JP7482740B2 - Expandable vinyl chloride resin particles, expanded particles thereof, and foamed molded article using the same - Google Patents
Expandable vinyl chloride resin particles, expanded particles thereof, and foamed molded article using the same Download PDFInfo
- Publication number
- JP7482740B2 JP7482740B2 JP2020162882A JP2020162882A JP7482740B2 JP 7482740 B2 JP7482740 B2 JP 7482740B2 JP 2020162882 A JP2020162882 A JP 2020162882A JP 2020162882 A JP2020162882 A JP 2020162882A JP 7482740 B2 JP7482740 B2 JP 7482740B2
- Authority
- JP
- Japan
- Prior art keywords
- chloride resin
- polyvinyl chloride
- resin particles
- expandable
- graphite
- 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.)
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- 239000011347 resin Substances 0.000 title claims description 269
- 229920005989 resin Polymers 0.000 title claims description 269
- 239000002245 particle Substances 0.000 title claims description 182
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 136
- 239000004800 polyvinyl chloride Substances 0.000 claims description 112
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 112
- 229910002804 graphite Inorganic materials 0.000 claims description 82
- 239000010439 graphite Substances 0.000 claims description 82
- 238000012546 transfer Methods 0.000 claims description 48
- 230000005855 radiation Effects 0.000 claims description 47
- 239000003112 inhibitor Substances 0.000 claims description 45
- 239000000178 monomer Substances 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 239000004088 foaming agent Substances 0.000 claims description 34
- 229920001577 copolymer Polymers 0.000 claims description 31
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- 150000002825 nitriles Chemical class 0.000 claims description 20
- 239000004604 Blowing Agent Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 229920000178 Acrylic resin Polymers 0.000 claims description 9
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 238000000790 scattering method Methods 0.000 claims description 6
- 239000004801 Chlorinated PVC Substances 0.000 claims description 5
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 2
- 238000004898 kneading Methods 0.000 description 37
- 238000005259 measurement Methods 0.000 description 32
- 239000006260 foam Substances 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 230000000694 effects Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 17
- 239000000523 sample Substances 0.000 description 17
- 239000011324 bead Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 13
- 238000005187 foaming Methods 0.000 description 13
- 238000000465 moulding Methods 0.000 description 13
- 239000008188 pellet Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000009413 insulation Methods 0.000 description 12
- -1 2-ethylhexyl Chemical group 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 10
- 229910052801 chlorine Inorganic materials 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 9
- 229910001868 water Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004793 Polystyrene Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000003381 stabilizer Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229920002223 polystyrene Polymers 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 239000011810 insulating material Substances 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 238000000691 measurement method Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 4
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000004698 Polyethylene Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920005990 polystyrene resin Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003440 styrenes Chemical class 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- CDOOAUSHHFGWSA-UPHRSURJSA-N (z)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C/C(F)(F)F CDOOAUSHHFGWSA-UPHRSURJSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000003796 beauty Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000010097 foam moulding Methods 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002667 nucleating agent Substances 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229920006327 polystyrene foam Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
- CDOOAUSHHFGWSA-OWOJBTEDSA-N (e)-1,3,3,3-tetrafluoroprop-1-ene Chemical compound F\C=C\C(F)(F)F CDOOAUSHHFGWSA-OWOJBTEDSA-N 0.000 description 1
- LDTMPQQAWUMPKS-OWOJBTEDSA-N (e)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C\Cl LDTMPQQAWUMPKS-OWOJBTEDSA-N 0.000 description 1
- LDTMPQQAWUMPKS-UPHRSURJSA-N (z)-1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)\C=C/Cl LDTMPQQAWUMPKS-UPHRSURJSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- KJUGUADJHNHALS-UHFFFAOYSA-N 1H-tetrazole Substances C=1N=NNN=1 KJUGUADJHNHALS-UHFFFAOYSA-N 0.000 description 1
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- IVRFYNSETZKRSJ-UHFFFAOYSA-N ClC=C.N#CC=CC=CC1=CC=CC=C1 Chemical compound ClC=C.N#CC=CC=CC1=CC=CC=C1 IVRFYNSETZKRSJ-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 239000004609 Impact Modifier Substances 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
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- DIQMPQMYFZXDAX-UHFFFAOYSA-N Pentyl formate Chemical compound CCCCCOC=O DIQMPQMYFZXDAX-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229920002433 Vinyl chloride-vinyl acetate copolymer Polymers 0.000 description 1
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- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
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- 150000004056 anthraquinones Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 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
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000011489 building insulation material Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
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- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
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- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
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- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
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- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- ZJPJECQPVMSILT-UHFFFAOYSA-N chloroethene 3-(2-phenylethenyl)furan-2,5-dione Chemical compound ClC=C.O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 ZJPJECQPVMSILT-UHFFFAOYSA-N 0.000 description 1
- KRGNPJFAKZHQPS-UHFFFAOYSA-N chloroethene;ethene Chemical group C=C.ClC=C KRGNPJFAKZHQPS-UHFFFAOYSA-N 0.000 description 1
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
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- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 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
- 150000004662 dithiols Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
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- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000005526 organic bromine compounds Chemical class 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 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
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- 229920005671 poly(vinyl chloride-propylene) Polymers 0.000 description 1
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- 239000004926 polymethyl methacrylate Substances 0.000 description 1
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- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
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- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、発泡性塩化ビニル系樹脂粒子、その発泡粒子およびこれらを用いた発泡成形体に関する。 The present invention relates to expandable polyvinyl chloride resin particles, expanded particles thereof, and foamed molded articles using these.
樹脂発泡体は、軽量性、断熱性、緩衝性等を有し、住宅等の断熱材や配管等の保温材として従来より広く使用されている。その中でも、発泡剤を含有した発泡性スチレン系樹脂粒子を用いて得られるスチレン系樹脂発泡成形体は、形状の自由度が高く、押出発泡法等で得られるボード形状の様な単純形状の発泡体では施工困難な部位にも適用できる断熱材として、広く活用されている。スチレン系樹脂は燃えやすい樹脂であるところ、スチレン系樹脂発泡成形体には難燃剤が添加され、ある程度の難燃性能は確保されているが、断熱性能を向上させるために輻射伝熱抑制剤を添加すると難燃性能が悪化することが知られている。近年の工事現場での火災事故や、高層マンションでの火災事例などから、建築用の断熱材には、断熱材の断熱性能を向上させるとともに、従来よりも高い難燃性能が求められつつある。 Resin foams have light weight, insulating properties, and cushioning properties, and have been widely used as insulating materials for houses and heat retaining materials for pipes. Among them, styrene resin foam molded products obtained using expandable styrene resin particles containing a foaming agent have a high degree of freedom in shape and are widely used as insulating materials that can be applied to areas where simple foam shapes such as board shapes obtained by extrusion foaming methods are difficult to apply. Since styrene resins are flammable resins, flame retardants are added to styrene resin foam molded products to ensure a certain degree of flame retardancy, but it is known that the flame retardancy deteriorates when a radiation heat transfer inhibitor is added to improve the insulating performance. In recent years, fire accidents at construction sites and fire cases in high-rise apartment buildings have led to a demand for insulating materials for construction that not only improve the insulating performance of the insulating material, but also have higher flame retardancy than before.
例えば、特許文献１には、処理により３５ｇ／ｌ又はこれより小さい密度を有するポリスチレン発泡体をもたらすことができ、かつ均斉に分布されたグラファイト粉末を含有することを特徴とする粒子状膨張性スチレン重合体（発泡性スチレン系樹脂粒子）が提案されている。 For example, Patent Document 1 proposes a particulate expandable styrene polymer (expandable styrene-based resin particulate) that can be processed to produce a polystyrene foam having a density of 35 g/l or less and that is characterized by containing uniformly distributed graphite powder.
また、特許文献２には、塩素化塩化ビニル樹脂と相溶性を呈する溶剤と発泡剤とを含有してなる塩素化塩化ビニル樹脂発泡粒子を型内発泡成形して得られた発泡体について記載されている。 Patent Document 2 describes a foam obtained by in-mold expansion molding of chlorinated polyvinyl chloride resin foam particles that contain a solvent compatible with chlorinated polyvinyl chloride resin and a blowing agent.
ところで、特許文献１には、グラファイト粉末を用いると難燃性の低下が問題点として挙げられている。この問題点を解決するために、難燃化剤として、７０重量％又はこれより多い臭素分を有する有機臭素化合物を含有する技術が提案されている。また、特許文献２では、塩素化塩化ビニル樹脂発泡粒子及びその成形体について開示されているが、輻射伝熱抑制剤についての記載なく、また熱伝導率についても言及がない。 However, Patent Document 1 cites the problem of reduced flame retardancy when graphite powder is used. To solve this problem, a technology has been proposed in which an organic bromine compound with a bromine content of 70% by weight or more is used as a flame retardant. Patent Document 2 discloses chlorinated polyvinyl chloride resin foam particles and molded bodies thereof, but makes no mention of a radiation heat transfer inhibitor, nor does it mention thermal conductivity.
本発明の目的は、高い断熱性能、難燃性能および発泡倍率を有する塩化ビニル系樹脂発泡成形体を与えうる発泡性塩化ビニル系樹脂粒子を提供することにある。 The object of the present invention is to provide expandable polyvinyl chloride resin particles that can give polyvinyl chloride resin foamed molded articles having high thermal insulation performance, flame retardancy and expansion ratio.
本願の発明者らは、上述した課題を解決すべく鋭意検討を重ねた結果、塩化ビニル系樹脂の難燃性を低下させることなく、優れた断熱性と発泡性を兼ね備えた発泡成形体を製造することに成功し、本発明を完成するに至った。 As a result of extensive research into solving the above-mentioned problems, the inventors of the present application have succeeded in producing a foamed molded product that combines excellent heat insulation and foaming properties without reducing the flame retardancy of the polyvinyl chloride resin, thus completing the present invention.
即ち、本発明は、
［１］次の（ａ）、（ｂ）及び（ｃ）を満たす発泡性塩化ビニル系樹脂粒子：
（ａ）炭素系輻射伝熱抑制剤を０．５～８重量％含有する、
（ｂ）塩化ビニル系樹脂及び物理系発泡剤を含有する、
（ｃ）発泡性塩化ビニル系樹脂粒子の真密度が１２００ｋｇ／ｍ３以上である。
［２］前記炭素系輻射伝熱抑制剤が、グラファイト、グラフェン、活性炭およびカーボンブラックよりなる群から選ばれる少なくとも１種を含む、［１］に記載の発泡性塩化ビニル系樹脂粒子。
［３］前記炭素系輻射伝熱抑制剤が、グラファイトを含む、［１］又は［２］に記載の発泡性塩化ビニル系樹脂粒子。
［４］前記炭素系輻射伝熱抑制剤は、平均粒子径が２．５～９μｍであるグラファイトを含む、［１］～［３］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［５］前記発泡性塩化ビニル系樹脂粒子を、樹脂を溶解可能な有機溶媒に分散させた溶液をレーザー回折散乱法により波長６３２ｎｍのレーザー光を用いて測定した、前記グラファイトの単位含有量当たりのレーザー散乱強度が５｛％／（ｍｇ／ｍｌ）｝／重量％以上である、［２］～［４］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［６］前記塩化ビニル系樹脂が塩素化塩化ビニル樹脂を含有する、［１］～［５］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［７］前記物理系発泡剤が炭素数４～６の飽和炭化水素の少なくとも１種を含有する、［１］～［６］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［８］前記物理系発泡剤がケトンを含有する、［１］～［７］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［９］前記発泡性塩化ビニル系樹脂粒子が、芳香族ビニル単量体及び不飽和ニトリルを構造単位に有する共重合体、アクリル系樹脂および塩素化ポリエチレンからなる群から選択される少なくとも一種を含む、［１］～［８］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子。
［１０］［１］～［９］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子の発泡粒子。
［１１］［１］～［９］のいずれか一項に記載の発泡性塩化ビニル系樹脂粒子または［１０］に記載の発泡性塩化ビニル系樹脂粒子の発泡粒子を用いた発泡成形体。
That is, the present invention provides:
[1] Expandable polyvinyl chloride resin particles that satisfy the following (a), (b), and (c):
(a) containing 0.5 to 8 wt % of a carbon-based radiation heat transfer inhibitor;
(b) a polyvinyl chloride resin and a physical foaming agent;
(c) The true density of the expandable polyvinyl chloride resin particles is 1,200 kg/m3 or more.
[2] The expandable polyvinyl chloride resin particles according to [1], wherein the carbon-based radiation heat transfer inhibitor contains at least one selected from the group consisting of graphite, graphene, activated carbon, and carbon black.
[3] The expandable polyvinyl chloride resin particles according to [1] or [2], wherein the carbon-based radiation heat transfer inhibitor contains graphite.
[4] The expandable polyvinyl chloride resin particles according to any one of [1] to [3], wherein the carbon-based radiation heat transfer inhibitor contains graphite having an average particle size of 2.5 to 9 μm.
[5] The expandable polyvinyl chloride resin particles according to any one of [2] to [4], wherein a laser scattering intensity per unit content of the graphite is 5 {%/(mg/ml)}/wt % or more when a solution obtained by dispersing the expandable polyvinyl chloride resin particles in an organic solvent capable of dissolving a resin is measured by a laser diffraction scattering method using a laser beam having a wavelength of 632 nm.
[6] The expandable polyvinyl chloride resin particles according to any one of [1] to [5], wherein the polyvinyl chloride resin contains a chlorinated polyvinyl chloride resin.
[7] The expandable polyvinyl chloride resin particles according to any one of [1] to [6], wherein the physical blowing agent contains at least one saturated hydrocarbon having 4 to 6 carbon atoms.
[8] The expandable polyvinyl chloride resin particles according to any one of [1] to [7], wherein the physical foaming agent contains a ketone.
[9] The expandable polyvinyl chloride resin particles according to any one of [1] to [8], which contain at least one selected from the group consisting of a copolymer having an aromatic vinyl monomer and an unsaturated nitrile as a structural unit, an acrylic resin, and a chlorinated polyethylene.
[10] Expanded particles of the expandable vinyl chloride resin particles according to any one of [1] to [9].
[11] A foamed molded article using the expandable polyvinyl chloride resin particles according to any one of [1] to [9] or the expanded particles of the expandable polyvinyl chloride resin particles according to [10].
本発明の発泡性塩化ビニル系樹脂粒子によれば、高い断熱性、難燃性および発泡倍率を有する塩化ビニル系樹脂発泡成形体が得られる。 The expandable vinyl chloride resin particles of the present invention can produce vinyl chloride resin foamed molded articles with high thermal insulation, flame retardancy and expansion ratio.
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Ｂ以下」を意味する。また、「Ａおよび／またはＢ」は、「Ａ、Ｂ、ならびに、ＡおよびＢ」を意味する。 Unless otherwise specified in this specification, "A to B" representing a numerical range means "A or more and B or less." Also, "A and/or B" means "A, B, and A and B."
（発泡性塩化ビニル系樹脂粒子）
本発明の発泡性塩化ビニル系樹脂粒子は、次の（ａ）、（ｂ）及び（ｃ）を満たす。
（ａ）炭素系輻射伝熱抑制剤を０．５～８重量％含有する。
（ｂ）物理系発泡剤を含有する。
（ｃ）発泡性塩化ビニル系樹脂の真密度が１２００ｋｇ／ｍ３以上である。
(Expandable polyvinyl chloride resin particles)
The expandable polyvinyl chloride resin particles of the present invention satisfy the following (a), (b), and (c).
(a) Contains 0.5 to 8 weight percent of a carbon-based radiation heat transfer inhibitor.
(b) Contains a physical foaming agent.
(c) The true density of the foamable polyvinyl chloride resin is 1,200 kg/m3 or more.
特許文献１に開示されるようにグラファイト等の炭素系輻射伝熱抑制剤はポリスチレン系樹脂発泡体に断熱性を付与するものの、ポリスチレン系樹脂発泡体の難燃性を低化させる傾向にある。本発明者らは、発泡性塩化ビニル系樹脂粒子にグラファイトを含有させることで、グラファイトを含有しない発泡性塩化ビニル系樹脂粒子と比較して、断熱性が向上するだけでなく、驚くべきことに得られる発泡成形体の難燃性が向上することを見出した。 As disclosed in Patent Document 1, carbon-based radiation heat transfer inhibitors such as graphite impart heat insulating properties to polystyrene-based resin foams, but tend to reduce the flame retardancy of the polystyrene-based resin foams. The present inventors have discovered that by incorporating graphite into expandable polyvinyl chloride resin particles, not only is the heat insulating property improved compared to expandable polyvinyl chloride resin particles that do not contain graphite, but surprisingly, the flame retardancy of the resulting foamed molded article is also improved.
また、炭素系輻射伝熱抑制剤は基材樹脂中に均一に分散されることで断熱性が図られるものの、高い断熱性を得るためには炭素系輻射伝熱抑制剤を基材樹脂中で分散させる必要があり、中でもグラファイトは基材樹脂中での分散性が劣ることが知られている。そのため、一般的には、基材樹脂との混錬前に前処理を行ったり、基材樹脂への分散性を高めるために混練性の強い条件としたりするため、工程の煩わしさや、基材樹脂や難燃剤などの劣化を抑制する対応が必要になる。本発明者らは、塩化ビニル系樹脂中における炭素系輻射伝熱抑制剤の分散性が高く、塩化ビニル系樹脂やその他成分の性能を劣化させずに高い断熱性を達成しやすいこと、中でも、グラファイトを使用する形態では、塩化ビニル系樹脂とグラファイトとの混錬時にグラファイトの粒子数が増大しやすく、グラファイトの少量使用で高断熱を奏することを新たに見出した。例えば、従来より、発泡性スチレン系樹脂粒子を製造する際にグラファイトを高分散させる技術としてグラファイトに対して事前に強混練を与えてマスターバッチ化する方法があるが、基材樹脂として塩化ビニル系樹脂を使用することで、事前にマスターバッチ化する工程を経なくても、発泡性塩化ビニル系樹脂粒子中における炭素系輻射伝熱抑制剤の高分散を達成できる。したがって、本発明の発泡性塩化ビニル系樹脂粒子を製造するにあたり、炭素系輻射伝熱抑制剤をマスターバッチ化する工程を用いない場合には、コストおよび生産性に優れる発泡性塩化ビニル系樹脂粒子を得ることができる。なお、本発明の発泡性塩化ビニル系樹脂粒子を製造する際には、マスターバッチ化した炭素系輻射伝熱抑制剤を用いてもよい。 Although the carbon-based radiation heat transfer inhibitor is uniformly dispersed in the base resin to achieve heat insulation, it is necessary to disperse the carbon-based radiation heat transfer inhibitor in the base resin to obtain high heat insulation, and graphite is known to have poor dispersibility in the base resin. Therefore, in general, pretreatment is performed before mixing with the base resin, or conditions for strong mixing are set to increase dispersibility in the base resin, which makes the process complicated and requires measures to suppress deterioration of the base resin and flame retardants. The present inventors have newly discovered that the carbon-based radiation heat transfer inhibitor has high dispersibility in the polyvinyl chloride resin, making it easy to achieve high heat insulation without deteriorating the performance of the polyvinyl chloride resin and other components, and that in particular, in a form in which graphite is used, the number of graphite particles is likely to increase when the polyvinyl chloride resin and graphite are mixed, and high heat insulation is achieved with a small amount of graphite. For example, in the past, a technique for highly dispersing graphite when producing expandable styrene-based resin particles has been to subject the graphite to intensive kneading in advance to form a masterbatch. However, by using a vinyl chloride-based resin as the base resin, it is possible to achieve high dispersion of the carbon-based radiation heat transfer inhibitor in the expandable vinyl chloride-based resin particles without going through a step of forming a masterbatch in advance. Therefore, when the expandable vinyl chloride-based resin particles of the present invention are produced without using a step of forming a carbon-based radiation heat transfer inhibitor into a masterbatch, it is possible to obtain expandable vinyl chloride-based resin particles that are excellent in cost and productivity. Note that, when producing the expandable vinyl chloride-based resin particles of the present invention, a masterbatch carbon-based radiation heat transfer inhibitor may be used.
本発明の発泡性塩化ビニル系樹脂粒子は、さらに特定の真密度を同時に有するため、上述の優れた効果を奏するととともに、優れた発泡性を有することが可能となる。 The expandable vinyl chloride resin particles of the present invention also have a specific true density, which allows them to have excellent expandability while also achieving the excellent effects described above.
（塩化ビニル系樹脂）
塩化ビニル系樹脂は、特に限定されないが、例えば、ポリ塩化ビニル（塩化ビニル単独重合体）；塩化ビニル・酢酸ビニル共重合体、塩化ビニル・（メタ）アクリル酸共重合体、塩化ビニル・（メタ）アクリル酸メチル共重合体、塩化ビニル・（メタ）アクリル酸エチル共重合体、塩化ビニル・マレイン酸エステル共重合体、塩化ビニル・エチレン共重合体、塩化ビニル・プロピレン共重合体、塩化ビニル・スチレン共重合体、塩化ビニル・イソブチレン共重合体、塩化ビニル・塩化ビニリデン共重合体、塩化ビニル・スチレン・無水マレイン酸三元共重合体、塩化ビニル・スチレン・アクリロニトリル三元共重合体、塩化ビニル・ブタジエン共重合体、塩化ビニル・イソプレン共重合体、塩化ビニル・塩素化プロピレン共重合体、塩化ビニル・塩化ビニリデン・酢酸ビニル三元共重合体、塩化ビニル・アクリロニトリル共重合体、塩化ビニル・各種ビニルエーテル共重合体等の塩化ビニルと塩化ビニルと共重合可能な他のモノマーとの塩化ビニル系共重合体；後塩素化したビニル共重合体等のポリ塩化ビニルや、後塩素化したポリ塩化ビニル、後塩素化した塩化ビニル系共重合体等の、塩化ビニル系重合体（ポリ塩化ビニルおよびポリ塩化ビニル系共重合体を総称して「塩化ビニル系重合体」と称することがある。）を改質（塩素化等）したものなどを挙げることができる。更には塩素化ポリエチレン等の、化学構造がポリ塩化ビニルと類似する塩素化ポリオレフィンを用いてもよい。これらの中で、難燃性の観点から、塩化ビニル系重合体、塩素化塩化ビニル系重合体が含まれることが好ましく、中でも難燃性および発泡性に優れる点から塩素化塩化ビニル系重合体が特に好ましい。塩化ビニル系樹脂としては、これらを１種又は２種以上の混合物を用いることができる。なお、本明細書では、塩素化塩化ビニル系重合体は塩素化塩化ビニル樹脂と同義である。
(Vinyl chloride resin)
The vinyl chloride resin is not particularly limited, but examples thereof include polyvinyl chloride (vinyl chloride homopolymer); vinyl chloride-vinyl acetate copolymer, vinyl chloride-(meth)acrylic acid copolymer, vinyl chloride-methyl (meth)acrylate copolymer, vinyl chloride-ethyl (meth)acrylate copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile terpolymer, vinyl chloride-butadiene ... Examples of the vinyl chloride copolymers include vinyl chloride copolymers of vinyl chloride and other monomers copolymerizable with vinyl chloride, such as vinyl chloride copolymers of vinyl ethers, vinyl chloride copolymers of vinyl chloride and vinyl chloride copolymers of ...
塩素化塩化ビニル系重合体は、通常、原料として塩化ビニル系重合体を用い、同塩化ビニル系重合体を水性媒体中に分散した状態で塩素を供給し、それに水銀灯を照射し光塩素化するか、あるいは加熱塩素化するなど水性媒体中で塩素化する方法、塩化ビニル系重合体を気層中、水銀灯の照射下で塩素化を行うなど気層中で塩素化する方法などにより製造される。原料となる塩化ビニル系重合体としては、上述で例示したポリ塩化ビニルおよび塩化ビニル系共重合体が同様に挙げられる。 Chlorinated vinyl chloride polymers are usually produced by using vinyl chloride polymers as raw materials, supplying chlorine to the vinyl chloride polymer dispersed in an aqueous medium, and chlorinating the polymer in an aqueous medium by irradiating it with a mercury lamp for photochlorination or by heating it for chlorination, or by chlorinating the vinyl chloride polymer in the gas phase by irradiating it with a mercury lamp. Examples of vinyl chloride polymers as raw materials include the polyvinyl chloride and vinyl chloride copolymers exemplified above.
塩化ビニル系重合体の平均重合度は、特に限定されないが、下限は３００以上が好ましく、４００以上がより好ましい。一方、上限は３０００以下であることが好ましく、より好ましくは１５００以下である。平均重合度が前記範囲であれば、高い発泡倍率を得られる傾向にある。 尚、塩素化塩化ビニル系重合体の平均重合度は、実質的に塩素化前の塩化ビニル系重合体の平均重合度とみなす。平均重合度はＪＩＳ Ｋ６７２０－２に準拠して測定される。 The average degree of polymerization of the vinyl chloride polymer is not particularly limited, but the lower limit is preferably 300 or more, and more preferably 400 or more. On the other hand, the upper limit is preferably 3000 or less, and more preferably 1500 or less. If the average degree of polymerization is within the above range, a high expansion ratio tends to be obtained. The average degree of polymerization of the chlorinated vinyl chloride polymer is regarded as the average degree of polymerization of the vinyl chloride polymer before chlorination. The average degree of polymerization is measured in accordance with JIS K6720-2.
塩化ビニル系重合体の重量平均分子量は、特に限定されないが、３０，０００以上４００，０００以下の範囲であることが好ましい。重量平均分子量が前記範囲であれば、高い発泡倍率を得られる傾向にある。重量平均分子量は、ゲルパーミエーションクロマトグラフィーによって、ポリスチレン換算分子量で評価される。 The weight average molecular weight of the vinyl chloride polymer is not particularly limited, but is preferably in the range of 30,000 to 400,000. If the weight average molecular weight is in this range, a high expansion ratio tends to be obtained. The weight average molecular weight is evaluated in terms of polystyrene by gel permeation chromatography.
塩素化塩化ビニル系重合体の塩素含有量は、６０重量％以上７５重量％以下の範囲であることが発泡性を確保する観点から好ましい。より好ましくは６４重量％以上７０重量％以下である。塩素含有量が高いほど高い発泡倍率を得られる傾向にあるが、一方で塩素含有量が高すぎると溶融粘度の上昇により、加工性が著しく損なわれる傾向にある。 塩素化塩化ビニル系重合体の塩素含有量は、ＪＩＳ Ｋ７３８５ Ｂ法に準拠して測定される。 From the viewpoint of ensuring foamability, the chlorine content of the chlorinated vinyl chloride polymer is preferably in the range of 60% by weight to 75% by weight. More preferably, it is 64% by weight to 70% by weight. The higher the chlorine content, the higher the foaming ratio tends to be, but if the chlorine content is too high, the melt viscosity increases and the processability tends to be significantly impaired. The chlorine content of the chlorinated vinyl chloride polymer is measured in accordance with JIS K7385 B method.
本発明の一実施形態として、塩素化塩化ビニル系重合体は１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。 As one embodiment of the present invention, a single type of chlorinated vinyl chloride polymer may be used, or two or more types may be used in combination.
本発明の一実施形態として、塩化ビニル系樹脂は、発泡性の観点から、塩素化塩化ビニル系重合体が含まれることが好ましい。特に限定するわけではないが、塩化ビニル系樹脂１００重量％において、塩素化塩化ビニル系重合体が５０重量％以上含まれることが好ましく、より好ましくは６０重量％以上であり、さらに好ましくは７０重量％であり、もっと好ましくは８０重量％以上である。一方、上限は塩化ビニル系樹脂１００重量％において、塩素化塩化ビニル系重合体が１００重量％であることが好ましい。 In one embodiment of the present invention, the vinyl chloride resin preferably contains a chlorinated vinyl chloride polymer from the viewpoint of foaming properties. Although not particularly limited, it is preferable that the chlorinated vinyl chloride polymer is contained in 50% by weight or more of 100% by weight of the vinyl chloride resin, more preferably 60% by weight or more, even more preferably 70% by weight or more, and most preferably 80% by weight or more. On the other hand, the upper limit is preferably 100% by weight of the chlorinated vinyl chloride polymer in 100% by weight of the vinyl chloride resin.
（炭素系輻射伝熱抑制剤）
本発明において、「輻射伝熱抑制剤」とは、発泡成形体中を伝わる伝熱機構のうち輻射伝熱を抑制することができる物質であって、同一の樹脂、発泡剤、セル構造、密度の発泡成形体において、輻射伝熱抑制剤を添加することによって、無添加系に比較して、熱伝導率を低くする効果を有する物質を言う。
(Carbon-based radiation heat transfer inhibitor)
In the present invention, the term "radiation heat transfer inhibitor" refers to a substance that can suppress radiation heat transfer, which is one of the heat transfer mechanisms that propagate through a foamed molded product, and that has the effect of lowering the thermal conductivity of a foamed molded product of the same resin, foaming agent, cell structure, and density when added thereto, compared to an additive-free system.
本発明で用いられる炭素系輻射伝熱抑制剤としては、近赤外または赤外領域（例えば、８００～３０００ｎｍ程度の波長域）の光を反射・散乱・吸収する特性を有する物質であれば特に限定されるものではない。 The carbon-based radiation heat transfer inhibitor used in the present invention is not particularly limited as long as it is a substance that has the property of reflecting, scattering, and absorbing light in the near-infrared or infrared region (e.g., a wavelength region of about 800 to 3000 nm).
本発明で用いられる炭素系輻射伝熱抑制剤としては、上述の輻射伝熱抑制剤の特性を有する炭素材であれば特に問わないが、グラファイト、グラフェン、活性炭、カーボンブラックが熱伝導率低減効果とコストのバランスが優れる点から好ましい。比較的少量の含有量で熱伝導率低減効果が発揮される点から、グラファイト、グラフェンがより好ましく、コストの面からグラファイトが特に好ましい。これら炭素系輻射伝熱抑制剤は、単独で使用してもよく、２種以上を混合して使用してもよい。 The carbon-based radiation heat transfer inhibitor used in the present invention may be any carbon material having the above-mentioned properties of the radiation heat transfer inhibitor, but graphite, graphene, activated carbon, and carbon black are preferred because they provide an excellent balance between the thermal conductivity reducing effect and cost. Graphite and graphene are more preferred because they provide a thermal conductivity reducing effect with a relatively small content, and graphite is particularly preferred from the standpoint of cost. These carbon-based radiation heat transfer inhibitors may be used alone or in combination of two or more types.
本発明の一実施形態では、グラファイトは、例えば、鱗片状黒鉛、土状黒鉛、球状黒鉛、熱膨張性黒鉛又は人造黒鉛等が挙げられるが、中でも鱗片状黒鉛、土状黒鉛、球状黒鉛、および人造黒鉛からなる群から選択される少なくとも一種が好ましい。なお、本明細書において、「鱗片状」という用語は、鱗状、薄片状又は板状のものをも包含する。これらの黒鉛は１種を単独で又は２種以上を組み合わせて使用できる。これらの中でも、輻射伝熱抑制効果が高い点から、鱗片状黒鉛を主成分とする黒鉛混合物が望ましく、鱗片状黒鉛がより望ましい。 In one embodiment of the present invention, the graphite may be, for example, flake graphite, earthy graphite, spherical graphite, thermally expandable graphite, or artificial graphite, and among these, at least one selected from the group consisting of flake graphite, earthy graphite, spherical graphite, and artificial graphite is preferred. In this specification, the term "flake" also includes scaly, flaky, or plate-like graphite. These graphites may be used alone or in combination of two or more. Among these, a graphite mixture mainly composed of flake graphite is preferred, and flake graphite is more preferred, in terms of its high radiation heat transfer suppression effect.
本発明の一実施形態では、発泡性塩化ビニル系樹脂粒子の含有するグラファイトの平均粒径、言い換えると、発泡性塩化ビニル系樹脂粒子中に存在するグラファイトの平均粒径が２．５～９μｍであることが望ましい。さらに３～６μｍであることがより望ましく、４～６μｍであることが最も望ましい。本明細書において、グラファイトの平均粒径は、ＩＳＯ１３３２０：２００９，ＪＩＳ Ｚ８８２５－１に準拠したＭｉｅ理論に基づくレーザー回折散乱法により粒度分布を測定・解析し、全粒子の体積に対する累積体積が５０％になる時の粒径（レーザー回折散乱法による体積平均粒径）を平均粒径とする。 In one embodiment of the present invention, the average particle size of the graphite contained in the expandable polyvinyl chloride resin particles, in other words, the average particle size of the graphite present in the expandable polyvinyl chloride resin particles, is preferably 2.5 to 9 μm. It is more preferably 3 to 6 μm, and most preferably 4 to 6 μm. In this specification, the average particle size of the graphite is determined by measuring and analyzing the particle size distribution using a laser diffraction scattering method based on the Mie theory in accordance with ISO13320:2009 and JIS Z8825-1, and the particle size at which the cumulative volume of the total particles is 50% (volume average particle size measured by the laser diffraction scattering method) is the average particle size.
本発明の一実施形態では、グラファイトは平均粒径が大きいほど製造コストが低くなる。特に平均粒径が２．５μｍ以上であるグラファイトは、粉砕のコストを含む製造コストが低いため、非常に安価であり、発泡性塩化ビニル系樹脂粒子のコストが低くなる傾向がある。さらに、グラファイトの平均粒径が２．５μｍ以上であると、得られる発泡性塩化ビニル系樹脂粒子から、断熱性の良好な塩化ビニル系樹脂発泡成形体を製造することが可能となる。平均粒径が９μｍ以下であると、発泡性塩化ビニル系樹脂粒子から発泡粒子及び塩化ビニル系樹脂発泡成形体を製造する際に、セル膜が破れにくくなるため、高発泡化が容易であったり、成形容易性が増加する傾向がある。 In one embodiment of the present invention, the larger the average particle size of the graphite, the lower the manufacturing cost. In particular, graphite with an average particle size of 2.5 μm or more is very inexpensive because the manufacturing cost, including the cost of crushing, is low, and the cost of the expandable polyvinyl chloride resin particles tends to be low. Furthermore, when the average particle size of the graphite is 2.5 μm or more, it is possible to manufacture a polyvinyl chloride resin foam molded product with good thermal insulation from the resulting expandable polyvinyl chloride resin particles. When the average particle size is 9 μm or less, the cell membrane is less likely to break when manufacturing expanded particles and polyvinyl chloride resin foam molded products from the expandable polyvinyl chloride resin particles, so that high expansion tends to be easily achieved and the ease of molding tends to increase.
本発明の発泡性塩化ビニル系樹脂粒子は、炭素系輻射伝熱抑制剤の含有量が０．５～８重量％である。目的とする発泡倍率に制御しやすいと共に、熱伝導率低減効果等のバランスの点から１．５～７重量％が好ましく、２～６重量％がより好ましい。含有量が０．５重量％以上では、熱伝導率低減効果が十分となる傾向があり、一方、８重量％以下では、発泡性塩化ビニル系樹脂粒子から、発泡粒子及び塩化ビニル系樹脂発泡成形体を製造する際に、セル膜が破れにくくなるため、高発泡化が容易であり、発泡倍率の制御が容易になる傾向がある。 The expandable polyvinyl chloride resin particles of the present invention have a carbon-based radiation heat transfer inhibitor content of 0.5 to 8% by weight. In terms of ease of control to the desired expansion ratio and balance of the thermal conductivity reduction effect, etc., 1.5 to 7% by weight is preferred, and 2 to 6% by weight is more preferred. If the content is 0.5% by weight or more, the thermal conductivity reduction effect tends to be sufficient, while if the content is 8% by weight or less, the cell membrane is less likely to break when producing expanded particles and polyvinyl chloride resin foam molded articles from the expandable polyvinyl chloride resin particles, making it easy to achieve high expansion and easy to control the expansion ratio.
（レーザー散乱強度）
発泡性塩化ビニル系樹脂粒子中における炭素系輻射伝熱抑制剤の分散性は、炭素系輻射伝熱抑制剤の単位溶液濃度あたりのレーザー散乱強度（以下、単に「レーザー散乱強度」と称することがある。）によって表すことができる。レーザー散乱強度は、以下のようにして求められる。まず、発泡剤および炭素系輻射伝熱抑制剤を含有しない樹脂粒子を所定量含有するテトラヒドロフラン（ＴＨＦ）溶液に波長６３２．８ｎｍのＨｅ－Ｎｅレーザー光を照射した際の透過光の強度Ｌｂと、発泡性塩化ビニル系樹脂粒子を所定重量含有するＴＨＦ溶液に波長６３２．８ｎｍのＨｅ－Ｎｅレーザー光を照射した際の透過光の強度Ｌｓとから、レーザー散乱強度Ｏｂ（％）を式Ｏｂ＝（１－Ｌｓ／Ｌｂ）×１００から求める。次に、求めたレーザー散乱強度Ｏｂから発泡性塩化ビニル系樹脂粒子の単位溶液濃度あたりのレーザー散乱強度を求める。そして、求めた単位溶液濃度あたりのレーザー散乱強度を所定重量の発泡性塩化ビニル系樹脂粒子内の炭素系輻射伝熱抑制剤の含有量（重量％）で割って算出されるレーザー散乱強度が、炭素系輻射伝熱抑制剤単位溶液濃度あたりのレーザー散乱強度である。
(Laser scattering intensity)
The dispersibility of the carbon-based radiation heat transfer inhibitor in the expandable polyvinyl chloride resin particles can be represented by the laser scattering intensity per unit solution concentration of the carbon-based radiation heat transfer inhibitor (hereinafter, sometimes simply referred to as "laser scattering intensity"). The laser scattering intensity is determined as follows. First, the intensity Lb of the transmitted light when a tetrahydrofuran (THF) solution containing a predetermined amount of resin particles not containing a foaming agent and a carbon-based radiation heat transfer inhibitor is irradiated with a He-Ne laser beam having a wavelength of 632.8 nm, and the intensity Ls of the transmitted light when a THF solution containing a predetermined weight of expandable polyvinyl chloride resin particles is irradiated with a He-Ne laser beam having a wavelength of 632.8 nm are used to determine the laser scattering intensity Ob (%) from the formula Ob = (1 - Ls / Lb) x 100. Next, the laser scattering intensity per unit solution concentration of the expandable polyvinyl chloride resin particles is determined from the determined laser scattering intensity Ob. The laser scattering intensity per unit solution concentration thus determined is divided by the content (weight %) of the carbon-based radiation heat transfer inhibitor in a predetermined weight of the expandable polyvinyl chloride resin particles to calculate the laser scattering intensity per unit solution concentration of the carbon-based radiation heat transfer inhibitor.
本発明の一実施形態は、炭素系輻射伝熱抑制剤単位溶液濃度あたりのレーザー散乱強度が５｛％／（ｍｇ／ｍｌ）｝／重量％以上であることが望ましい。このレーザー散乱強度が５｛％／（ｍｇ／ｍｌ）｝／重量％以上であると、炭素系輻射伝熱抑制剤の含有量に対して高い熱伝導率低減効果を得ることが可能となる。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。また、本発明の一実施形態は、発泡性塩化ビニル系樹脂粒子を、樹脂を溶解可能な有機溶媒に分散させた溶液をレーザー回折散乱法により波長６３２ｎｍのレーザー光を用いて測定した、グラファイトの単位含有量当たりのレーザー散乱強度が５｛％／（ｍｇ／ｍｌ）｝／重量％以上であることが望ましい。レーザー散乱強度が５｛％／（ｍｇ／ｍｌ）｝／重量％以上であると、グラファイトの含有量に対して高い熱伝導率低減効果を得ることが可能となる。すなわち、高発泡倍率で低い熱伝導率、従って高い断熱性、を得ることができる。グラファイトの単位含有量当たりのレーザー散乱強度は、５．５｛％／（ｍｇ／ｍｌ）｝／重量％以上であることがより望ましく、９｛％／（ｍｇ／ｍｌ）｝／重量％以下であることがより望ましい。このレーザー散乱強度が５．５｛％／（ｍｇ／ｍｌ）｝／重量％以上であると、より十分な熱伝導率低減効果が得ることができる。また、レーザー散乱強度が９｛％／（ｍｇ／ｍｌ）｝／重量％以下であると、グラファイトの平均粒子径が小さすぎることがなく、熱伝導率改善効果が得られ易くなる。 In one embodiment of the present invention, it is desirable that the laser scattering intensity per unit solution concentration of the carbon-based radiation heat transfer inhibitor is 5 {%/(mg/ml)}/wt% or more. If this laser scattering intensity is 5 {%/(mg/ml)}/wt% or more, it is possible to obtain a high thermal conductivity reduction effect relative to the content of the carbon-based radiation heat transfer inhibitor. In other words, it is possible to obtain low thermal conductivity and therefore high thermal insulation at a high expansion ratio. In addition, in one embodiment of the present invention, it is desirable that the laser scattering intensity per unit content of graphite, measured using a laser light with a wavelength of 632 nm by a laser diffraction scattering method, is 5 {%/(mg/ml)}/wt% or more. If the laser scattering intensity is 5 {%/(mg/ml)}/wt% or more, it is possible to obtain a high thermal conductivity reduction effect relative to the content of graphite. In other words, it is possible to obtain low thermal conductivity and therefore high thermal insulation at a high expansion ratio. The laser scattering intensity per unit graphite content is more preferably 5.5%/(mg/ml)/weight% or more, and more preferably 9%/(mg/ml)/weight% or less. If the laser scattering intensity is 5.5%/(mg/ml)/weight% or more, a more sufficient thermal conductivity reduction effect can be obtained. Also, if the laser scattering intensity is 9%/(mg/ml)/weight% or less, the average particle size of the graphite is not too small, and the thermal conductivity improvement effect can be easily obtained.
（発泡剤）
本発明の発泡性塩化ビニル系樹脂粒子は、物理系発泡剤を含有する。物理系発泡剤としては公知の発泡剤を使用でき、特に限定されないが、例えば下記の発泡剤が挙げられる。例えば、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、ネオペンタン、シクロペンタン、ノルマルヘキサン、又はシクロヘキサン等の炭化水素、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、イソプロピルエーテル、ｎ－ブチルエーテル、ジイソプロピルエーテル、フラン、フルフラール、２－メチルフラン、テトラヒドロフラン、テトラヒドロピランなどのエーテル、ジメチルケトン（アセトン）、メチルエチルケトン、ジエチルケトン、メチルｎ－プロピルケトン、メチル－ｎ－ブチルケトン、メチル－ｉ－ブチルケトン、メチル－ｎ－ヘキシルケトン、エチル－ｎ－プロピルケトン、エチル－ｎ－ブチルケトンなどのケトン、メタノール、エタノール、プロピルアルコール、ｉ－プロピルアルコール、ブチルアルコール、ｉ－ブチルアルコール、ｔ－ブチルアルコールなどの炭素数１～４の飽和アルコール、蟻酸メチルエステル、蟻酸エチルエステル、蟻酸プロピルエステル、蟻酸ブチルエステル、蟻酸アミルエステル、プロピオン酸メチルエステル、プロピオン酸エチルエステルなどのカルボン酸エステル、塩化メチル、塩化エチルなどのハロゲン化アルキル、トランス－１，３，３，３－テトラフルオロプロペン（トランス－ＨＦＯ－１２３４ｅ）、シス－１，３，３，３－テトラフルオロプロペン（シス－ＨＦＯ－１２３４ｚｅ）、２，３，３，３－テトラフルオロプロペン（トランス－ＨＦＯ－１２３４ｙｆ）、トランス－１－クロロ－３，３，３－トリフルオロプロペン（トランス－ＨＣＦＯ－１２３３ｚｄ）、シス－１－クロロ－３，３，３－トリフルオロプロペン（シス－ＨＣＦＯ－１２３３ｚｄ）などのハイドロフルオロオレフィンあるいは塩素化されたハイドロフルオロオレフィン、水、二酸化炭素、窒素などの無機系発泡剤などが挙げられる。これら他の発泡剤は、単独で用いてもよいし、２種以上を混合して用いてもよい。
(Foaming Agent)
The expandable vinyl chloride resin particles of the present invention contain a physical foaming agent. Known foaming agents can be used as the physical foaming agent, and are not particularly limited, but examples thereof include the following foaming agents. For example, hydrocarbons such as normal butane, isobutane, normal pentane, isopentane, neopentane, cyclopentane, normal hexane, and cyclohexane; ethers such as dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether, furan, furfural, 2-methylfuran, tetrahydrofuran, and tetrahydropyran; ketones such as dimethyl ketone (acetone), methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, methyl i-butyl ketone, methyl n-hexyl ketone, ethyl n-propyl ketone, and ethyl n-butyl ketone; saturated alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, and t-butyl alcohol; ants. Examples of the blowing agent include carboxylic acid esters such as methyl formate, ethyl formate, propyl formate, butyl formate, amyl formate, methyl propionate, and ethyl propionate, alkyl halides such as methyl chloride and ethyl chloride, hydrofluoroolefins or chlorinated hydrofluoroolefins such as trans-1,3,3,3-tetrafluoropropene (trans-HFO-1234e), cis-1,3,3,3-tetrafluoropropene (cis-HFO-1234ze), 2,3,3,3-tetrafluoropropene (trans-HFO-1234yf), trans-1-chloro-3,3,3-trifluoropropene (trans-HCFO-1233zd), and cis-1-chloro-3,3,3-trifluoropropene (cis-HCFO-1233zd), and inorganic blowing agents such as water, carbon dioxide, and nitrogen. These other blowing agents may be used alone or in combination of two or more.
本発明の一実施形態としては、発泡剤として、炭化水素系発泡剤が含有されることが好ましく、中でも炭素数４～６（炭素数４、５および６）の飽和炭化水素の少なくとも１種が含有されることがより好ましく、炭素数４および／または炭素数５の炭化水素がより好ましい。 In one embodiment of the present invention, the foaming agent preferably contains a hydrocarbon foaming agent, and more preferably contains at least one saturated hydrocarbon having 4 to 6 carbon atoms (4, 5, and 6 carbon atoms), and more preferably contains a hydrocarbon having 4 and/or 5 carbon atoms.
発泡剤の炭素数が４以上であると揮発性が低くなり、発泡性塩化ビニル系樹脂粒子から発泡剤が逸散しにくくなるため、実際に使用する際に発泡工程で発泡剤が十分に残り、十分な発泡力を得ることが可能となり、高倍率化が容易となるため好ましい。また、炭素数が６以下であると、発泡剤の沸点が高すぎないため、予備発泡時の加熱で十分な発泡力を得やすく、高発泡化が易しい傾向となる。 When the carbon number of the blowing agent is 4 or more, the volatility is low and the blowing agent is less likely to escape from the expandable polyvinyl chloride resin particles, so that when actually used, sufficient blowing agent remains in the foaming process, making it possible to obtain sufficient foaming power and facilitating high expansion, which is preferable. Also, when the carbon number is 6 or less, the boiling point of the blowing agent is not too high, so sufficient foaming power can be easily obtained by heating during pre-expansion, and high expansion tends to be easier.
炭素数４～６の飽和炭化水素としては、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、ネオペンタン、シクロペンタン、ノルマルヘキサン、又はシクロヘキサンが例示される。これらは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。なお、本明細書では、発泡粒子を得るために発泡性樹脂粒子を発泡させることを予備発泡と称することがある。 Examples of saturated hydrocarbons having 4 to 6 carbon atoms include normal butane, isobutane, normal pentane, isopentane, neopentane, cyclopentane, normal hexane, and cyclohexane. These may be used alone or in combination of two or more. In this specification, the expansion of expandable resin particles to obtain expanded particles may be referred to as pre-expansion.
本発明の一実施形態として、発泡剤としてケトンが含まれることが発泡剤の溶解性向上の観点から好ましい。例えば、炭素数４～６の飽和炭化水素とケトンとを併用することにより、炭素数４～６の飽和炭化水素の樹脂への溶解性を更に向上しうる。 As one embodiment of the present invention, it is preferable that a ketone is included as a foaming agent from the viewpoint of improving the solubility of the foaming agent. For example, by using a ketone in combination with a saturated hydrocarbon having 4 to 6 carbon atoms, the solubility of the saturated hydrocarbon having 4 to 6 carbon atoms in the resin can be further improved.
本発明の一実施形態としては、物理系発泡剤の含有量は、発泡性塩化ビニル系樹脂粒子１００重量％に対して１～４０重量％であることが好ましい。前記所定の範囲に発泡剤の含有量を制御することにより、高い発泡倍率を有する発泡粒子及び表面美麗性に優れた発泡成形体を得やすい、という効果を奏する。より好ましい範囲としては、３～２５重量％であり、更に好ましくは４～２０重量％である。 In one embodiment of the present invention, the content of the physical foaming agent is preferably 1 to 40% by weight relative to 100% by weight of the expandable polyvinyl chloride resin particles. By controlling the content of the foaming agent within the above-mentioned range, it is possible to easily obtain foamed particles with a high expansion ratio and foamed molded products with excellent surface beauty. A more preferred range is 3 to 25% by weight, and even more preferably 4 to 20% by weight.
本発明の一実施形態では、本発明の効果を損なわない範囲で、アゾ化合物、テトラゾールなどの化学発泡剤を併用してもよい。 In one embodiment of the present invention, chemical foaming agents such as azo compounds and tetrazoles may be used in combination as long as the effects of the present invention are not impaired.
（加工助剤）
本発明の好ましい一実施形態として、加工助剤を含有してもよい。加工助剤としては、塩化ビニル系樹脂に一般的に使用される加工助剤で特に問われないが、例えば、スチレンーアクリロニトリル共重合体のような芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体、アクリル系樹脂、メタクリル酸メチル－ブタジエン－スチレン系重合体のような耐衝撃改良剤、塩素化ポリエチレンなどが挙げられる。高発泡倍率の発泡粒子並びに発泡成形体を得やすい点から、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体、アクリル系樹脂および塩素化ポリエチレンからなる群から選択される少なくとも１種が含有されることが好ましい。中でも、塩化ビニル系樹脂の流動性を改善し、成形加工性を改善する観点から、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体および／またはアクリル系樹脂と、塩素化ポリエチレンとを併用することがより好ましい。
(Processing aids)
As a preferred embodiment of the present invention, a processing aid may be contained. The processing aid may be any processing aid commonly used for vinyl chloride resins, and may include, for example, copolymers having aromatic vinyl monomers and unsaturated nitrile monomers as structural units, such as styrene-acrylonitrile copolymers, impact modifiers such as methyl methacrylate-butadiene-styrene polymers, and chlorinated polyethylene. In order to easily obtain expanded particles and foamed molded articles with a high expansion ratio, it is preferable to contain at least one selected from the group consisting of copolymers having aromatic vinyl monomers and unsaturated nitrile monomers as structural units, acrylic resins, and chlorinated polyethylene. Among them, from the viewpoint of improving the flowability of vinyl chloride resins and improving molding processability, it is more preferable to use a copolymer having aromatic vinyl monomers and unsaturated nitrile monomers as structural units and/or an acrylic resin in combination with chlorinated polyethylene.
本発明の一実施形態では、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体を塩化ビニル系樹脂に用いることにより、水蒸気加熱条件での予備発泡や発泡成形において、高発泡倍率の発泡粒子並びに発泡成形体を得やすい効果に優れる。 In one embodiment of the present invention, a copolymer having structural units of an aromatic vinyl monomer and an unsaturated nitrile monomer is used in a vinyl chloride resin, which is excellent in the effect of easily obtaining foamed particles and foamed molded articles with high expansion ratios during pre-expansion and foam molding under steam heating conditions.
芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体の芳香族ビニル単量体としては、スチレン、α―メチルスチレン、エチルスチレン、ハロゲン化スチレン等のスチレン誘導体が挙げられる。不飽和ニトリル単量体としては、アクニロニトリル、メタクリロニトリル等が挙げられる。 The aromatic vinyl monomer of the copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units includes styrene derivatives such as styrene, α-methylstyrene, ethylstyrene, and halogenated styrene. The unsaturated nitrile monomer includes acrylonitrile, methacrylonitrile, etc.
本発明の効果を損なわない範囲で、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体は、上記芳香族ビニル単量体及び不飽和ニトリル単量体以外の単量体由来の構造単位（その他共重合可能な単量体）を有していても良い。その他共重合可能な単量体としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸Ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸２－エチルヘキシル等の（メタ）アクリル酸エステル、（メタ）アクリル酸、無水マレイン酸、Ｎ－置換マレイミドなどが挙げられる。 As long as the effect of the present invention is not impaired, the copolymer having structural units of an aromatic vinyl monomer and an unsaturated nitrile monomer may have structural units derived from monomers other than the aromatic vinyl monomer and the unsaturated nitrile monomer (other copolymerizable monomers). Examples of other copolymerizable monomers include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, N-butyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, (meth)acrylic acid, maleic anhydride, and N-substituted maleimide.
芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体中における不飽和二トリル単量体の好ましい範囲としては、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体全体を１００重量％として、５～４５重量％であり、より好ましくは、８～３５重量％であり、更に好ましくは、１０～３０重量％である。前記範囲であることで、高発泡倍率の発泡粒子並びに発泡成形体を得られやすい。 The preferred range of the unsaturated nitrile monomer in the copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units is 5 to 45% by weight, more preferably 8 to 35% by weight, and even more preferably 10 to 30% by weight, based on 100% by weight of the entire copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units. This range makes it easier to obtain expanded beads and expanded molded products with a high expansion ratio.
好ましい芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体としては、スチレンーアクリロニトリル共重合体が挙げられる。芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体は、１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。好ましい実施形態としては、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体の少なくとも１種としてスチレンーアクリロニトリル共重合体が使用される。芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体は、その重量平均分子量が、使用される塩化ビニル系樹脂の重量平均分子量よりも高いのものを使用することが高発泡倍率を確保しやすい点から好ましい。尚、芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィーによって、ポリスチレン換算分子量で評価される。芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体として、例えばＧａｌａｔａ製のＢｌｅｎｄｅｘ８６９等が使用できる。 A preferred example of a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units is a styrene-acrylonitrile copolymer. The copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units may be used alone or in combination of two or more. In a preferred embodiment, a styrene-acrylonitrile copolymer is used as at least one of the copolymers having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units. It is preferable to use a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units whose weight average molecular weight is higher than the weight average molecular weight of the vinyl chloride resin used, since it is easy to ensure a high expansion ratio. The weight average molecular weight of the copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units is evaluated in terms of polystyrene molecular weight by gel permeation chromatography. As a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units, for example, Blendex 869 manufactured by Galata can be used.
芳香族ビニル単量体及び不飽和ニトリル単量体を構造単位に有する共重合体の含有量は、本発明の効果を損なわない範囲であれば特に限定されないが、塩化ビニル系樹脂１００重量部に対して１～５０重量部であることが好ましく、３～４０重量部がより好ましく、５～３５重量部がさらに好ましく、８～３０重量部が特に好ましい。１重量部以上であると、高い発泡倍率を有する発泡粒子および／または発泡成形体を得やすくなり、５０重量部以下であると、難燃性能に優れた発泡粒子および／または発泡成形体を得ることができる。 The content of the copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 1 to 50 parts by weight, more preferably 3 to 40 parts by weight, even more preferably 5 to 35 parts by weight, and particularly preferably 8 to 30 parts by weight, per 100 parts by weight of vinyl chloride resin. If it is 1 part by weight or more, it becomes easier to obtain expanded beads and/or expanded molded products with a high expansion ratio, and if it is 50 parts by weight or less, it becomes possible to obtain expanded beads and/or expanded molded products with excellent flame retardant performance.
アクリル系樹脂の具体例としては、たとえばメタクリル酸メチルを重合させてえられるポリメタクリル酸メチル、メタクリル酸メチルと、メタクリル酸ｎ－ブチルなどのアルキル基の炭素数が２～８のメタクリル酸アルキルエステル、アクリル酸エチルなどのアルキル基の炭素数が１～８のアクリル酸アルキルエステル、およびブチレン、置換スチレン、アクリロニトリルなどのこれらと共重合可能な単量体の少なくとも１種との共重合体などがあげられる。アクリル系樹脂は、その重量平均分子量が、使用される塩化ビニル系樹脂の重量平均分子量よりも高いのものを使用することが高発泡倍率を確保しやすい点から好ましい。尚、アクリル系樹脂の重量平均分子量は、ゲルパーミエーションクロマトグラフィーによって、ポリスチレン換算分子量で評価される。アクリル系樹脂として、例えばカネカ製のカネエースＰＡ－４０等を使用することができる。 Specific examples of acrylic resins include polymethyl methacrylate obtained by polymerizing methyl methacrylate, methacrylic acid alkyl esters having 2 to 8 carbon atoms in the alkyl group such as n-butyl methacrylate, acrylic acid alkyl esters having 1 to 8 carbon atoms in the alkyl group such as ethyl acrylate, and copolymers of at least one monomer copolymerizable with these, such as butylene, substituted styrene, and acrylonitrile. It is preferable to use an acrylic resin whose weight average molecular weight is higher than that of the vinyl chloride resin used, since this makes it easier to ensure a high expansion ratio. The weight average molecular weight of the acrylic resin is evaluated in terms of polystyrene molecular weight by gel permeation chromatography. For example, Kane Ace PA-40 manufactured by Kaneka can be used as the acrylic resin.
アクリル系樹脂の含有量は、本発明の効果を損なわない範囲であれば特に限定されないが、塩化ビニル系樹脂１００重量部に対して１～５０重量部であることが好ましく、５～５０重量部がより好ましく、８～３０重量部が更に好ましい。１重量部以上であると、高い発泡倍率を有する発泡粒子および／または発泡成形体を得やすくなり、５０重量部以下であると、難燃性能に優れた発泡粒子および／または発泡成形体を得ることができる。 The content of the acrylic resin is not particularly limited as long as it is within a range that does not impair the effects of the present invention, but is preferably 1 to 50 parts by weight, more preferably 5 to 50 parts by weight, and even more preferably 8 to 30 parts by weight, per 100 parts by weight of the vinyl chloride resin. If the content is 1 part by weight or more, it becomes easier to obtain expanded beads and/or expanded molded products with a high expansion ratio, and if it is 50 parts by weight or less, it becomes possible to obtain expanded beads and/or expanded molded products with excellent flame retardant performance.
塩素化ポリエチレンの使用量は、本発明の効果を損なわない範囲であれば、特に限定されないが、塩化ビニル系樹脂１００重量部に対して１～３０重量部であることが好ましく、２～２５重量部であることがより好ましく、３～２０重量部であることがさらに好ましい。尚、塩素化ポリエチレンの塩素含有量は、ＪＩＳ Ｋ７３８５ Ｂ法に準拠して測定される。 The amount of chlorinated polyethylene used is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts by weight, and even more preferably 3 to 20 parts by weight, per 100 parts by weight of vinyl chloride resin. The chlorine content of the chlorinated polyethylene is measured in accordance with JIS K7385 B method.
（その他添加剤）
本発明の効果を損なわない範囲で、必要に応じて、難燃剤、安定剤、滑剤、造核剤、発泡助剤、帯電防止剤、輻射伝熱抑制剤、可塑剤、溶剤及び顔料・染料などの着色剤等を含有しても良い。
(Other additives)
As necessary, the composition may contain flame retardants, stabilizers, lubricants, nucleating agents, foaming assistants, antistatic agents, radiation heat transfer inhibitors, plasticizers, solvents, and colorants such as pigments and dyes, etc., within the scope of the invention that does not impair the effects of the invention.
難燃剤としては、公知の難燃剤を使用することができ、例えば、臭素系難燃剤、リン系難燃剤、ホウ素系難燃剤、ポリリン酸アンモニウム、メラミンシアヌレート等のイントメッセント系難燃剤、水酸化アルミニウム、水酸化マグネシウム等の水酸化化合物、酸化アンチモン、酸化亜鉛、ホウ酸亜鉛などの難燃助剤が挙げられる。 As the flame retardant, known flame retardants can be used, for example, bromine-based flame retardants, phosphorus-based flame retardants, boron-based flame retardants, intumescent flame retardants such as ammonium polyphosphate and melamine cyanurate, hydroxide compounds such as aluminum hydroxide and magnesium hydroxide, and flame retardant assistants such as antimony oxide, zinc oxide, and zinc borate.
安定剤としては、従来より塩化ビニル系樹脂に用いられるものを使用することができる。例えば、錫系安定剤、フェノール系化合物、リン系化合物、アミン系化合物などの酸化防止剤、エポキシ系安定剤、ゼオライト等が挙げられる。其々の安定剤の使用量は、本発明の効果を損なわない範囲であれば、特に限定されないが、塩化ビニル系樹脂１００重量部に対して１０重量部以下であることが好ましい。 As the stabilizer, those conventionally used for vinyl chloride resins can be used. Examples include tin-based stabilizers, antioxidants such as phenolic compounds, phosphorus-based compounds, and amine-based compounds, epoxy-based stabilizers, and zeolites. The amount of each stabilizer used is not particularly limited as long as it does not impair the effects of the present invention, but it is preferable that the amount is 10 parts by weight or less per 100 parts by weight of vinyl chloride resin.
滑剤としては、エステルワックス、ポリエチレンワックス等のワックス、ステアリン酸カルシウム、ステアリン酸亜鉛等の脂肪酸金属塩などが挙げられる。 Examples of lubricants include waxes such as ester wax and polyethylene wax, and fatty acid metal salts such as calcium stearate and zinc stearate.
造核剤としては、シリカ、ケイ酸カルシウム、ワラストナイト、カオリン、クレイ、マイカ、酸化亜鉛、炭酸カルシウム、炭酸水素ナトリウム、ゼオライトもしくはタルク等の無機化合物が挙げられる。 Nucleating agents include inorganic compounds such as silica, calcium silicate, wollastonite, kaolin, clay, mica, zinc oxide, calcium carbonate, sodium bicarbonate, zeolite, or talc.
輻射伝熱抑制剤としては、上述の炭素系輻射伝熱抑制剤以外のものを使用できる。例えば、アルミニウム、酸化アルミニウム等のアルミニウム系化合物、アルミン酸亜鉛等の亜鉛系化合物；ハイドロタルサイト等のマグネシウム系化合物；銀等の銀系化合物：チタン、酸化チタン、チタン酸ストロンチウム等のチタン系化合物；ステンレス、ニッケル、錫、銀、銅、ブロンズ、シラスバルーン、セラミックバルーン、マイクロバルーン、パールマイカ等の熱線反射剤や、硫酸バリウム、硫酸ストロンチウム、硫酸カルシウム、メルカライト、ハロトリ石、ミョウバン石、鉄ミョウバン石等の硫酸金属塩；三酸化アンチモン、酸化アンチモン、無水アンチモン酸亜鉛等のアンチモン系化合物；酸化錫、酸化インジウム、酸化亜鉛、酸化インジニウム錫、等の金属酸化物；アンモニウム系、尿素系、イモニウム系、アミニウム系、シアニン系、ポリメチン系、アントラキノン系、ジチオール系、銅イオン系、フェニレンジアミン系、フタロシアニン系、ベンゾトリアゾール系、ベンゾフェノン系、シュウ酸アニリド系、シアノアクリレート系、ベンゾトリアゾール系等の熱線吸収剤が挙げられる。熱伝導率低減効果とコストのバランスの点からチタン系化合物が好ましく、酸化チタンがより好ましい。 Radiation heat transfer inhibitors other than the carbon-based radiation heat transfer inhibitors mentioned above can be used. Examples of the antimony include aluminum, aluminum compounds such as aluminum oxide, and zinc compounds such as zinc aluminate; magnesium compounds such as hydrotalcite; silver compounds such as silver; titanium compounds such as titanium oxide and strontium titanate; heat ray reflectors such as stainless steel, nickel, tin, silver, copper, bronze, shirasu balloons, ceramic balloons, microballoons, and pearl mica; and metal sulfates such as barium sulfate, strontium sulfate, calcium sulfate, mercalite, halotrite, alumite, and ferric alumite; antimony compounds such as antimony trioxide, antimony oxide, and zinc antimonate anhydride; metal oxides such as tin oxide, indium oxide, zinc oxide, and indinium tin oxide; and heat ray absorbers such as ammonium, urea, immonium, aminium, cyanine, polymethine, anthraquinone, dithiol, copper ion, phenylenediamine, phthalocyanine, benzotriazole, benzophenone, oxalic acid anilide, cyanoacrylate, and benzotriazole. Titanium compounds are preferred in terms of the balance between the thermal conductivity reduction effect and cost, with titanium oxide being more preferred.
本発明の効果を損なわない範囲で、塩化ビニル系樹脂に他の樹脂（熱可塑性樹脂や熱硬化性樹脂）を併用してもよい。 Vinyl chloride resins may be used in combination with other resins (thermoplastic resins or thermosetting resins) as long as the effects of the present invention are not impaired.
他の樹脂を併用する場合、他の樹脂の配合量は、本発明の効果を損なわない範囲であれば特に限定されないが、塩化ビニル系樹脂１００重量部に対して０～９９重量部が好ましい。 When other resins are used in combination, the amount of the other resins is not particularly limited as long as it does not impair the effects of the present invention, but it is preferable that the amount is 0 to 99 parts by weight per 100 parts by weight of the vinyl chloride resin.
本発明の発泡性塩化ビニル系樹脂粒子は、後述するような発泡性樹脂粒子を予備発泡・発泡成形できる形状の粒子であれば、粒子の形状は特に問わないが、一般的な粒状物（例えば、球状、略球状、凸レンズ状、凹レンズ状、紡錘状などの丸みを帯びた小さい粒子）だけでなく、凹みのある粒子も含まれるものとする。尚、本発明の発泡性塩化ビニル系樹脂粒子の粒重量は発泡粒子の成形金型への充填性、ひいては発泡成形体の表面美麗性などの成形性を確保する観点から、０．５～１０ｍｇ／粒であることが好ましく、１～８ｍｇ／粒がより好ましく、３～７ｍｇ／粒が更に好ましい。 The shape of the expandable polyvinyl chloride resin particles of the present invention is not particularly limited as long as the shape of the particles allows the expandable resin particles to be pre-expanded and expanded as described below, but this includes not only typical granular objects (for example, small rounded particles such as spherical, nearly spherical, convex lens-like, concave lens-like, and spindle-like), but also particles with indentations. The particle weight of the expandable polyvinyl chloride resin particles of the present invention is preferably 0.5 to 10 mg/particle, more preferably 1 to 8 mg/particle, and even more preferably 3 to 7 mg/particle, from the viewpoint of ensuring the fillability of the expanded particles into a molding die and thus the moldability such as the surface beauty of the expanded molded product.
本発明の発泡性塩化ビニル系樹脂粒子は、発泡性塩化ビニル系樹脂粒子からの発泡剤の逸散速度を小さくする、あるいはより発泡倍率を向上させる観点から、真密度は１２００ｋｇ／ｍ３以上であり、１２３０ｋｇ／ｍ３以上がより好ましく、１２６０ｋｇ／ｍ３以上がさらに好ましい。ここでいう真密度は、後述する測定方法で求めることができる。 From the viewpoint of reducing the rate at which the foaming agent escapes from the foamable vinyl chloride resin particles of the present invention or further improving the expansion ratio, the true density is 1200 kg/m 3 or more, more preferably 1230 kg/m 3 or more, and even more preferably 1260 kg/m 3 or more. The true density here can be determined by the measurement method described below.
（発泡性塩化ビニル系樹脂粒子の製造方法）
発泡性塩化ビニル系樹脂粒子を製造する方法としては、押出機を用いて塩化ビニル系樹脂と炭素系輻射伝熱抑制剤と各種成分とを溶融混練した後、粒子状に切断する溶融混練法、を用いることが望ましい。本発明の一実施形態に係る溶融混練法には、以下の第１の溶融混練法及び第２の溶融混練法の２つがあり、適宜選択することができる。
(Method for producing expandable polyvinyl chloride resin particles)
As a method for producing expandable polyvinyl chloride resin particles, it is preferable to use a melt-kneading method in which a polyvinyl chloride resin, a carbon-based radiation heat transfer inhibitor, and various components are melt-kneaded using an extruder, and then cut into particles. The melt-kneading method according to one embodiment of the present invention includes the following two methods, the first melt-kneading method and the second melt-kneading method, which can be appropriately selected.
第１の溶融混練法としては、塩化ビニル系樹脂、炭素系輻射伝熱抑制剤、および必要に応じて各種添加剤を押出機に供給して溶融混練し、発泡剤を前記押出機または押出機以降の分散設備によって溶融混練物に溶解・分散させ、押出機以降に取り付けた、小孔を多数有するダイを通じて、加圧循環水で満たされたカッターチャンバー内に発泡剤含有塩化ビニル系樹脂組成物の溶融混練物を押し出し、押し出し直後から、ダイと接する回転カッターにより前記溶融混練物を切断すると共に加圧循環水により冷却固化し、発泡性塩化ビニル系樹脂粒子を得る製造方法が挙げられる。 The first melt-kneading method is a manufacturing method in which vinyl chloride resin, a carbon-based radiation heat transfer inhibitor, and various additives, as necessary, are fed to an extruder and melt-kneaded, a foaming agent is dissolved and dispersed in the molten mixture by the extruder or a dispersing device downstream of the extruder, the molten mixture of the foaming agent-containing vinyl chloride resin composition is extruded through a die with many small holes attached downstream of the extruder into a cutter chamber filled with pressurized circulating water, and immediately after extrusion, the molten mixture is cut by a rotating cutter in contact with the die and cooled and solidified by the pressurized circulating water to obtain expandable vinyl chloride resin particles.
第１の溶融混練法は、発泡剤と塩化ビニル系樹脂を溶融混練することで、溶融樹脂の粘度を低下させることができ、塩化ビニル系樹脂の成形加工温度を下げることが可能となり、熱分解が生じにくくなる。中でも、炭素系輻射伝熱抑制剤としてグラファイトを含有する形態においては、塩化ビニル系樹脂とグラファイトとの混錬強度を上げることできるため、グラファイトの一部が剥離し、グラファイトの粒子数が増加しやすくなると推測され、グラファイトの高分散化を達成しやすい。 In the first melt-kneading method, the foaming agent and the polyvinyl chloride resin are melt-kneaded to reduce the viscosity of the molten resin, making it possible to lower the molding processing temperature of the polyvinyl chloride resin and making it less likely for thermal decomposition to occur. In particular, in a form that contains graphite as a carbon-based radiation heat transfer inhibitor, the kneading strength between the polyvinyl chloride resin and the graphite can be increased, which is thought to cause some of the graphite to peel off and increase the number of graphite particles, making it easier to achieve high dispersion of the graphite.
第１の溶融混練法において、押出機としては一般的な押出機を使用することができ、具体的には、単軸押出機、二軸押出機、タンデム押出機などが挙げられる。タンデム押出機としては、単軸押出機を二機連結したものや、二軸押出機に単軸押出機を連結したものなどが挙げられる。また、押出機とスタティックミキサーやスクリューを有さない攪拌機などの分散設備を併用してもよい。 In the first melt-kneading method, a general extruder can be used as the extruder, and specific examples include a single-screw extruder, a twin-screw extruder, and a tandem extruder. Examples of a tandem extruder include two single-screw extruders connected together, and a twin-screw extruder connected to a single-screw extruder. In addition, an extruder may be used in combination with dispersion equipment such as a static mixer or an agitator without a screw.
尚、溶融混練法において、塩化ビニル系樹脂は十分にゲル化させることが好ましい。十分にゲル化が行われないと、発泡性樹脂粒子とした場合に、発泡剤の発泡性樹脂粒子からの散逸速度が大きくなる場合があり、発泡に発泡剤が寄与し難い傾向にあり、結果として高発泡倍率あるいは高独立気泡率を有する発泡粒子及び発泡成形体を得ることが困難となる場合がある。 In the melt kneading method, it is preferable to gel the vinyl chloride resin sufficiently. If gelation is not sufficient, when the resin is made into expandable resin particles, the speed at which the foaming agent escapes from the expandable resin particles may increase, and the foaming agent may not contribute much to the foaming. As a result, it may be difficult to obtain expanded particles and foamed molded articles with a high expansion ratio or a high closed cell ratio.
第１の溶融混練法において、樹脂溶融混練時の樹脂温度については、塩化ビニル系樹脂及び添加剤の分解に影響を及ぼす可能性があることから、押出機先端の樹脂溶融物の樹脂温度が１３０～２５０℃であることが好ましく、より好ましくは１４０～２４０℃であり、更に好ましくは１５０～２２０℃である。押出機先端の樹脂溶融物の樹脂温度は、押出機先端に取り付けられた温度センサーにて測定される値である。ダイより上流側に押出機が二つ以上取り付けられている場合は、最も下流側の押出機の先端温度を、本明細書中の押出機先端の樹脂溶融物の樹脂温度とする。樹脂温度が１３０℃以上であれば、樹脂粘度が下がり押出機内での十分な溶融混練が可能となる。樹脂温度が２５０℃を超えると塩化ビニル系樹脂及び添加剤の分解の恐れがあり、結果として発泡性塩化ビニル系樹脂粒子の劣化を誘発し、発泡性能の低下に繋がる恐れがある。 In the first melt-kneading method, the resin temperature during resin melt-kneading may affect the decomposition of the vinyl chloride resin and additives, so the resin temperature of the resin melt at the tip of the extruder is preferably 130 to 250°C, more preferably 140 to 240°C, and even more preferably 150 to 220°C. The resin temperature of the resin melt at the tip of the extruder is a value measured by a temperature sensor attached to the tip of the extruder. When two or more extruders are attached upstream of the die, the tip temperature of the most downstream extruder is taken as the resin temperature of the resin melt at the tip of the extruder in this specification. If the resin temperature is 130°C or higher, the resin viscosity decreases and sufficient melt-kneading in the extruder is possible. If the resin temperature exceeds 250°C, there is a risk of decomposition of the vinyl chloride resin and additives, which may result in deterioration of the expandable vinyl chloride resin particles and lead to a decrease in the expandability.
（造粒工程の各条件）
第１の溶融混練法における造粒工程の条件について説明する。
(Conditions of granulation process)
The conditions for the granulation step in the first melt-kneading method will be described.
ダイから溶融混練物を押出す実施形態においては、ダイは特に限定されないが、例えば、好ましくは直径０．３ｍｍ～２．０ｍｍ、より好ましくは０．４ｍｍ～１．５ｍｍの小孔を有するものが挙げられる。 In an embodiment in which the molten mixture is extruded from a die, the die is not particularly limited, but examples include dies having small holes preferably with a diameter of 0.3 mm to 2.0 mm, more preferably 0.4 mm to 1.5 mm.
第１の溶融混練法において、ダイより上流側に取り付けられた押出機の先端圧力が４～２０ＭＰａであることが好ましく、より好ましくは６～１８ＭＰａであり、７～１５ＭＰａであるこことが更に好ましい。なお、押出機先端圧力は、押出機先端に取り付けられた圧力センサーにて測定される値である。ダイより上流側に押出機が二つ以上取り付けられている場合は、最も下流側の押出機の先端圧力を、本明細書中の押出機先端圧力とする。押出機先端圧力が４ＭＰａ以上であれば、溶融混練時に樹脂への発泡剤の溶解分散が容易になり、安定的に発泡性塩化ビニル系樹脂粒子を得ることができる。一方で、押出機先端圧力が２０ＭＰａ以下であれば、溶融混練時のせん断発熱を抑制することができ、塩化ビニル系樹脂、必要により併用される塩化ビニル系樹脂及び添加剤の分解が生じにくくなる。 In the first melt-kneading method, the tip pressure of the extruder attached upstream of the die is preferably 4 to 20 MPa, more preferably 6 to 18 MPa, and even more preferably 7 to 15 MPa. The extruder tip pressure is a value measured by a pressure sensor attached to the tip of the extruder. When two or more extruders are attached upstream of the die, the tip pressure of the most downstream extruder is defined as the extruder tip pressure in this specification. If the extruder tip pressure is 4 MPa or more, the foaming agent is easily dissolved and dispersed in the resin during melt-kneading, and foamable vinyl chloride resin particles can be obtained stably. On the other hand, if the extruder tip pressure is 20 MPa or less, shear heat generation during melt-kneading can be suppressed, and decomposition of the vinyl chloride resin, the vinyl chloride resin used in combination as necessary, and additives is less likely to occur.
第１の溶融混練法において、ダイより押出される直前の溶融樹脂の温度は、発泡剤を含まない状態での樹脂のガラス転移温度をＴｇとすると、Ｔｇ＋２０℃以上であることが好ましく、Ｔｇ＋２０℃～Ｔｇ＋１３０℃がより好ましく、Ｔｇ＋３０℃～Ｔｇ＋１１０℃であることがさらに好ましく、Ｔｇ＋４０℃～Ｔｇ＋９０℃であることが特に好ましい。尚、塩化ビニル系樹脂については、塩素含有量の増加に伴い、ガラス転移温度が上昇するため、使用する塩化ビニル系樹脂の塩素含有量に伴い、適宜調整することが好ましい。Ｔｇ＋２０℃以上であれば、押出された溶融樹脂の粘度が低くなり、小孔詰まりが発生しにくく、実質小孔開口率の低下が起きないため、得られる発泡性塩化ビニル系樹脂粒子の形状が歪もしくは不揃いとなる事態を避けることができる。一方で、Ｔｇ＋１３０℃以下であれば、押出された溶融樹脂が固化し易くなり、回転カッターに巻き付き難くなり、安定的に切断できる。 In the first melt-kneading method, the temperature of the molten resin immediately before being extruded from the die is preferably Tg+20°C or higher, more preferably Tg+20°C to Tg+130°C, even more preferably Tg+30°C to Tg+110°C, and particularly preferably Tg+40°C to Tg+90°C, where Tg is the glass transition temperature of the resin without the foaming agent. Note that, for vinyl chloride resins, the glass transition temperature increases with an increase in the chlorine content, so it is preferable to adjust the temperature appropriately according to the chlorine content of the vinyl chloride resin used. If the temperature is Tg+20°C or higher, the viscosity of the extruded molten resin is low, small pore clogging is unlikely to occur, and there is no decrease in the actual small pore opening rate, so that it is possible to avoid a situation in which the shape of the resulting expandable vinyl chloride resin particles becomes distorted or irregular. On the other hand, if the temperature is Tg+130°C or lower, the extruded molten resin is easily solidified, is less likely to wrap around the rotary cutter, and can be cut stably.
第１の溶融混練法における加圧循環冷却水に押出された溶融樹脂を切断する切断装置としては、特に限定されないが、例えば、ダイに接触する回転カッターで切断されて小球化され、加圧循環冷却水中で発泡することなく、遠心脱水機まで移送されて脱水・集約される装置、等が挙げられる。 The cutting device for cutting the molten resin extruded into the pressurized circulating cooling water in the first melt kneading method is not particularly limited, but examples include a device in which the molten resin is cut into small pellets by a rotating cutter that contacts a die, and then transported to a centrifugal dehydrator to be dehydrated and aggregated without foaming in the pressurized circulating cooling water.
加圧循環冷却水の条件については、使用する樹脂、添加剤、発泡剤などの種類や、各含有量によって調整すべきであるが、ダイより押し出される溶融樹脂の発泡が抑制され、安定的にカッターで切断される条件が好ましい。具体的には、加圧循環冷却水の温度条件としては、好ましくは４０℃～９９℃、より好ましくは６０～９０℃である。 The conditions for the pressurized circulating cooling water should be adjusted depending on the type and content of the resin, additives, foaming agent, etc. used, but it is preferable that the molten resin extruded from the die is prevented from foaming and is cut stably with the cutter. Specifically, the temperature condition for the pressurized circulating cooling water is preferably 40°C to 99°C, more preferably 60°C to 90°C.
圧力条件としては、得られる発泡性塩化ビニル系樹脂粒子の発泡倍率が１．０～１．２５倍となるよう、圧力を調整することが好ましい。尚、前記発泡性塩化ビニル系樹脂粒子の発泡倍率は、基材樹脂の真密度（ｋｇ／ｍ３）を発泡性塩化ビニル系樹脂粒子の真密度（ｋｇ／ｍ３）で除した値を指す。ここでいう基材樹脂及び発泡性塩化ビニル系樹脂粒子の真密度は、重量Ｗ（ｋｇ）の塩化ビニル系樹脂ペレットまたは発泡性塩化ビニル系樹脂粒子を、エタノールの入ったメスシリンダー内に沈め、メスシリンダーの液面上昇分（水没法）から体積Ｖ（ｍ３）を求め、算出される。具体的には後述する測定方法から求めることができる。 As for the pressure conditions, it is preferable to adjust the pressure so that the expansion ratio of the resulting expandable vinyl chloride resin particles is 1.0 to 1.25 times. The expansion ratio of the expandable vinyl chloride resin particles refers to the value obtained by dividing the true density (kg/m 3 ) of the base resin by the true density (kg/m 3 ) of the expandable vinyl chloride resin particles. The true density of the base resin and the expandable vinyl chloride resin particles referred to here is calculated by submerging a weight W (kg) of vinyl chloride resin pellets or expandable vinyl chloride resin particles in a graduated cylinder containing ethanol, and determining the volume V (m 3 ) from the rise in the liquid level of the graduated cylinder (submersion method). Specifically, it can be determined by the measurement method described below.
使用する発泡剤の種類にも依存するが、圧力条件は、好ましくは０．６～２．０ＭＰａ、より好ましくは０．７～１．８ＭＰａ、更に好ましくは０．８～１．６ＭＰａである。 Although it depends on the type of foaming agent used, the pressure conditions are preferably 0.6 to 2.0 MPa, more preferably 0.7 to 1.8 MPa, and even more preferably 0.8 to 1.6 MPa.
第１の溶融混練法の利点は発泡性樹脂粒子まで同じ設備で製造できるため、次に述べる第２の溶融混練法と比較してランニングコストが低くなることである。一方、グラファイト量、グラファイト粒径がダイスの小孔開口率に影響を与えるため、第１の溶融混練法の生産安定性は、次の第２の溶融混練法と比較すると低くなる。 The advantage of the first melt-kneading method is that it can produce expandable resin particles using the same equipment, resulting in lower running costs compared to the second melt-kneading method described below. On the other hand, the amount of graphite and the graphite particle size affect the die hole opening rate, so the production stability of the first melt-kneading method is lower than that of the second melt-kneading method described below.
第２の溶融混練法としては、塩化ビニル系樹脂と炭素系輻射伝熱抑制剤を押出機で溶融混練し、コールドカット法又はホットカット法等を用いて樹脂ペレットを得た後、該樹脂ペレットを水中等に懸濁させると共に、該ペレットに発泡剤を含有させる方法がある。 The second melt-kneading method involves melt-kneading a vinyl chloride resin and a carbon-based radiation heat transfer inhibitor in an extruder, obtaining resin pellets using a cold cut method or a hot cut method, etc., and then suspending the resin pellets in water, etc., and incorporating a foaming agent into the pellets.
さらに詳しくは、第２の溶融混練法は、まず、塩化ビニル系樹脂、及び炭素系輻射伝熱抑制剤、並びに必要に応じて、他の添加材を押出機で溶融混練してもよい。その後溶融混練物を、小孔を有するダイスを通じて押出した後カッターで切断することにより樹脂粒子を得た後、該樹脂粒子を水中に懸濁させると共に、物理系発泡剤を供給して、発泡性樹脂粒子を得る製造方法が挙げられる。 More specifically, the second melt-kneading method may involve first melt-kneading a vinyl chloride resin, a carbon-based radiation heat transfer inhibitor, and, if necessary, other additives in an extruder. The melt-kneaded mixture is then extruded through a die with small holes and cut with a cutter to obtain resin particles, which are then suspended in water and a physical foaming agent is supplied to obtain expandable resin particles.
第２の溶融混練法における押出機の溶融混練部の設定温度は、１００℃～２５０℃が望ましい。また、押出機に材料を供給してから溶融混練終了までの押出機内滞留時間が１５分以下であることが望ましい。 In the second melt-kneading method, the set temperature of the melt-kneading section of the extruder is preferably 100°C to 250°C. In addition, it is preferable that the residence time in the extruder from when the material is fed to the extruder until the end of melt-kneading is 15 minutes or less.
押出機の溶融混練部での設定温度が２５０℃以下の場合、及び／又は、溶融混練終了までの押出機内滞留時間が１５分以下の場合には、塩化ビニル系樹脂の分解が起こりにくく、樹脂の劣化を抑制することで所定の発泡性が得られ易い効果を奏する。 When the temperature setting in the melt-kneading section of the extruder is 250°C or less, and/or the residence time in the extruder until the end of melt-kneading is 15 minutes or less, decomposition of the vinyl chloride resin is unlikely to occur, and deterioration of the resin is suppressed, making it easier to obtain the desired foamability.
一方、押出機の溶融混練部の設定温度が１００℃以上の場合には、押出機の負荷が小さくなって押出が安定となる。 On the other hand, if the set temperature of the melt-kneading section of the extruder is 100°C or higher, the load on the extruder is reduced and extrusion becomes stable.
第２の溶融混練法で用いられるダイスは特に限定されないが、例えば、直径０．３ｍｍ～２．０ｍｍ、望ましくは０．８ｍｍ～１．６ｍｍの小孔を有するものが挙げられる。 The die used in the second melt-kneading method is not particularly limited, but examples include dies with small holes having a diameter of 0.3 mm to 2.0 mm, preferably 0.8 mm to 1.6 mm.
第２の溶融混練法の利点は、一般的な発泡性樹脂粒子の製造に使用される装置を使用して樹脂粒子に発泡剤を含浸できるため、大きな設備投資又は設備変更が必要ないこと、及び、炭素系輻射伝熱抑制剤の使用量等を変更しても樹脂粒子の生産安定性が高いことにある。一方、樹脂粒子の生産と発泡性樹脂粒子の生産とを別プラントで実施するためにランニングコストは第１の溶融混練法よりも高くなる。 The advantage of the second melt-kneading method is that the resin particles can be impregnated with the blowing agent using equipment commonly used in the production of expandable resin particles, so no major capital investment or equipment changes are required, and the production stability of the resin particles is high even if the amount of carbon-based radiation heat transfer inhibitor used is changed. On the other hand, the production of resin particles and the production of expandable resin particles are carried out in separate plants, so the running costs are higher than those of the first melt-kneading method.
（塩化ビニル系樹脂発泡粒子及びその製造方法）
本発明の発泡性塩化ビニル系樹脂粒子は、加熱空気や水蒸気などの加熱媒体により、２～１１０倍に予備発泡されて塩化ビニル系樹脂発泡粒子にされたのち、発泡成形体に使用されうる。使用できる水蒸気は、飽和水蒸気であってもよいし過熱水蒸気であってもよい。
(Polyvinyl chloride resin foam particles and their manufacturing method)
The expandable polyvinyl chloride resin particles of the present invention can be used for a foamed molded article after being pre-expanded 2 to 110 times by a heating medium such as heated air or steam to form expanded polyvinyl chloride resin particles. The steam that can be used may be saturated steam or superheated steam.
発泡時の加熱温度は、樹脂のガラス転移温度や融点、更には発泡剤の含有量によって適宜調整すべきであるが、９０℃以上が好ましく、１００℃以上がより好ましい。一方、発泡粒子間の発泡倍率バラつきの抑制や発泡粒子の収縮防止の観点から１５０℃以下が好ましく、１３０℃以下がより好ましい。 The heating temperature during foaming should be adjusted appropriately depending on the glass transition temperature and melting point of the resin, as well as the amount of foaming agent, but is preferably 90°C or higher, and more preferably 100°C or higher. On the other hand, from the viewpoint of suppressing the variation in the expansion ratio between the foamed beads and preventing the shrinkage of the foamed beads, it is preferably 150°C or lower, and more preferably 130°C or lower.
（塩化ビニル系樹脂発泡成形体及びその製造方法）
得られた塩化ビニル系樹脂発泡粒子は、従来公知の成形機を用い、例えば水蒸気によって成形（例えば型内成形）されて塩化ビニル系樹脂発泡成形体が作製される。使用される金型の形状により、複雑な形の型物成形体やブロック状の成形体を得ることができる。
(Polyvinyl chloride resin foam molded product and its manufacturing method)
The obtained polyvinyl chloride resin foamed particles are molded (e.g., molded in a mold) using a conventional molding machine, for example, with steam to produce a polyvinyl chloride resin foamed molded article. Depending on the shape of the mold used, a molded article with a complex shape or a block-like molded article can be obtained.
（独立気泡率）
本発明に係る塩化ビニル系樹脂発泡粒子及びその塩化ビニル系樹脂発泡成形体は、独立気泡率が好ましくは７０％以上、より好ましくは８０％以上、更に好ましくは９０％以上である。独立気泡率が前述の範囲にあることによって、成形時にも発泡粒子が２次発泡しやすく、発泡粒子の成形性が良くなり、得られる発泡成形体の表面性等が良化する等の効果を奏する。また、独立気泡率が前述の範囲にあることによって、発泡成形体の圧縮強度等の強度を高くできる傾向にある。
(Closed bubble ratio)
The vinyl chloride resin foamed beads and the vinyl chloride resin foamed molded article thereof according to the present invention preferably have a closed cell ratio of 70% or more, more preferably 80% or more, and even more preferably 90% or more. By having the closed cell ratio in the above-mentioned range, the foamed beads are easily subjected to secondary expansion during molding, the moldability of the foamed beads is improved, and the surface properties of the resulting foamed molded article are improved. In addition, by having the closed cell ratio in the above-mentioned range, the strength of the foamed molded article, such as the compressive strength, tends to be increased.
（発泡成形体の用途）
本発明の発泡性塩化ビニル系樹脂粒子を用いて成形される発泡成形体は、優れた断熱性と難燃性を示すうえに、高い発泡倍率を有しうる。従って、例えば、建築用断熱材、天井材、金属サンドイッチパネルの芯材、食品容器箱、保冷箱、緩衝材、農水産箱、浴室用断熱材及び貯湯タンク断熱材、配管断熱材のような各種用途に好適である。
(Applications of foamed molded products)
The foamed molded article formed using the expandable polyvinyl chloride resin particles of the present invention exhibits excellent heat insulation and flame retardancy, and can have a high expansion ratio, and is therefore suitable for various applications such as building insulation materials, ceiling materials, core materials for metal sandwich panels, food container boxes, cold storage boxes, cushioning materials, agricultural and fishery boxes, bathroom insulation materials, hot water tank insulation materials, and piping insulation materials.
本発明の一実施形態は前述した各実施形態に限定されるものではなく、請求項に示した範囲で種々の変更が可能であり、異なる実施形態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についても本発明の一実施形態の技術的範囲に含まれる。 One embodiment of the present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. An embodiment obtained by appropriately combining the technical means disclosed in different embodiments is also included in the technical scope of one embodiment of the present invention.
以下、実施例及び比較例に基づいて本発明の一実施形態を具体的に説明するが、本発明はこれらに限定されるものではない。 Below, an embodiment of the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited to these.
なお、以下の実施例及び比較例における測定方法及び評価方法は、以下のとおりである。 The measurement and evaluation methods used in the following examples and comparative examples are as follows:
（塩化ビニル系樹脂発泡成形体の熱伝導率の測定）
一般的に熱伝導率の測定平均温度が大きい方が熱伝導率の値は大きくなることが知られており、断熱性を比較するためには測定平均温度を定める必要がある。本明細書では発泡プラスチック保温材の規格であるＪＩＳ Ａ９５１１：２００６Ｒで定められた２３℃を基準に採用している。
以下の実施例及び比較例では、熱伝導率は、塩化ビニル系樹脂発泡成形体から熱伝導率測定用サンプルを切り出し、当該サンプルを６０℃温度下で２８日間静置し、さらに、２３℃の温度下にて２４時間静置した後に測定した。
より詳しくは、塩化ビニル系樹脂発泡成形体から、長さ３００ｍｍ×幅３００ｍｍ×２５ｍｍのサンプルを切り出した。厚み方向は塩化ビニル系樹脂発泡成形体の厚さ２５ｍｍをそのまま使用した。従って、サンプルの長さ３００ｍｍ×幅３００ｍｍの２面は塩化ビニル系樹脂発泡成形体の成形された時の表面のままである。サンプルを６０℃温度下にて２８日間静置し、さらに、２３℃温度下にて２４時間静置した後、熱伝導率測定装置（英弘精機（株）製、ＨＣ－０７４）を用いて、ＪＩＳ Ａ１４１２－２：１９９９に準拠して熱流計法にて平均温度２３℃、温度差２０℃で熱伝導率を測定した。
(Measurement of thermal conductivity of polyvinyl chloride resin foam molded body)
It is generally known that the higher the average temperature at which thermal conductivity is measured, the higher the thermal conductivity value, and therefore it is necessary to determine the average temperature at which it is measured in order to compare thermal insulation properties. In this specification, the standard used is 23°C, as defined in JIS A9511:2006R, the standard for foamed plastic insulation materials.
In the following Examples and Comparative Examples, the thermal conductivity was measured by cutting a sample for measuring the thermal conductivity from a polyvinyl chloride resin foam molded article, leaving the sample at 60°C for 28 days, and then leaving it at 23°C for 24 hours.
More specifically, a sample of 300 mm length x 300 mm width x 25 mm was cut out from the polyvinyl chloride resin foam molded body. The thickness direction was 25 mm of the polyvinyl chloride resin foam molded body. Therefore, the two surfaces of the sample with a length of 300 mm x width of 300 mm remained as the surface of the polyvinyl chloride resin foam molded body when it was molded. The sample was left at 60°C for 28 days and then at 23°C for 24 hours, and then the thermal conductivity was measured at an average temperature of 23°C and a temperature difference of 20°C using a thermal conductivity measuring device (HC-074, manufactured by Eiko Seiki Co., Ltd.) by the heat flow meter method in accordance with JIS A1412-2:1999.
（グラファイト含有量の測定）
実施例１および比較例１で得られた発泡性塩化ビニル系樹脂粒子を約１０ｍｇ採取し、また、参考例１および参考例２で得られたポリスチレン系樹脂発泡成形体約１０ｍｇを試験片として切り出し、サンプルとした。このサンプルを、熱分析システム：ＥＸＳＴＡＲ６０００を備えた熱重量測定装置（エスアイアイ・ナノテクノロジー（株）製、ＴＧ／ＤＴＡ ２２０Ｕ）を用いて、下記Ｉ～ＩＩＩを連続で実施し、ＩＩＩにおける重量減少量をグラファイト重量とし、試験片重量に対するパーセントで表した。
Ｉ． ２００ｍＬ／分の窒素気流下で４０℃から６００℃まで２０℃／分で昇温した後６００℃で１０分保持、
ＩＩ． ２００ｍＬ／分の窒素気流下で６００℃から４００℃まで１０℃／分で降温した後４００℃で５分保持、
ＩＩＩ．２００ｍＬ／分の空気気流下で４００℃から８００℃まで２０℃／分で昇温した後８００℃で１５分保持。
(Measurement of Graphite Content)
Approximately 10 mg of the expandable vinyl chloride resin particles obtained in Example 1 and Comparative Example 1 was collected, and approximately 10 mg of the polystyrene resin foamed molded article obtained in Reference Examples 1 and 2 was cut out as a test piece to prepare a sample. The sample was subjected to the following steps I to III in succession using a thermogravimetric analyzer (TG/DTA 220U, manufactured by SII NanoTechnology Co., Ltd.) equipped with a thermal analysis system: EXSTAR6000, and the weight loss amount in III was taken as the graphite weight and expressed as a percentage of the test piece weight.
I. Heat from 40° C. to 600° C. at a rate of 20° C./min under a nitrogen flow of 200 mL/min, then hold at 600° C. for 10 minutes;
II. Under a nitrogen flow of 200 mL/min, the temperature was lowered from 600° C. to 400° C. at a rate of 10° C./min, and then the temperature was held at 400° C. for 5 minutes;
III. The temperature was increased from 400° C. to 800° C. at a rate of 20° C./min under an air flow of 200 mL/min, and then held at 800° C. for 15 minutes.
（グラファイトの平均粒径Ｄ５０（μｍ）及びレーザー散乱強度（％）の測定）
（１）試料溶液調整条件
（ａ）測定対象が、発泡性塩化ビニル系樹脂粒子又は発泡成形体の場合
試料５００ｍｇを０．１％（ｗ／ｗ）スパン８０ＴＨＦ溶液２０ｍＬに溶解・分散させる。
（ｂ）測定対象が、混練前のグラファイト、即ち原材料のグラファイト自体の場合
グラファイト２０ｍｇ及び塩化ビニル系樹脂（Ａ）４８０ｍｇを０．１％（ｗ／ｗ）スパン８０ＴＨＦ溶液２０ｍＬに溶解・分散させる。
上記（ａ）（ｂ）において、分散とは、樹脂が溶解して、グラファイトが分散している状態のことをいう。
次いで、超音波洗浄器にて、前記の試料溶液に超音波を照射し、グラファイトの凝集を緩和させる。
(Measurement of Graphite Average Particle Size D50 (μm) and Laser Scattering Intensity (%))
(1) Conditions for preparing sample solution (a) When the measurement subject is expandable polyvinyl chloride resin particles or foamed molded products, 500 mg of sample is dissolved/dispersed in 20 mL of 0.1% (w/w) Span 80 THF solution.
(b) When the measurement subject is graphite before kneading, i.e., the raw material graphite itself, 20 mg of graphite and 480 mg of polyvinyl chloride resin (A) are dissolved/dispersed in 20 mL of 0.1% (w/w) Span 80 THF solution.
In the above (a) and (b), "dispersion" refers to a state in which the resin is dissolved and the graphite is dispersed.
Next, the sample solution is irradiated with ultrasonic waves in an ultrasonic cleaner to relax the agglomeration of graphite.
（２）超音波照射条件
使用装置 ：アズワン株式会社製 超音波洗浄器 型番ＵＳＭ
発振周波数：４２ｋＨｚ
照射時間 ：１０分
温度 ：室温
(2) Ultrasonic irradiation conditions Equipment used: Ultrasonic cleaner manufactured by AS ONE Corporation, model number USM
Oscillation frequency: 42kHz
Irradiation time: 10 minutes Temperature: Room temperature
（３）平均粒子径測定条件
測定装置 ：マルバーン社製 レーザー回折式粒度分布測定装置 マスターサイザー３０００
光源 ：６３２．８ｎｍ赤色Ｈｅ－Ｎｅレーザー及び４７０ｎｍ青色ＬＥＤ
分散ユニット：湿式分散ユニット Ｈｙｄｒｏ ＭＶ
以下の設定で分析を実施し、ＩＳＯ１３３２０：２００９，ＪＩＳ Ｚ８８２５－１に準拠したＭｉｅ理論に基づくレーザー回折・散乱法による測定・解析により、体積分布を求め、サンプル中のグラファイトのＤ５０粒径を算出し、グラファイトの平均粒子径とした。なお、グラファイトの平均粒子径の測定結果に影響を与える他の材料を含有する場合は、グラファイトのみを分離して評価を行う。グラファイトのみの分離が困難な場合においては、原料として使用するグラファイトで評価を行い、測定結果をグラファイトの平均粒子径とする。
粒子の種類 ：非球形
グラファイト屈折率 ：２．４２
グラファイト吸収率 ：１．０
分散媒体 ：０．１％（ｗ／ｗ）スパン８０ＴＨＦ溶液
分散媒体の屈折率 ：１．４９
分散ユニット中の攪拌数：２５００ｒｐｍ
解析モデル ：汎用、単一モードを維持
測定温度 ：室温
(3) Average particle size measurement conditions Measuring device: Malvern Laser Diffraction Particle Size Distribution Measurement Device Mastersizer 3000
Light source: 632.8 nm red He-Ne laser and 470 nm blue LED
Dispersion unit: Wet dispersion unit Hydro MV
The analysis was carried out under the following settings, and the volume distribution was obtained by measurement and analysis using a laser diffraction/scattering method based on the Mie theory in accordance with ISO13320:2009 and JIS Z8825-1, and the D50 particle size of the graphite in the sample was calculated and used as the average particle size of the graphite. When other materials that affect the measurement results of the average particle size of graphite are contained, only the graphite is separated and evaluated. When it is difficult to separate only the graphite, evaluation is carried out using the graphite used as the raw material, and the measurement result is used as the average particle size of graphite.
Particle type: non-spherical graphite Refractive index: 2.42
Graphite absorption rate: 1.0
Dispersion medium: 0.1% (w/w) Span 80 in THF solution Refractive index of dispersion medium: 1.49
Agitation speed in the dispersion unit: 2500 rpm
Analysis model: General purpose, maintains single mode Measurement temperature: Room temperature
（４）測定手順
０．１％（ｗ／ｗ）スパン８０ＴＨＦ溶液１２０ｍＬを分散ユニットに注入し、２５００ｒｐｍで攪拌し、安定化させた。測定セルに試料溶液サンプルが存在せず、分散媒体のみの状態で６３２．８ｎｍ赤色Ｈｅ－Ｎｅレーザー光を照射した際の中央検出器で測定された光の強度を透過光の強度Ｌｂとした。次いで、超音波処理した試料溶液を２ｍＬ採取し、分散ユニットに追加した。試料溶液を追加して１分後の６３２．８ｎｍ赤色Ｈｅ－Ｎｅレーザー光を照射した際の中央検出器で測定された光の強度を透過光の強度Ｌｓとした。また、同時に粒径（Ｄ５０）を測定した。得られたＬｓ及びＬｂより、以下の式で試料溶液のレーザー散乱強度Ｓを算出した。
(4) Measurement procedure 120 mL of 0.1% (w/w) Span 80 THF solution was poured into the dispersion unit, stirred at 2500 rpm, and stabilized. The light intensity measured by the central detector when irradiating 632.8 nm red He-Ne laser light in a state where there was no sample solution sample in the measurement cell and only the dispersion medium was used as the transmitted light intensity Lb. Next, 2 mL of the ultrasonically treated sample solution was collected and added to the dispersion unit. The light intensity measured by the central detector when irradiating 632.8 nm red He-Ne laser light 1 minute after adding the sample solution was used as the transmitted light intensity Ls. At the same time, the particle size (D50) was measured. From the obtained Ls and Lb, the laser scattering intensity S of the sample solution was calculated using the following formula.
Ｓ＝（１－Ｌｓ／Ｌｂ）×１００（％）
中央検出器はレーザー光の出力に対して対向した正面に位置する検出部であり、ここで検出される光が散乱に使用されなかった透過光の尺度である。レーザー散乱強度とは、解析装置のレーザーに試料を散乱させた際に失われるレーザー光の量の尺度である。
S = (1 - Ls / Lb) x 100 (%)
The central detector is a detector located in front of and facing the output of the laser light, and the light detected here is a measure of the transmitted light that was not used for scattering. The laser scattering intensity is a measure of the amount of laser light lost when the sample is scattered by the laser of the analytical device.
（５）発泡性塩化ビニル系樹脂粒子又は発泡成形体単位溶液濃度あたりのレーザー散乱強度の算出
以下の式にて、発泡性塩化ビニル系樹脂粒子又は発泡成形体単位溶液濃度あたりのレーザー散乱強度Ｔを算出した。
発泡性塩化ビニル系樹脂粒子又は発泡成形体単位溶液濃度あたりのレーザー散乱強度Ｔ（％／（ｍｇ／ｍｌ））＝レーザー散乱強度(Ｓ)／｛サンプル重量（５００ｍｇ）／ＴＨＦ量（２０ｍＬ）×試料注入量（２ｍＬ）／分散ユニット内の全ＴＨＦ量（１２０ｍＬ＋２ｍＬ）｝
単位溶液濃度あたりのレーザー散乱強度とは、測定したレーザー散乱強度をＴＨＦ中のサンプル濃度で割った値である。この測定装置は溶液で測定する必要のある装置であるため、ＴＨＦ溶液中のサンプル濃度を一定とし、一定のサンプル量における測定値を得ている。
(5) Calculation of Laser Scattering Intensity per Unit Solution Concentration of Expandable PVC Resin Particles or Foam Molded Product The laser scattering intensity T per unit solution concentration of expandable PVC resin particles or foam molded product was calculated by the following formula.
Laser scattering intensity T per unit solution concentration of expandable polyvinyl chloride resin particles or foamed molded product (%/(mg/ml))=laser scattering intensity (S)/{sample weight (500 mg)/amount of THF (20 mL)×amount of sample injected (2 mL)/total amount of THF in dispersion unit (120 mL+2 mL)}
The laser scattering intensity per unit solution concentration is the measured laser scattering intensity divided by the sample concentration in THF. Since this measurement device requires measurement in a solution, the sample concentration in the THF solution is kept constant, and the measured value is obtained for a constant sample amount.
（６）発泡性塩化ビニル系樹脂粒子中のグラファイト単位溶液濃度あたりのレーザー散乱強度の算出
以下の式にて、発泡性塩化ビニル系樹脂粒子中に含有されるグラファイト単位溶液濃度あたりのレーザー散乱強度を算出した。
発泡性塩化ビニル系樹脂粒子中のグラファイト単位溶液濃度あたりのレーザー散乱強度｛％／（ｍｇ／ｍｌ）｝／重量％＝（Ｔ－Ｔ１）／発泡性塩化ビニル系樹脂粒子のグラファイト含有量（重量％）
ここで、Ｔ１は、グラファイトを含有しない以外は同組成の発泡性塩化ビニル系樹脂粒子から測定した発泡性塩化ビニル系樹脂粒子単位溶液濃度あたりのレーザー散乱強度の値であり、グラファイト由来のレーザー散乱強度を算出するために測定したものである。なお、Ｔ１測定用の発泡性塩化ビニル系樹脂粒子は、上記「（５）発泡性塩化ビニル系樹脂粒子又は発泡成形体単位溶液濃度あたりのレーザー散乱強度の算出」における発泡性塩化ビニル系樹脂粒子の測定と同様にして、発泡性塩化ビニル系樹脂粒子単位溶液濃度あたりのレーザー散乱強度を求めた。
同じ重量のグラファイトであっても発泡性塩化ビニル系樹脂粒子に含有されるグラファイトの状態、即ち分散されている濃度を調節することによって断熱性を向上できることが本発明の一実施形態の本質である。前記グラファイト単位溶液濃度あたりのレーザー散乱強度を用いることによって本発明の一実施形態を表現することができる。
(6) Calculation of Laser Scattering Intensity per Graphite Unit Solution Concentration in Expandable PVC Resin Particles The laser scattering intensity per graphite unit solution concentration contained in the expandable PVC resin particles was calculated using the following formula.
Laser scattering intensity per unit solution concentration of graphite in expandable polyvinyl chloride resin particles {%/(mg/ml)}/weight %=(T−T 1 )/graphite content of expandable polyvinyl chloride resin particles (weight %)
Here, T1 is the value of the laser scattering intensity per unit solution concentration of the expandable vinyl chloride resin particles measured from expandable vinyl chloride resin particles having the same composition except that it does not contain graphite, and is measured to calculate the laser scattering intensity derived from graphite. Note that, for the expandable vinyl chloride resin particles for measuring T1 , the laser scattering intensity per unit solution concentration of the expandable vinyl chloride resin particles was calculated in the same manner as in the measurement of the expandable vinyl chloride resin particles in the above "(5) Calculation of the laser scattering intensity per unit solution concentration of the expandable vinyl chloride resin particles or foamed molded product".
The essence of one embodiment of the present invention is that even if the weight of graphite is the same, the heat insulating property can be improved by adjusting the state of graphite contained in the expandable polyvinyl chloride resin particles, i.e., the concentration of the graphite dispersed therein. One embodiment of the present invention can be expressed by using the laser scattering intensity per unit solution concentration of the graphite.
（７）発泡成形体中のグラファイト単位溶液濃度あたりのレーザー散乱強度の算出
以下の式にて、発泡成形体中に含有されるグラファイト単位溶液濃度あたりのレーザー散乱強度を算出した。
(7) Calculation of laser scattering intensity per unit graphite solution concentration in foam molded product The laser scattering intensity per unit graphite solution concentration contained in the foam molded product was calculated using the following formula.
発泡成形体中のグラファイト単位溶液濃度あたりのレーザー散乱強度｛％／（ｍｇ／ｍｌ）｝／重量％＝（Ｔ－Ｔ２）／発泡成形体のグラファイト含有量（重量％）
ここで、Ｔ２はグラファイトのみを含有しない同組成の発泡成形体から測定した発泡成形体単位溶液濃度あたりのレーザー散乱強度の値であり、グラファイト由来のレーザー散乱強度を算出するために測定したものである。なお、Ｔ２測定用発泡成形体は、上記「（５）発泡性塩化ビニル系樹脂粒子又は発泡成形体単位溶液濃度あたりのレーザー散乱強度の算出」における発泡成形体の測定と同様にして発泡成形体単位溶液濃度あたりのレーザー散乱強度を求めた。
Laser scattering intensity per unit graphite solution concentration in foamed molded product {%/(mg/ml)}/weight %=(T−T 2 )/graphite content (weight %) of foamed molded product
Here, T2 is the value of the laser scattering intensity per foam-molded unit solution concentration measured from a foam-molded product of the same composition that does not contain only graphite, and was measured in order to calculate the laser scattering intensity derived from graphite. The foam-molded product for T2 measurement was measured for the laser scattering intensity per foam-molded unit solution concentration in the same manner as in the measurement of the foam-molded product in the above "(5) Calculation of the laser scattering intensity per expandable vinyl chloride resin particle or foam-molded product unit solution concentration".
（燃焼性の評価）
発泡成形体から１０ｃｍ×１０ｃｍ×２．５ｃｍになるようにコーンカロリーメーター試験用サンプルを切り出し、６０℃で２８日間養生した後、ＩＳＯ－５６６０に準拠し、放射熱強度５０ｋＷ／ｍ２にて２０分間加熱したときの最大発熱速度、総発熱量を測定した。この測定方法は、建築基準法施行令第１０８条の２に規定される公的機関である建築総合試験所にて、コーンカロリーメーター法による基準に対応するものとして規定された試験法であり、ＩＳＯ－５６６０の試験方法に準拠したものである。
(Evaluation of flammability)
A cone calorimeter test sample measuring 10 cm x 10 cm x 2.5 cm was cut out from the foamed molded article, and after curing at 60°C for 28 days, the maximum heat release rate and total heat release were measured when heated for 20 minutes at a radiant heat intensity of 50 kW/ m2 in accordance with ISO-5660. This measurement method is a test method specified by the General Building Research Institute, a public institution specified in Article 108-2 of the Enforcement Order of the Building Standards Act, as a test method corresponding to the standards based on the cone calorimeter method, and complies with the test method of ISO-5660.
（発泡性塩化ビニル系樹脂粒子の粒重量の測定）
０．０１ｍｇまで測定できる電子天秤を用いて、ランダムにサンプリングした発泡性塩化ビニル系樹脂粒子１００粒の重量を測定し、以下の式で粒重量を算出した。
(Measurement of particle weight of expandable polyvinyl chloride resin particles)
Using an electronic balance capable of measuring to the nearest 0.01 mg, the weight of 100 randomly sampled expandable polyvinyl chloride resin particles was measured, and the particle weight was calculated using the following formula.
粒重量（ｍｇ）＝［粒子１００粒の重量（ｍｇ）］／１００ Grain weight (mg) = [Weight of 100 grains (mg)]/100
（発泡性塩化ビニル系樹脂粒子の真密度測定）
重量Ｗ（ｋｇ）の発泡性塩化ビニル系樹脂粒子を、エタノールの入ったメスシリンダー内に沈め、メスシリンダーの液面上昇分（水没法）から体積Ｖ（ｍ３）を求め、以下の式で算出した。
(Measurement of true density of expandable polyvinyl chloride resin particles)
The expandable polyvinyl chloride resin particles having a weight W (kg) were submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) was obtained from the rise in the liquid level of the measuring cylinder (submersion method) and calculated using the following formula.
発泡性塩化ビニル系樹脂粒子の真密度（ｋｇ／ｍ３）＝（Ｗ／Ｖ） True density of expandable polyvinyl chloride resin particles (kg/m 3 )=(W/V)
（塩化ビニル系樹脂ペレット（基材樹脂）の真密度測定）
塩化ビニル系樹脂と加工助剤、安定剤、滑剤等の副原料をブレンドし均一な配合物を得た後、押出機にて溶融混練し、得られた塩化ビニル系樹脂ペレット重量Ｗ（ｋｇ）を、エタノールの入ったメスシリンダー内に沈め、メスシリンダーの液面上昇分（水没法）から体積Ｖ（ｍ３）を求め、以下の式で算出した。
(Measurement of true density of polyvinyl chloride resin pellets (base resin))
After blending vinyl chloride resin with secondary raw materials such as processing aids, stabilizers, and lubricants to obtain a uniform mixture, the mixture was melt-kneaded in an extruder, and the weight W (kg) of the obtained vinyl chloride resin pellets was submerged in a measuring cylinder containing ethanol, and the volume V ( m3 ) was calculated from the rise in the liquid level in the measuring cylinder (submersion method) and calculated using the following formula.
塩化ビニル系樹脂ペレットの真密度（ｋｇ／ｍ３）＝（Ｗ／Ｖ）
前述の方法に基づき、測定された塩化ビニル系樹脂ペレットの真密度は１４３０ｋｇ／ｍ３であり、この値を実施例および比較例で用いる基材樹脂の密度とした。
True density of polyvinyl chloride resin pellets (kg/m 3 )=(W/V)
The true density of the vinyl chloride resin pellets measured based on the above-mentioned method was 1,430 kg/m 3 , and this value was used as the density of the base resin used in the examples and comparative examples.
（塩化ビニル系樹脂発泡粒子のかさ倍率測定）
塩化ビニル系樹脂発泡粒子を、内容積３２５０ｃｃの容器に充填し、その際の重量Ｗ（ｇ）を測定し、以下の式で算出した。基材樹脂密度は、前述の＜塩化ビニル系樹脂ペレット（基材樹脂）の真密度測定＞から、１．４３ｇ／ｃｃを用いた。
塩化ビニル系樹脂発泡粒子のかさ倍率（倍）＝１．４３／（Ｗ／３２５０）
(Measurement of bulk magnification of polyvinyl chloride resin foam particles)
The polyvinyl chloride resin foamed particles were filled into a container having an internal volume of 3250 cc, and the weight W (g) was measured and calculated using the following formula: The density of the base resin was 1.43 g/cc, as determined in the above-mentioned <Measurement of true density of polyvinyl chloride resin pellets (base resin)>.
Bulk magnification of polyvinyl chloride resin foamed particles (times) = 1.43 / (W / 3250)
＜塩化ビニル系樹脂発泡粒子の独立気泡率の測定＞
適当量の発泡粒子を、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、体積Ｖｃ（ｃｍ３）を測定した。次に測定後の同じ発泡粒子をエタノールの入ったメスシリンダー内に沈め、メスシリンダーの液面上昇分（水没法）から体積Ｖａ（ｃｍ３）を求め、下記の式に従って独立気泡率（％）を算出した。
<Measurement of Closed Cell Ratio of Expanded Polyvinyl Chloride Resin Beads>
The volume Vc ( cm3 ) of an appropriate amount of expanded beads was measured using an air pycnometer (air comparative specific gravity meter model 1000 manufactured by Tokyo Science Co., Ltd.) in accordance with the method described in ASTM D2856. Next, the same expanded beads after measurement were submerged in a measuring cylinder containing ethanol, and the volume Va ( cm3 ) was calculated from the rise in the liquid level in the measuring cylinder (submersion method), and the closed cell ratio (%) was calculated according to the following formula.
独立気泡率（％）＝（Ｖｃ／Ｖａ）×１００ Closed bubble rate (%) = (Vc/Va) x 100
＜塩化ビニル系樹脂発泡成形体の倍率測定＞
発泡成形体の縦寸法Ｘ（ｍｍ）、横寸法Ｙ（ｍｍ）、及び厚み寸法Ｚ（ｍｍ）をノギスで計測し、発泡成形体の重量Ｗ（ｇ）を電子天秤にて測定し、下記式から発泡成形体の倍率を求めた。前述の＜塩化ビニル系樹脂ペレット（基材樹脂）の真密度測定＞から、基材樹脂密度１４３０ｋｇ／ｍ３を用いた。
<Measurement of magnification of polyvinyl chloride resin foam molded body>
The longitudinal dimension X (mm), lateral dimension Y (mm), and thickness dimension Z (mm) of the foamed molded article were measured with a vernier caliper, and the weight W (g) of the foamed molded article was measured with an electronic balance, and the magnification of the foamed molded article was calculated from the following formula: The density of the base resin, 1430 kg/ m3 , was used from the above-mentioned <Measurement of true density of vinyl chloride resin pellets (base resin)>.
発泡成形体の倍率（倍） ＝ １４３０／（Ｗ ／（Ｘ×Ｙ×Ｚ）×１０６）
以下に、実施例及び比較例で用いた原材料を示す。
Magnification of foamed molded article (times) = 1430/(W/(X x Y x Z) x 106 )
The raw materials used in the examples and comparative examples are shown below.
（樹脂）
（Ａ－１）塩化ビニル樹脂［（株）カネカ製、Ｈ７１６Ｓ、平均重合度６００、塩素含有量６７．６重量％］
（Ａ－２）ポリスチレン樹脂［ＰＳジャパン製、Ｇ９４０１］
（炭素系輻射伝熱抑制剤）
（Ｂ－１）グラファイト：ＳＧＰ－４０Ｂ（林化成製）
（発泡剤）
（Ｃ－１）ノルマルペンタン［富士フィルム和光純薬（株）製］
（Ｃ－２）アセトン［富士フィルム和光純薬（株）製］
（Ｃ－３）ジメチルエーテル［岩谷産業（株）製］
(resin)
(A-1) Vinyl chloride resin [H716S, manufactured by Kaneka Corporation, average degree of polymerization 600, chlorine content 67.6% by weight]
(A-2) Polystyrene resin [G9401, manufactured by PS Japan]
(Carbon-based radiation heat transfer inhibitor)
(B-1) Graphite: SGP-40B (manufactured by Hayashi Kasei)
(Foaming Agent)
(C-1) Normal pentane [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(C-2) Acetone [manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.]
(C-3) Dimethyl ether [manufactured by Iwatani Corporation]
（実施例１）
［発泡性塩化ビニル系樹脂粒子の作製］
塩化ビニル樹脂（Ａ－１）１００重量部に対し、ブチル錫メルカプト系安定剤５重量部、滑剤（エステルワックス、ポリエチレンワックス）３重量部、スチレン－アクリロニトリル共重合体（重量平均分子量２８６万、共重合体中のアクリロニトリル由来の成分比率２０重量％）１３重量部、塩素含有量３５重量％のポリエチレン５重量部を加え、上記配合物に対して炭素系輻射伝熱抑制剤（Ｂ－１）を４重量％となるように加え、この配合物をブレンドし均一な配合物を得た後、同方向噛み合い二軸押出機にて溶融混練し、上記配合比率のペレットを得た。得られたペレットを、φ４０ｍｍ同方向噛み合い二軸押出機に４０ｋｇ／ｈｒのフィード量で溶融混練した。
Example 1
[Preparation of expandable polyvinyl chloride resin particles]
To 100 parts by weight of vinyl chloride resin (A-1), 5 parts by weight of butyltin mercapto stabilizer, 3 parts by weight of lubricant (ester wax, polyethylene wax), 13 parts by weight of styrene-acrylonitrile copolymer (weight average molecular weight 2.86 million, acrylonitrile-derived component ratio in copolymer 20% by weight), 5 parts by weight of polyethylene with a chlorine content of 35% by weight were added, and 4% by weight of carbon-based radiation heat transfer inhibitor (B-1) was added to the above blend, and this blend was blended to obtain a uniform blend, and then melt-kneaded in a co-rotating intermeshing twin screw extruder to obtain pellets with the above blending ratio. The obtained pellets were melt-kneaded in a φ40 mm co-rotating intermeshing twin screw extruder at a feed rate of 40 kg/hr.
φ４０ｍｍ同方向噛み合い二軸押出機の途中から、ノルマルペンタン（Ｃ－１）３．５ｋｇ／ｈとアセトン（Ｃ－２）１．５ｋｇ／ｈを圧入した。その後、二軸押出機先端に取り付けられた継続管、単軸押出機、ギアポンプ、ダイバータバルブを経て、樹脂温度１６０℃に冷却し、ダイバータバルブの下流に取り付けられた直径１．０ｍｍ、ランド長３．５ｍｍの小孔を３０個有する２３０℃に設定したダイから、吐出量４５ｋｇ／ｈｒで、温度７０℃及び１．４ＭＰａの加圧循環水中に押出した。この際の押出機先端圧力は１４ＭＰａであり、溶融物の樹脂温度（すなわち、押出機先端の樹脂溶融物の樹脂温度）は１６２℃であった。押出された溶融樹脂は、ダイに接触する回転カッターを用いて、切断・小粒化され、遠心脱水機に移送されて、粒重量５．６ｍｇの発泡性塩化ビニル系樹脂粒子を得た。発泡性塩化ビニル系樹脂粒子を、前述の＜発泡性塩化ビニル系樹脂粒子の真密度測定＞にて真密度を測定した結果、１３１０ｋｇ／ｍ３であった。 Normal pentane (C-1) 3.5 kg/h and acetone (C-2) 1.5 kg/h were pressed into the middle of the φ40 mm co-rotating intermeshing twin screw extruder. Thereafter, the resin was cooled to a resin temperature of 160 ° C. through a continuous pipe attached to the tip of the twin screw extruder, a single screw extruder, a gear pump, and a diverter valve, and extruded into pressurized circulating water at a temperature of 70 ° C. and 1.4 MPa at a discharge rate of 45 kg/hr from a die set at 230 ° C. having 30 small holes with a diameter of 1.0 mm and a land length of 3.5 mm attached downstream of the diverter valve. The extruder tip pressure at this time was 14 MPa, and the resin temperature of the melt (i.e., the resin temperature of the resin melt at the tip of the extruder) was 162 ° C. The extruded molten resin was cut and pelletized using a rotary cutter in contact with the die, and transferred to a centrifugal dehydrator to obtain foamable polyvinyl chloride resin particles with a particle weight of 5.6 mg. The true density of the expandable polyvinyl chloride resin particles was measured by the above-mentioned <Measurement of true density of expandable polyvinyl chloride resin particles>, and was found to be 1,310 kg/m 3 .
（水蒸気雰囲気下での成形用発泡粒子の作製）
得られた発泡性塩化ビニル系樹脂粒子を１０℃で７日保管した後、発泡性塩化ビニル系樹脂粒子１０００ｇを予備発泡機（大開工業株式会社製）に投入し、０．１６ＭＰａの水蒸気を予備発泡機に導入し、予備発泡機内部の温度１１０℃の条件で発泡させ、かさ倍率３０倍、独立気泡率９３％の発泡粒子を得た。
(Preparation of foamed particles for molding under water vapor atmosphere)
The obtained expandable polyvinyl chloride resin particles were stored at 10°C for 7 days, and then 1,000 g of the expandable polyvinyl chloride resin particles were placed in a pre-expander (manufactured by Daikai Kogyo Co., Ltd.), 0.16 MPa of steam was introduced into the pre-expander, and the particles were expanded under conditions of an internal temperature of 110°C, to obtain expanded particles with a bulk expansion ratio of 30 times and a closed cell ratio of 93%.
［塩化ビニル系樹脂発泡成形体の作製］
上記水蒸気雰囲気下で得られたかさ倍率３０倍の発泡粒子を、発泡スチロール用成形機に取り付けた縦４００ｍｍ×横４００ｍｍ×厚み２５ｍｍの型内成形用金型内に充填して、０．１３ＭＰａの水蒸気を導入して型内発泡させた後、金型に水を２０秒間噴霧して冷却した。塩化ビニル系樹脂発泡成形体が金型を押す圧力が０．０５ＭＰａ（ゲージ圧力）なるまで塩化ビニル系樹脂発泡成形体を金型内に保持した後に、塩化ビニル系樹脂発泡成形体を取り出して、直方体状の塩化ビニル系樹脂発泡成形体を得た。発泡成形体の倍率は、２９倍であった。
上述の各測定結果及び評価結果を表１に示す。
[Preparation of polyvinyl chloride resin foam molded body]
The foamed beads with a bulk magnification of 30 times obtained under the above water vapor atmosphere were filled into a mold for in-mold molding with a length of 400 mm, a width of 400 mm, and a thickness of 25 mm attached to a polystyrene foam molding machine, and 0.13 MPa of water vapor was introduced to cause in-mold foaming, and then water was sprayed into the mold for 20 seconds to cool it. The vinyl chloride resin foamed molded body was held in the mold until the pressure of the vinyl chloride resin foamed molded body pressing the mold reached 0.05 MPa (gauge pressure), and then the vinyl chloride resin foamed molded body was taken out to obtain a rectangular parallelepiped vinyl chloride resin foamed molded body. The magnification of the foamed molded body was 29 times.
The above-mentioned measurement results and evaluation results are shown in Table 1.
（比較例１）
実施例１において、炭素系輻射伝熱抑制剤を０重量％（添加しない）、加圧循環水圧力を１．３ＭＰａに変更した以外は実施例１と同様にして、粒重量５．７ｍｇの発泡性塩化ビニル系樹脂粒子を得た。この際の押出機先端圧力は１４ＭＰａであり、溶融物の樹脂温度は１６２℃であった。
得られた発泡性塩化ビニル系樹脂粒子を、前述の＜発泡性塩化ビニル系樹脂粒子の真密度測定＞にて真密度を測定した結果、１３００ｋｇ／ｍ３であった。
得られた発泡性塩化ビニル系樹脂粒子を実施例１と同様にして水蒸気雰囲気下で成形用発泡粒子を作製した。発泡粒子のかさ倍率は３１倍、独立気泡率は９７％であった。
得られた成形用発泡粒子を、実施例１と同様にして塩化ビニル系樹脂発泡成形体を作製した。発泡成形体の倍率は３０倍であった。
(Comparative Example 1)
Expandable polyvinyl chloride resin particles having a particle weight of 5.7 mg were obtained in the same manner as in Example 1, except that the carbon-based radiation heat transfer inhibitor was changed to 0% by weight (not added) and the pressure of the pressurized circulating water was changed to 1.3 MPa in Example 1. The extruder tip pressure in this case was 14 MPa, and the resin temperature of the molten material was 162°C.
The true density of the resulting expandable polyvinyl chloride resin particles was measured by the above-mentioned <Measurement of true density of expandable polyvinyl chloride resin particles>, and was found to be 1,300 kg/m 3 .
The resulting expandable vinyl chloride resin particles were used to prepare expanded beads for molding in a water vapor atmosphere in the same manner as in Example 1. The expanded beads had a bulk expansion ratio of 31 times and a closed cell ratio of 97%.
The obtained foamed molding beads were used to prepare a vinyl chloride resin foamed molded article in the same manner as in Example 1. The expansion ratio of the foamed molded article was 30 times.
（参考例１）
ポリスチレン系樹脂Ｇ９４０１（ＰＳジャパン製）１００重量部に対して、気泡径調整剤としてタルク（林化成製、タルカンパウダーＰＫ－Ｚ）１重量部加え、この配合物をブレンドし均一な配合物を得た後、φ４０ｍｍ同方向噛み合い二軸押出機に４０ｋｇ／ｈｒのフィード量で溶融混練した。
φ４０ｍｍ同方向噛み合い二軸押出機の途中から、ジメチルエーテル（Ｃ－３）２．８ｋｇ／ｈを圧入した。その後、二軸押出機先端に取り付けられた継続管、φ９０ｍｍ単軸押出機を経て、樹脂温度を１２２℃に冷却し、単軸押出機先端に設けた厚さ２ｍｍ、幅５０ｍｍの長方形断面のスリットダイより、大気中へ押出発泡させた後、スリットダイに密着させて設置した成形金型ととの下流側に設置した成形ロールにより、厚さ４５ｍｍ、幅１４０ｍｍである断面形状の押出発泡成形体を得た。
上述の各測定結果及び評価結果を表１に示す。
(Reference Example 1)
To 100 parts by weight of polystyrene resin G9401 (manufactured by PS Japan), 1 part by weight of talc (manufactured by Hayashi Kasei, Talcan Powder PK-Z) was added as a cell size regulator, and this mixture was blended to obtain a uniform mixture, which was then melt-kneaded in a φ40 mm co-rotating intermeshing twin-screw extruder at a feed rate of 40 kg/hr.
Dimethyl ether (C-3) was injected at 2.8 kg/h from the middle of a φ40 mm co-rotating intermeshing twin-screw extruder. The resin was then cooled to 122° C. through a continuation pipe attached to the tip of the twin-screw extruder and a φ90 mm single-screw extruder, and extruded and foamed into the atmosphere through a slit die with a rectangular cross section of 2 mm thick and 50 mm wide provided at the tip of the single-screw extruder. An extruded foam molded product with a cross section of 45 mm thick and 140 mm wide was obtained by a molding roll provided downstream of a molding die provided in close contact with the slit die.
The above-mentioned measurement results and evaluation results are shown in Table 1.
（参考例２）
参考例１において、輻射伝熱抑制剤（Ｂ－１）が４重量％となるように加え、またタルクを添加しないとした以外は、参考例１と同様にして発泡成形体を得た。
(Reference Example 2)
A foamed molded article was obtained in the same manner as in Reference Example 1, except that the radiation heat transfer inhibitor (B-1) was added in an amount of 4% by weight and no talc was added.
上述の各測定結果及び評価結果を表１に示す。 The above measurement and evaluation results are shown in Table 1.
Claims (11)
（ａ）炭素系輻射伝熱抑制剤を０．５～８重量％含有する、
（ｂ）塩化ビニル系樹脂及び物理系発泡剤を含有する、
（ｃ）発泡性塩化ビニル系樹脂粒子の真密度が１２００ｋｇ／ｍ３以上である。 Expandable polyvinyl chloride resin particles satisfying the following (a), (b), and (c):
(a) containing 0.5 to 8 wt % of a carbon-based radiation heat transfer inhibitor;
(b) a polyvinyl chloride resin and a physical foaming agent;
(c) The true density of the expandable polyvinyl chloride resin particles is 1,200 kg/m3 or more.
11. A foamed molded article using the expandable polyvinyl chloride resin particles according to any one of claims 1 to 9 or the expandable polyvinyl chloride resin particles according to claim 10.
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| JP3167237B2 (en) | 1993-12-24 | 2001-05-21 | 株式会社イトーキクレビオ | Desk shelf equipment |
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| WO2019198790A1 (en) | 2018-04-11 | 2019-10-17 | 株式会社カネカ | Expandable thermoplastic resin particles |
| JP2020136100A (en) | 2019-02-20 | 2020-08-31 | 積水化学工業株式会社 | Fireproof sheet and battery |
| JP2020164707A (en) | 2019-03-29 | 2020-10-08 | 株式会社カネカ | Foamable chlorinated vinyl chloride-based resin particle, foamed particle thereof, and chlorinated vinyl chloride-based resin foam molded body using the same |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3167237B2 (en) | 1993-12-24 | 2001-05-21 | 株式会社イトーキクレビオ | Desk shelf equipment |
| CN108623933A (en) | 2017-03-21 | 2018-10-09 | 洛阳尖端技术研究院 | A kind of polyvinyl chloride foam and preparation method thereof |
| WO2019198790A1 (en) | 2018-04-11 | 2019-10-17 | 株式会社カネカ | Expandable thermoplastic resin particles |
| JP2020136100A (en) | 2019-02-20 | 2020-08-31 | 積水化学工業株式会社 | Fireproof sheet and battery |
| JP2020164707A (en) | 2019-03-29 | 2020-10-08 | 株式会社カネカ | Foamable chlorinated vinyl chloride-based resin particle, foamed particle thereof, and chlorinated vinyl chloride-based resin foam molded body using the same |
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