the microcrosslinked resin containing the branched density polyethylene was prepared as follows. The branched low-density polyethylene "C410" and the ethylene / α-olefin copolymer "0540F" are blended at a ratio of 75:25, and 2,5-dimethyl-2,5- is added to 100 parts by weight of the polyethylene-based resin. Di (t-butylperoxy) hexane diluted with silica, perhexa 25B-40 made by Nichiyu, was added so as to be 0.044 parts by weight, and the mixture was uniformly mixed and set at 210 ° C. A microcrosslinked resin containing branched low-density polyethylene was obtained by performing extrusion processing using the above-mentioned twin-screw extruder. (Ethylene polymer B)
B-1: Linear low-density polyethylene "0540F" (made of Ube-Maruzen polyethylene, MFR 4.0 g / 10 minutes, density 904 kg / m 3 )
B-2: Ethylene / α-olefin copolymer "A-20090S" (manufactured by Mitsui Chemicals, Inc., MFR 18 g / 10 minutes, density 893 kg / m 3 )
＜気泡核形成剤＞
Ｃ−１：熱分解型発泡剤と有機酸（塩）との混合物[永和化成製「ＥＥ２７５Ｆ」]、ＥＥ２７５Ｆは、炭酸水素ナトリウムとクエン酸（塩）との混合物を含むマスターバッチである。
<Bubble nucleating agent>
C-1: A mixture of a heat-decomposable foaming agent and an organic acid (salt) [Eiwa Kasei "EE275F"], EE275F is a master batch containing a mixture of sodium hydrogen carbonate and citric acid (salt).
＜収縮防止剤＞
Ｄ−１：ステアリン酸モノグリセライド
<Anti-shrinkage agent>
D-1: Monoglyceride stearate
（実施例１）
エチレン系重合体Ａおよびエチレン系重合体Ｂ各々を表１に示す配合量で、気泡核形成剤Ｃ−１を２重量部、並びに、収縮防止剤Ｄ−１を０．５重量部準備した。準備した原料を、タンデム押出機装置の第１押出機に供給した。ここで、タンデム押出機装置としては、第１押出機として口径４０ｍｍの二軸押出機と、第２押出機として口径９０ｍｍの単軸押出機とが連結されたタンデム押出機装置を使用した。第１押出機は、２１０℃に設定しており、すなわち第１押出機に供給した混合物を２１０℃にて溶融混錬した。ここで、得られた混合物に対して、発泡剤としてイソブタン３．５重量部を、第１押出機の途中から圧入した。かかる操作により、樹脂溶融物を調製した。
(Example 1)
2 parts by weight of the bubble nucleating agent C-1 and 0.5 part by weight of the shrinkage inhibitor D-1 were prepared in the amounts shown in Table 1 for each of the ethylene-based polymer A and the ethylene-based polymer B. The prepared raw material was supplied to the first extruder of the tandem extruder apparatus. Here, as the tandem extruder device, a tandem extruder device in which a twin-screw extruder having a diameter of 40 mm is connected as the first extruder and a single-screw extruder having a diameter of 90 mm is connected as the second extruder is used. The first extruder was set at 210 ° C., that is, the mixture supplied to the first extruder was melt-kneaded at 210 ° C. Here, 3.5 parts by weight of isobutane as a foaming agent was press-fitted into the obtained mixture from the middle of the first extruder. By such an operation, a resin melt was prepared.
続いて、得られた樹脂溶融物を第１押出機から第２押出機（口径９０ｍｍ）に吐出した。その後、第２押出機中で、樹脂溶融物を、バレル温度およびスクリュ回転数の調整により樹脂温度が表１に示す温度になるように冷却した。続いて、第２押出機の先端に取り付けられたダイスから、大気圧下に４０ｋｇ／時間の吐出量Ｑにて樹脂溶融物を吐出して、押出発泡した。ここで、ダイスは矩形の形状を有しており、ダイスの開口部の大きさは５．０ｍｍ×５０ｍｍであった。 Subsequently, the obtained resin melt was discharged from the first extruder to the second extruder (diameter 90 mm). Then, in the second extruder, the resin melt was cooled so that the resin temperature became the temperature shown in Table 1 by adjusting the barrel temperature and the screw rotation speed. Subsequently, the resin melt was discharged from the die attached to the tip of the second extruder at a discharge rate Q of 40 kg / hour under atmospheric pressure to extrude and foam. Here, the die had a rectangular shape, and the size of the opening of the die was 5.0 mm × 50 mm.
続いて、フリーの発泡体サンプル及び板状の発泡体を得た。具体的には、ダイスから押出された発泡体を、成形ダイを用いずに無負荷の状態で発泡させることでフリーの発泡体サンプルを得た。板状の発泡体は、ダイスから吐出された発泡体を成形ダイで矩形化するとともに、当該発泡体を成形機で引取速度を調整しつつサイズを調整し、幅１４０ｍｍおよび厚さ５２ｍｍの板状に成型することで板状発泡体を得た。得られた板状の発泡体は、巣の発生状況が良好でかつ独立気泡率も高かった。得られた発泡体について各種物性を測定および評価した結果を表１に示す。 Subsequently, a free foam sample and a plate-shaped foam were obtained. Specifically, a foam sample extruded from a die was foamed in a no-load state without using a molding die to obtain a free foam sample. The plate-shaped foam is a plate-shaped foam having a width of 140 mm and a thickness of 52 mm by rectangularizing the foam discharged from the die with a molding die and adjusting the size of the foam while adjusting the take-up speed with a molding machine. A plate-shaped foam was obtained by molding into. The obtained plate-shaped foam had good nesting conditions and a high closed cell ratio. Table 1 shows the results of measuring and evaluating various physical properties of the obtained foam.
（実施例２〜６、比較例１〜５）
表１の通りに各配合および各配合に適した樹脂温度となるように樹脂温度を変更した以外は、実施例１と同じ方法にて板状の発泡体を得た。得られた発泡体について各種物性を測定および評価した結果を表１に示す。
(Examples 2 to 6, Comparative Examples 1 to 5)
A plate-shaped foam was obtained by the same method as in Example 1 except that the resin temperature was changed so as to be the resin temperature suitable for each formulation and each formulation as shown in Table 1. Table 1 shows the results of measuring and evaluating various physical properties of the obtained foam.
表１に示される通り、実施例１〜７では、平均気泡径が小さく、高い独立気泡率を有しており、かつ巣が無い板状発泡体が得られた。 As shown in Table 1, in Examples 1 to 7, a plate-shaped foam having a small average cell diameter, a high closed cell ratio, and no nest was obtained.
表１に示される通り、比較例１では、要件（ｂ）を満たさず、板状とすることで独立気泡率の低下がみられ、また「巣」評価点の低いものであった。 As shown in Table 1, in Comparative Example 1, the requirement (b) was not satisfied, the closed cell ratio was lowered by forming the plate shape, and the "nest" evaluation score was low.
比較例２では、要件（ｂ）の上限を満たさず、板状発泡体とすることで独立気泡率の顕著な低下がみられた。なお、成形によって発泡体が潰れた箇所もあったため、「巣」の評価は行えなかった。 In Comparative Example 2, the upper limit of the requirement (b) was not satisfied, and the closed cell ratio was significantly reduced by using a plate-shaped foam. Since the foam was crushed in some places due to molding, the "nest" could not be evaluated.
比較例３で使用したポリエチレン系樹脂は、図２および図３のグラフに示されるように、低温化に伴って伸長粘度が増大し始めるとすぐに固化してしまう特性を有し、要件（ａ）および（ｂ）を満たさず、成形をかけないフリーの状態においても独立気泡率の高い発泡体を得ることができなかった。なお、本比較例に用いた樹脂のひずみ硬化度は１６．８であり、ひずみ硬化度が２．０〜３０の範囲内であるものの、発泡倍率も上がらず、独立気泡率に劣るものであった。 As shown in the graphs of FIGS. 2 and 3, the polyethylene-based resin used in Comparative Example 3 has a property of solidifying as soon as the extensional viscosity starts to increase as the temperature decreases, and the requirement (a). ) And (b) were not satisfied, and a foam having a high closed cell ratio could not be obtained even in a free state without molding. The strain curing degree of the resin used in this comparative example was 16.8, and although the strain curing degree was in the range of 2.0 to 30, the foaming ratio did not increase and the closed cell ratio was inferior. rice field.
比較例４では、要件（ａ）および（ｂ）いずれも満たさず、成形をかけないフリーの状態においても独立気泡率の高い発泡体を得ることができなかった。 In Comparative Example 4, neither of the requirements (a) and (b) was satisfied, and a foam having a high closed cell ratio could not be obtained even in a free state without molding.
比較例５では、要件（ｂ）を満たさず、「巣」評価点の低いものであった。 In Comparative Example 5, the requirement (b) was not satisfied and the "nest" evaluation score was low.
以上から、本発明の要件（ａ）（ｂ）を満たすポリエチレン系樹脂を用い平均気泡径が小さく、高い独立気泡率を有しており、かつ巣の発生が抑制されたポリエチレン系樹脂押出発泡体を得られることが明らかである。 Based on the above, a polyethylene-based resin extruded foam that uses a polyethylene-based resin that satisfies the requirements (a) and (b) of the present invention, has a small average cell diameter, has a high closed cell ratio, and suppresses the generation of nests. It is clear that
本発明の一実施形態によれば、平均気泡径が小さく、独立気泡率が高く、かつ巣が少ない、ポリエチレン系押出発泡体を提供できる。そのため、本発明の一実施形態は、各種緩衝材、包装材および断熱材などに好適に利用できる。 According to one embodiment of the present invention, it is possible to provide a polyethylene-based extruded foam having a small average cell diameter, a high closed cell ratio, and few nests. Therefore, one embodiment of the present invention can be suitably used for various cushioning materials, packaging materials, heat insulating materials, and the like.
Claims (7)
（ａ）固化温度＋１℃における伸長ひずみ０．５での伸長粘度が２．０Ｅ＋６Ｐａ・ｓ以上である、
（ｂ）伸長ひずみ０．５での伸長粘度が４．０Ｅ＋５Ｐａ・ｓ以上となる温度から、固化温度＋１℃までの温度範囲が４℃以上、９℃以下である。 A polyethylene-based extruded foam containing a polyethylene-based resin that satisfies the following (a) and (b) in the extensional viscosity measurement;
(A) The extensional viscosity at an extensional strain of 0.5 at a solidification temperature of + 1 ° C. is 2.0E + 6Pa · s or more.
(B) The temperature range from the temperature at which the extensional viscosity at an extension strain of 0.5 is 4.0 E + 5 Pa · s or more to the solidification temperature + 1 ° C. is 4 ° C. or more and 9 ° C. or less.
The polyethylene-based resin extruded foam according to any one of claims 1 to 6, wherein the polyethylene-based extruded foam is plate-shaped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020078363A JP2021172748A (en) | 2020-04-27 | 2020-04-27 | Polyethylene-based extrusion foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020078363A JP2021172748A (en) | 2020-04-27 | 2020-04-27 | Polyethylene-based extrusion foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021172748A true JP2021172748A (en) | 2021-11-01 |
Family
ID=78278951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020078363A Pending JP2021172748A (en) | 2020-04-27 | 2020-04-27 | Polyethylene-based extrusion foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021172748A (en) |
-
2020
- 2020-04-27 JP JP2020078363A patent/JP2021172748A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10941265B2 (en) | Polypropylene-type resin pre-expanded particles, and method for producing said pre-expanded particles | |
| US20170037214A1 (en) | Foamable masterbatch and polyolefin resin composition with excellent expandability and direct metallizing property | |
| US6653360B2 (en) | Flexible foamed polyethylene | |
| US6946495B2 (en) | Foamable composition using recycled or offgrade polypropylene | |
| WO2008041617A1 (en) | Polyolefin resin foam and process for production thereof | |
| US8222310B2 (en) | Extruded polypropylene resin foam and process for producing the same | |
| CN107108937B (en) | Foaming auxiliary material and foaming forming method | |
| EP4112678A1 (en) | Polypropylene-based resin foamed particles, method for producing same, and polypropylene-based resin foam molded body | |
| JP6739440B2 (en) | Compositions, foams and methods of preparing foams containing semi-crystalline polyolefins and sulfonyl azides | |
| US8361363B2 (en) | Foam board of polyolefin resin and method for its production | |
| WO2007004524A1 (en) | Constructional heat-insulating foam board and process for production thereof | |
| JP2021172749A (en) | Polyethylene-based extrusion foam | |
| JP2021172748A (en) | Polyethylene-based extrusion foam | |
| US6262138B1 (en) | Extrusion-foamed board of resin blend comprising modified polypropylene resin and polystyrene resin | |
| JP5044589B2 (en) | Polyvinylidene fluoride-based resin foamed particles, and polyvinylidene fluoride-based resin foamed particles | |
| KR101501836B1 (en) | Composition for preparing Ethylene Vinyl Acetate Copolymer, Ethylene Vinyl Acetate Copolymer, and Method of manufacturing thereof | |
| CN116162190A (en) | Polyolefin, resin composition and molded article | |
| JP2021113252A (en) | Polyethylene resin foam and method for producing the same | |
| JP7405549B2 (en) | Non-crosslinked extruded polyolefin resin foam and cushioning material | |
| JP2021113251A (en) | Method for producing polyolefin resin extruded foam | |
| JP7350482B2 (en) | Non-crosslinked polyethylene resin extruded foam board and its manufacturing method | |
| JP2023065202A (en) | Cushioning material for glass substrates | |
| JP6909394B2 (en) | Foam auxiliary material and foam molding method | |
| JP2019059861A (en) | Polypropylene injection foam molding | |
| JP7229754B2 (en) | Non-crosslinked polyethylene resin extruded foam board and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20231130 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20231226 |
|
| RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20240124 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20240618 |