JP2020164706A - Foamable chlorinated vinyl chloride-based resin particle, foamed particle thereof, and chlorinated vinyl chloride-based resin foam molded body using the same - Google Patents
Foamable chlorinated vinyl chloride-based resin particle, foamed particle thereof, and chlorinated vinyl chloride-based resin foam molded body using the same Download PDFInfo
- Publication number
- JP2020164706A JP2020164706A JP2019068364A JP2019068364A JP2020164706A JP 2020164706 A JP2020164706 A JP 2020164706A JP 2019068364 A JP2019068364 A JP 2019068364A JP 2019068364 A JP2019068364 A JP 2019068364A JP 2020164706 A JP2020164706 A JP 2020164706A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl chloride
- chloride resin
- chlorinated vinyl
- foamable
- resin particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920005989 resin Polymers 0.000 title claims abstract description 301
- 239000011347 resin Substances 0.000 title claims abstract description 301
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical class ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 268
- 239000002245 particle Substances 0.000 title claims abstract description 238
- 239000006260 foam Substances 0.000 title claims abstract description 69
- 238000005187 foaming Methods 0.000 claims abstract description 70
- 239000000178 monomer Substances 0.000 claims abstract description 64
- 239000004088 foaming agent Substances 0.000 claims abstract description 57
- 229920001577 copolymer Polymers 0.000 claims abstract description 48
- 150000002825 nitriles Chemical class 0.000 claims abstract description 35
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- 238000000465 moulding Methods 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000001125 extrusion Methods 0.000 claims description 9
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 8
- 238000010097 foam moulding Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 5
- 150000002576 ketones Chemical class 0.000 claims description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 5
- 238000005660 chlorination reaction Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 abstract description 20
- 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 abstract description 19
- 239000011810 insulating material Substances 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000011162 core material Substances 0.000 abstract description 2
- 235000013305 food Nutrition 0.000 abstract description 2
- 239000012774 insulation material Substances 0.000 abstract 2
- 238000010438 heat treatment Methods 0.000 description 29
- 238000000034 method Methods 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 21
- 238000002360 preparation method Methods 0.000 description 19
- -1 ethylene, propylene, vinyl Chemical group 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000001993 wax Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000003381 stabilizer Substances 0.000 description 8
- 238000009472 formulation Methods 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 230000001771 impaired effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 5
- 239000000314 lubricant Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002994 raw material 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
- FXRLMCRCYDHQFW-UHFFFAOYSA-N 2,3,3,3-tetrafluoropropene Chemical compound FC(=C)C(F)(F)F FXRLMCRCYDHQFW-UHFFFAOYSA-N 0.000 description 2
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-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
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-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
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920006328 Styrofoam Polymers 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000000691 measurement method Methods 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
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-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
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 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
- 239000011342 resin composition Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003440 styrenes Chemical class 0.000 description 2
- 239000008261 styrofoam Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- OYINILBBZAQBEV-UWJYYQICSA-N (17s,18s)-18-(2-carboxyethyl)-20-(carboxymethyl)-12-ethenyl-7-ethyl-3,8,13,17-tetramethyl-17,18,22,23-tetrahydroporphyrin-2-carboxylic acid Chemical compound N1C2=C(C)C(C=C)=C1C=C(N1)C(C)=C(CC)C1=CC(C(C)=C1C(O)=O)=NC1=C(CC(O)=O)C([C@@H](CCC(O)=O)[C@@H]1C)=NC1=C2 OYINILBBZAQBEV-UWJYYQICSA-N 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
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical compound CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 2-octanone Chemical compound CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical class CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- 206010000369 Accident Diseases 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 239000004801 Chlorinated PVC Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-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
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 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
- 235000013539 calcium stearate Nutrition 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229920000457 chlorinated polyvinyl chloride Polymers 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 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
- 239000006185 dispersion Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 230000001747 exhibiting effect Effects 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
- 238000011049 filling Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 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
- 239000001282 iso-butane Substances 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
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 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
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003536 tetrazoles Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
本発明は、発泡性塩素化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塩素化塩化ビニル系樹脂発泡成形体に関する。 The present invention relates to effervescent chlorinated vinyl chloride resin particles, the effervescent particles thereof, and a chlorinated vinyl chloride resin foam molded article 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。 The resin foam has light weight, heat insulating property, cushioning property and the like, and has been widely used as a heat insulating material for houses and heat insulating materials for pipes and the like. Among them, the styrene resin foam molded product obtained by using the foamable styrene resin particles containing a foaming agent has a high degree of freedom in shape, and foams in a simple shape such as a board shape obtained by an extrusion foaming method or the like. It is widely used as a heat insulating material that can be applied to parts that are difficult to construct with the body.
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。しかし、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、従来よりも高い難燃性能が求められつつある。 Where the styrene-based resin is a flammable resin, a flame retardant is added to the styrene-based resin foam molded product to ensure a certain degree of flame retardant performance. However, due to recent fire accidents at construction sites and fire cases in high-rise condominiums, heat insulating materials for buildings are required to have higher flame retardant performance than before.
難燃性能に優れる発泡体としては、例えば、難燃性能に優れる塩化ビニル系樹脂を基材樹脂とした塩化ビニル系樹脂発泡体が上げられる。
例えば、特許文献１には、塩化ビニル系重合体（ａ）と、不飽和ニトリル単位、芳香族ビニル単位および任意にこれらと共重合可能な１種以上のモノマー単位を含む共重合体であって、かつ当該共重合体１０重量％のメチルエチルケトン溶液の２５℃における粘度が３〜２０センチポイズである共重合体（ｂ）とからなる熱可塑性樹脂からなる粒子に、沸点６０℃以下の発泡剤を含浸し発泡させてなる難燃性樹脂発泡体粒子が記載されている。
しかしながら、難燃性能に優れる塩化ビニル系重合体の割合は最大でも６０重量％であることから難燃性能が十分とは言い難い。また、塩化ビニル系重合体の比率を上げると発泡倍率及び独立気泡率が低下する傾向にあり、より高度な難燃性能を発現し、かつ、軽量性に優れた塩化ビニル系樹脂発泡成形体は得られていない。
Examples of the foam having excellent flame-retardant performance include a vinyl chloride-based resin foam having a vinyl chloride-based resin having excellent flame-retardant performance as a base resin.
For example, Patent Document 1 describes a copolymer containing a vinyl chloride polymer (a), an unsaturated nitrile unit, an aromatic vinyl unit, and one or more monomer units that can be optionally copolymerized with these. And, the particles made of a thermoplastic resin composed of the copolymer (b) having a viscosity of 3 to 20 centipoise at 25 ° C. of the methyl ethyl ketone solution of 10% by weight of the copolymer are impregnated with a foaming agent having a boiling point of 60 ° C. or lower. Flame-retardant resin foam particles formed by foaming are described.
However, since the proportion of the vinyl chloride polymer having excellent flame retardant performance is 60% by weight at the maximum, it cannot be said that the flame retardant performance is sufficient. Further, when the ratio of the vinyl chloride polymer is increased, the foaming ratio and the closed cell ratio tend to decrease, and the vinyl chloride resin foam molded product exhibiting higher flame retardancy performance and being excellent in light weight Not obtained.
前記塩化ビニル樹脂よりも難燃性能に優れる塩素化塩化ビニル樹脂を基材樹脂に使用することで、発泡成形体の難燃性能を改善する手段が考えられる。
難燃性能、高独立気泡率、高発泡倍率の性能を兼ね備えている押出発泡体としては、例えば、次のような発明が提案されている。
特許文献２には、塩素化ポリ塩化ビニル樹脂、発泡剤、核剤、及び、６０℃を超えるＴｇ及び１．５を超える稀薄溶液粘度を有しかつ５０％より多いスチレン系モノマーと１０〜４０％の不飽和ニトリルの共重合体から選定された加工助剤を含んで成る組成物が記載されている。
特許文献３には、塩素化塩化ビニル系樹脂とアクリル系樹脂および／またはスチレン系樹脂とを主成分とする樹脂組成物を発泡成形してなる樹脂発泡成形体が記載されている。
By using a chlorinated vinyl chloride resin, which is superior in flame retardancy to the vinyl chloride resin, as the base resin, a means for improving the flame retardancy of the foamed molded product can be considered.
For example, the following inventions have been proposed as extruded foams having flame-retardant performance, high closed cell ratio, and high foaming ratio.
Patent Document 2 describes chlorinated polyvinyl chloride resins, foaming agents, nucleating agents, and styrene-based monomers having a Tg of more than 60 ° C. and a dilute solution viscosity of more than 1.5 and more than 50% and 10 to 40. A composition comprising a processing aid selected from a copolymer of% unsaturated nitrile is described.
Patent Document 3 describes a resin foam molded product obtained by foam molding a resin composition containing a chlorinated vinyl chloride resin and an acrylic resin and / or a styrene resin as main components.
一方、押出発泡体とは発泡プロセスが全く異なる、発泡性粒子を発泡成形してなる発泡成形体としては、次のような発明が提案されている。
特許文献４には、塩素化塩化ビニル樹脂と相溶性を呈する溶剤および発泡剤を含有してなる塩素化塩化ビニル樹脂予備発泡粒子が記載されている。基材樹脂は、塩化ビニル樹脂よりも難燃性能に優れる塩素化塩化ビニル樹脂であるため、難燃性能に優れる発泡成形体であるが、温暖化係数の高い発泡剤を使用し、かつ有機溶剤を大量に使用するため、環境、及びコスト面で課題がある。
On the other hand, the following inventions have been proposed as a foam molded product obtained by foam molding foamable particles, which has a completely different foaming process from the extruded foam.
Patent Document 4 describes chlorinated vinyl chloride resin pre-foamed particles containing a solvent and a foaming agent that are compatible with the chlorinated vinyl chloride resin. Since the base resin is a chlorinated vinyl chloride resin that has better flame retardancy than vinyl chloride resin, it is a foam molded product with excellent flame retardancy, but it uses a foaming agent with a high warming coefficient and is an organic solvent. Since a large amount of plastic is used, there are problems in terms of environment and cost.
以上のように、難燃性能に優れる塩化ビニル系樹脂、あるいは塩素化塩化ビニル系樹脂を基材とした発泡成形体は従来より存在するものの、難燃性能、軽量性、形状付与性、環境適合性、及びコスト面について改善の余地がある。 As described above, although vinyl chloride-based resins having excellent flame-retardant performance or foam moldings based on chlorinated vinyl chloride-based resin have existed in the past, they have flame-retardant performance, light weight, shape-impartability, and environmental friendliness. There is room for improvement in terms of sex and cost.
従って、本発明の目的は、難燃性能および高い発泡倍率を両立する塩素化塩化ビニル系樹脂発泡成形体を与えうる発泡性塩素化塩化ビニル系樹脂粒子を提供することにある。 Therefore, an object of the present invention is to provide foamable chlorinated vinyl chloride resin particles capable of providing a chlorinated vinyl chloride resin foam molded product having both flame retardancy and a high foaming 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、塩素化塩化ビニル系樹脂と、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を組み合わせて製造された発泡性樹脂粒子が、軽量性および独立気泡率に優れる塩素化塩化ビニル系樹脂発泡成形体を与え得ることを見出し、本発明を完成するに至った。 As a result of diligent studies to solve the above-mentioned problems, the inventors of the present application have made a chlorinated vinyl chloride resin and a copolymer having an aromatic vinyl chloride monomer and an unsaturated nitrile monomer as structural units. It has been found that the foamable resin particles produced in combination with the above can provide a chlorinated vinyl chloride resin foamed molded product having excellent lightness and closed cell ratio, and have completed the present invention.
即ち、本発明は、
［１］次の（Ａ）〜（Ｃ）を含有する、発泡性塩素化塩化ビニル系樹脂粒子：
（Ａ）塩素化塩化ビニル系樹脂、
（Ｂ）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、および、
（Ｃ）発泡剤、
［２］前記（Ａ）塩素化塩化ビニル系樹脂１００重量部に対して、前記（Ｂ）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が１〜５０重量部含有される、［１］記載の発泡性塩素化塩化ビニル系樹脂粒子、
［３］前記（Ａ）塩素化塩化ビニル系樹脂の塩素含有率量が６０重量％以上７５重量％以下である、［１］または［２］の発泡性塩素化塩化ビニル系樹脂粒子、
［４］前記（Ａ）塩素化塩化ビニル系樹脂の平均重合度が４００以上１５００以下である、［１］〜［３］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［５］前記（Ｂ）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の少なくとも一種がスチレンーアクリロニトリル共重合体である、［１］〜［４］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［６］前記（Ｂ）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の重量平均分子量が前記（Ａ）塩素化塩化ビニル系樹脂の重量平均分子量よりも高い、［１］〜［５］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［７］前記（Ｃ）発泡剤が物理発泡剤である、［１］〜［６］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［８］前記（Ｃ）発泡剤が炭素数４〜６の飽和炭化水素を含む、［７］に記載の発泡性塩素化塩化ビニル系樹脂粒子、
［９］前記炭素数４〜６の飽和炭化水素の少なくとも一種がペンタンである、［８］記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１０］前記（Ｃ）発泡剤がケトンを含む、［１］〜［９］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１１］前記（Ｃ）発泡剤が発泡性塩素化塩化ビニル系樹脂粒子１００重量％において１〜４０重量％含有されている、［１］〜［１０］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１２］塩素化ポリエチレンを含有する、［１］〜［１１］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１３］前記発泡性塩素化塩化ビニル系樹脂粒子の真密度が１２００ｋｇ／ｍ３以上である、［１］〜［１２］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１４］前記発泡性塩素化塩化ビニル系樹脂粒子の真密度が１３００ｋｇ／ｍ３以上である、［１］〜［１３］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、
［１５］次の工程（Ｉ）〜（ＩＩＩ）を含む、発泡性塩素化塩化ビニル系樹脂粒子の製造方法：
（Ｉ）塩素化塩化ビニル系樹脂、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、発泡剤を含有する溶融混練物を作製する工程
（ＩＩ）前記溶融混練物を、小孔を有するダイスを通じて、加圧循環水内に押し出す工程
（ＩＩＩ）前記押し出し直後の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する工程、
［１６］［１］〜［１４］のいずれかに記載の発泡性塩素化塩化ビニル系樹脂粒子、または、［１５］で得られた発泡性塩素化塩化ビニル系樹脂粒子を予備発泡してなる塩素化塩化ビニル系樹脂発泡粒子、
［１７］独立気泡率が７０％以上である、［１６］に記載の塩素化塩化ビニル系樹脂発泡粒子、
［１８］［１６］又は［１７］のいずれかに記載の塩素化塩化ビニル系樹脂発泡粒子を発泡成形してなる塩素化塩化ビニル系樹脂発泡成形体、
［１９］独立気泡率が７０％以上である、［１８］に記載の塩素化塩化ビニル系樹脂発泡成形体、
［２０］［１６］又は［１７］のいずれかに記載の塩素化塩化ビニル系樹脂発泡粒子を成形する工程を含む、塩素化塩化ビニル系樹脂発泡成形体の製造方法、
に関する。
That is, the present invention
[1] Effervescent chlorinated vinyl chloride resin particles containing the following (A) to (C):
(A) Chlorinated vinyl chloride resin,
(B) A copolymer having an aromatic vinyl monomer and an unsaturated nitrile as structural units, and
(C) Foaming agent,
[2] With respect to 100 parts by weight of the (A) chlorinated vinyl chloride resin, 1 to 50 parts by weight of the copolymer having the (B) aromatic vinyl monomer and unsaturated nitrile as structural units is contained. The foamable chlorinated vinyl chloride resin particles according to [1].
[3] The foamable chlorinated vinyl chloride resin particles according to [1] or [2], wherein the chlorine content of the (A) chlorinated vinyl chloride resin is 60% by weight or more and 75% by weight or less.
[4] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [3], wherein the (A) chlorinated vinyl chloride resin has an average degree of polymerization of 400 or more and 1500 or less.
[5] The above-described (1) to any one of [4], wherein at least one of the copolymers having the aromatic vinyl monomer and the unsaturated nitrile as structural units is a styrene-acrylonitrile copolymer. Effervescent chlorinated vinyl chloride resin particles,
[6] The weight average molecular weight of the copolymer having the (B) aromatic vinyl monomer and unsaturated nitrile as structural units is higher than the weight average molecular weight of the (A) chlorinated vinyl chloride resin [1]. ] To [5], the foamable chlorinated vinyl chloride resin particles,
[7] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [6], wherein the (C) foaming agent is a physical foaming agent.
[8] The foamable chlorinated vinyl chloride resin particles according to [7], wherein the foaming agent (C) contains saturated hydrocarbons having 4 to 6 carbon atoms.
[9] The foamable chlorinated vinyl chloride resin particles according to [8], wherein at least one of the saturated hydrocarbons having 4 to 6 carbon atoms is pentane.
[10] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [9], wherein the foaming agent (C) contains a ketone.
[11] The foamable chlorination according to any one of [1] to [10], wherein the foaming agent (C) is contained in an amount of 1 to 40% by weight based on 100% by weight of the foamable chlorinated vinyl chloride resin particles. Vinyl chloride resin particles,
[12] The effervescent chlorinated vinyl chloride resin particles according to any one of [1] to [11], which contain chlorinated polyethylene.
[13] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [12], wherein the effervescent chlorinated vinyl chloride resin particles have a true density of 1200 kg / m 3 or more.
[14] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [13], wherein the effervescent chlorinated vinyl chloride resin particles have a true density of 1300 kg / m 3 or more.
[15] A method for producing effervescent chlorinated vinyl chloride resin particles, which comprises the following steps (I) to (III):
(I) Step of producing a melt-kneaded product containing a chlorinated vinyl chloride resin, a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units, and a foaming agent (II). Step of extruding the melt-kneaded product into pressurized circulating water through a die having small holes (III) A step of cutting the melt-kneaded product immediately after the extrusion and cooling and solidifying the melt-kneaded product with pressurized circulating water.
[16] The foamable chlorinated vinyl chloride resin particles according to any one of [1] to [14] or the foamable chlorinated vinyl chloride resin particles obtained in [15] are prefoamed. Chlorinated vinyl chloride resin foam particles,
[17] The chlorinated vinyl chloride resin foamed particles according to [16], which have a closed cell ratio of 70% or more.
[18] A chlorinated vinyl chloride resin foam molded product obtained by foam molding the chlorinated vinyl chloride resin foam particles according to any one of [16] and [17].
[19] The chlorinated vinyl chloride resin foam molded product according to [18], which has a closed cell ratio of 70% or more.
[20] A method for producing a chlorinated vinyl chloride resin foam molded article, which comprises the step of molding the chlorinated vinyl chloride resin foamed particles according to any one of [16] and [17].
Regarding.
本発明の発泡性塩素化塩化ビニル系樹脂粒子によれば、難燃性能に優れ、且つ高発泡倍率及び高独立気泡率を有する塩素化塩化ビニル系樹脂発泡体が得られる。 According to the foamable vinyl chloride-based resin particles of the present invention, a chlorinated vinyl chloride-based resin foam having excellent flame retardancy, a high foaming ratio and a high closed cell ratio can be obtained.
（塩素化塩化ビニル系樹脂）
本発明では、塩素化塩化ビニル系樹脂を用いることにより、優れた難燃性能及び軽量性を両立した発泡成形体を得ることができる。
(Chlorinated vinyl chloride resin)
In the present invention, by using a chlorinated vinyl chloride resin, it is possible to obtain a foam molded product having both excellent flame retardancy and light weight.
本発明で用いられる塩素化塩化ビニル系樹脂は、通常、原料として塩化ビニル系樹脂を用い、同塩化ビニル系樹脂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、塩化ビニル系樹脂を気層中、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。 The chlorinated vinyl chloride resin used in the present invention usually uses a vinyl chloride resin as a raw material, supplies chlorine in a state where the vinyl chloride resin is dispersed in an aqueous medium, and irradiates it with a mercury lamp to perform photochlorine. Manufactured by chlorinating in an aqueous medium such as chlorinating or heating, or chlorinating a vinyl chloride resin in the air layer or under irradiation with a mercury lamp. To.
塩素化塩化ビニル系樹脂としては各種塩化ビニル系樹脂を塩素化したものが使用される。塩素化される塩化ビニル系樹脂としては、塩化ビニルの単独重合体、および塩化ビニルと他の共重合可能な単量体、例えば、エチレン、プロピレン、酢酸ビニル、塩化アリル、アリルグリシジルエーテル、アクリル酸エステル、ビニルエーテル等との共重合体等が挙げられる。 As the chlorinated vinyl chloride resin, chlorinated various vinyl chloride resins are used. The vinyl chloride-based resin to be chlorinated includes a homopolymer of vinyl chloride and other copolymerizable monomers with vinyl chloride, such as ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, and acrylic acid. Examples thereof include copolymers with esters and vinyl ethers.
原料の塩素化前の塩化ビニル系樹脂の平均重合度は、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樹脂の平均重合度は、実質的に塩素化前の塩化ビニル系樹脂の平均重合度と同一とみなす。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 resin before chlorination of the raw material 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, more preferably 1500 or less. If the average degree of polymerization is within the above range, a high foaming ratio tends to be obtained. The average degree of polymerization of the chlorinated vinyl chloride resin is considered to be substantially the same as the average degree of polymerization of the vinyl chloride resin before chlorination. The average degree of polymerization is measured according to JIS K6720-2.
塩素化塩化ビニル系樹脂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 chlorinated vinyl chloride resin is not particularly limited, but is preferably in the range of 30,000 or more and 400,000 or less. When the weight average molecular weight is in the above range, a high foaming ratio tends to be obtained. The weight average molecular weight is evaluated by gel permeation chromatography in terms of polystyrene equivalent molecular weight.
塩素化塩化ビニル系樹脂の塩素含有量は、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樹脂及び塩化ビニル系樹脂の塩素含有量は、ＪＩＳ Ｋ７３８５ Ｂ法に準拠して測定される。 The chlorine content of the chlorinated vinyl chloride resin is preferably in the range of 60% by weight or more and 75% by weight or less from the viewpoint of ensuring foamability. More preferably, it is 64% by weight or more and 70% by weight or less. The higher the chlorine content, the higher the foaming ratio tends to be obtained, but on the other hand, if the chlorine content is too high, the melt viscosity tends to increase and the workability tends to be significantly impaired. The chlorine content of the chlorinated vinyl chloride resin and the vinyl chloride resin is measured according to the JIS K7385 B method.
（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）
本発明では、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（以下、「共重合体（Ｂ）」を称することがある。）を塩素化塩化ビニル系樹脂に組み合わせて用いることにより、高発泡倍率並びに高独立気泡率の発泡粒子並びに発泡成形体を得ることができる。特に水蒸気加熱条件での予備発泡や発泡成形において当該効果が際立って優れる。
(Copolymer having aromatic vinyl monomer and unsaturated nitrile monomer as structural units)
In the present invention, a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units (hereinafter, may be referred to as "copolymer (B)") is a chlorinated vinyl chloride resin. By using in combination with, it is possible to obtain foamed particles and a foamed polymer having a high foaming ratio and a high closed cell ratio. In particular, the effect is remarkably excellent in pre-foaming and foam molding under steam heating conditions.
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。 Examples of the aromatic vinyl monomer include styrene derivatives such as styrene, α-methylstyrene, ethylstyrene, and halogenated styrene.
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。 Examples of the unsaturated nitrile monomer include acnironitrile and methacrylonitrile.
本発明の効果を損なわない範囲で、共重合体（Ｂ）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 effects of the present invention are not impaired, the copolymer (B) is a structural unit derived from a monomer other than the aromatic vinyl monomer and the unsaturated nitrile monomer (other copolymerizable monomers). ) May have. Other copolymerizable monomers include methyl (meth) acrylate, ethyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. (Meta) acrylic acid ester, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like.
共重合体（Ｂ）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、共重合体（Ｂ）全体を１００重量％として、１０〜４５重量％である。前記範囲であることで、高発泡倍率並びに高独立気泡率の発泡粒子並びに発泡成形体を得られやすい。 The preferable range of the unsaturated nitrile monomer in the copolymer (B) is 10 to 45% by weight, with the entire copolymer (B) as 100% by weight. Within the above range, foamed particles having a high foaming ratio and a high closed cell ratio and a foamed molded product can be easily obtained.
好ましい共重合体（Ｂ）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。共重合体（Ｂ）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、共重合体（Ｂ）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。共重合体（Ｂ）は、その重量平均分子量が、使用される塩素化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及び高独立気泡率を確保しやすい点から好ましい。尚、共重合体（Ｂ）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。共重合体（Ｂ）として、例えばＧａｌａｔａ製のＢｌｅｎｄｅｘ８６９等が使用できる。 Preferred copolymers (B) include styrene-acrylonitrile copolymers. As the copolymer (B), only one type may be used, or two or more types may be used in combination. In a preferred embodiment, a styrene-acrylonitrile copolymer is used as at least one of the copolymers (B). It is easy to secure a high foaming ratio and a high closed cell ratio by using a copolymer (B) having a weight average molecular weight higher than the weight average molecular weight of the chlorinated vinyl chloride resin used. Is preferable. The weight average molecular weight of the copolymer (B) is evaluated by gel permeation chromatography in terms of polystyrene-equivalent molecular weight. As the copolymer (B), for example, Blendex 869 manufactured by Galata or the like can be used.
共重合体（Ｂ）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、塩素化塩化ビニル系樹脂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、５重量部を超え、３０重量部以下が更に好ましい。１重量部以上であると、高い発泡倍率並びに高い独立気泡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 (B) 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 with respect to 100 parts by weight of the chlorinated vinyl chloride resin. It is more preferably 5 to 50 parts by weight, more preferably more than 5 parts by weight, and further preferably 30 parts by weight or less. When it is 1 part by weight or more, it becomes easy to obtain foamed particles and / or a foamed molded product having a high expansion ratio and a high closed cell ratio, and when it is 50 parts by weight or less, foamed particles and / or excellent flame retardant performance are easily obtained. A foam molded product can be obtained.
（発泡剤）
本発明で用いられる発泡剤は、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、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、窒素などの無機発泡剤などの物理発泡剤、アゾ化合物、テトラゾールなどの化学発泡剤などを用いることができる。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 foaming agent used in the present invention is not particularly limited, and examples thereof include the following foaming agents. For example, hydrocarbons such as normal butane, isobutane, normal pentane, isopentan, neopentane, cyclopentane, normal hexane, or cyclohexane, dimethyl ether, diethyl ether, methyl ethyl ether, isopropyl ether, n-butyl ether, diisopropyl ether, furan, furfural, 2 -Ethers such as methylfuran, tetrahydrofuran, tetrahydropyran, dimethyl ketone, methyl ethyl ketone, diethyl ketone, methyl n-propyl ketone, methyl-n-butyl ketone, methyl-i-butyl ketone, methyl-n-hexyl ketone, ethyl-n-propyl Ketones, ketones such as ethyl-n-butylketone, saturated alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propyl alcohol, i-propyl alcohol, butyl alcohol, i-butyl alcohol, t-butyl alcohol, methyl formate Caroic acid esters such as ethyl formic acid ester, propyl formic acid ester, butyl formic acid ester, amyl formic acid, methyl propionic acid ester, ethyl propionic acid ester, alkyl halides such as methyl chloride and ethyl chloride, 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), cis-1-chloro-3,3,3-trifluoropropene (cis-HCFO-1233zd), etc. Hydrofluoroolefins or chlorinated hydrofluoroolefins, physical foaming agents such as inorganic foaming agents such as water, carbon dioxide and nitrogen, chemical foaming agents such as azo compounds and tetrazole can be used. These other foaming agents may be used alone or in combination of two or more.
発泡剤としては、物理発泡剤を使用することが好ましく、中でも炭素数４〜６の飽和炭化水素がより好ましい。炭素数４〜６の飽和炭化水素として、発泡剤の樹脂への溶解性及び保持性の観点から、少なくともペンタンが含有されることが好ましい。 As the foaming agent, it is preferable to use a physical foaming agent, and among them, saturated hydrocarbons having 4 to 6 carbon atoms are more preferable. As the saturated hydrocarbon having 4 to 6 carbon atoms, it is preferable that at least pentane is contained from the viewpoint of solubility and retention of the foaming agent in the resin.
発泡剤としてケトンを含むことが、発泡剤の溶解性向上の観点から好ましい。例えば、ケトンを前記炭素数４〜６の飽和炭化水素と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。 It is preferable to include a ketone as the foaming agent from the viewpoint of improving the solubility of the foaming agent. For example, by using a ketone in combination with the 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.
本発明の発泡性塩素化塩化ビニル系樹脂粒子における発泡剤の含有量は、発泡性塩素化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、高い発泡倍率及び高い独立気泡率を有する発泡粒子及び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、５〜２０重量％である。 The content of the foaming agent in the foamable chlorinated vinyl chloride resin particles of the present invention is preferably 1 to 40% by weight with respect to 100% by weight of the foamable chlorinated vinyl chloride resin particles. By controlling the content of the foaming agent within the predetermined range, it is possible to easily obtain foamed particles and a foamed molded product having a high foaming ratio and a high closed cell ratio. A more preferable range is 5 to 20% by weight.
（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、加工助剤、滑剤、造核剤、発泡助剤、帯電防止剤、輻射伝熱抑制剤、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)
Flame retardants, stabilizers, processing aids, lubricants, nucleating agents, foaming aids, antistatic agents, radiant heat transfer inhibitors, solvents and pigments / dyes, as needed, to the extent that the effects of the present invention are not impaired. And the like may be contained.
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、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、酸化亜鉛などの難燃助剤が挙げられる。 As the flame retardant, a known flame retardant can be used. For example, a brominated flame retardant, a phosphorus flame retardant, an intomescent flame retardant such as ammonium polyphosphate or melamine cyanurate, aluminum hydroxide, or hydroxide. Examples thereof include hydroxide compounds such as magnesium, flame retardants such as antimony oxide and zinc oxide.
安定剤としては、従来より塩化ビニル系樹脂及び塩素化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、塩素化塩化ビニル系樹脂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-based resins and chlorinated vinyl chloride-based resins can be used. Examples thereof include tin-based stabilizers, phenol-based compounds, phosphorus-based compounds, antioxidants such as amine-based compounds, epoxy-based stabilizers, and zeolites. The amount of each stabilizer used is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 10 parts by weight or less with respect to 100 parts by weight of the chlorinated vinyl chloride resin.
加工助剤としては、ポリメチルメタクリレートを主成分とする塩化ビニル加工性改良剤、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。中でも、塩素化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、塩素化ポリエチレンを含有することが好ましい。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、塩素化塩化ビニル系樹脂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。 Examples of the processing aid include a vinyl chloride processability improver containing polymethylmethacrylate as a main component, an impact resistance improver such as a methyl methacrylate-butadiene-styrene polymer, and chlorinated polyethylene. Above all, it is preferable to contain chlorinated polyethylene from the viewpoint of improving the fluidity of the chlorinated vinyl chloride resin and improving the molding processability. 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 with respect to 100 parts by weight of the chlorinated vinyl chloride resin. The chlorine content of chlorinated polyethylene is measured according to the JIS K7385 B method.
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 the lubricant 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。 Examples of the nucleating agent include inorganic compounds such as silica, calcium silicate, wallastonite, kaolin, clay, mica, zinc oxide, calcium carbonate, sodium hydrogen carbonate, zeolite or talc.
輻射伝熱抑制剤としては、近赤外又は赤外領域の光を反射、散乱又は吸収する特性を有する物質が挙げられ、例えば、グラファイト、グラフェン、カーボンブラック、膨張黒鉛、酸化チタンなどがある。 Examples of the radiant heat transfer inhibitor include substances having a property of reflecting, scattering or absorbing light in the near infrared or infrared region, and examples thereof include graphite, graphene, carbon black, expanded graphite and titanium oxide.
本発明の効果を損なわない範囲で、塩素化塩化ビニル系樹脂に他の熱可塑性樹脂や熱硬化性樹脂を併用してもよい。難燃性能の点から、塩化ビニル系樹脂が好ましい。塩化ビニル系樹脂としては、塩化ビニルの単独重合体、および塩化ビニルと他の共重合可能な単量体、例えば、エチレン、プロピレン、酢酸ビニル、塩化アリル、アリルグリシジルエーテル、アクリル酸エステル、ビニルエーテル等との共重合体等が挙げられる。塩化ビニル系樹脂の平均重合度は、特に限定はされないが、３００以上７０００以下であることが好ましい。 Other thermoplastic resins and thermosetting resins may be used in combination with the chlorinated vinyl chloride resin as long as the effects of the present invention are not impaired. From the viewpoint of flame retardancy, vinyl chloride resin is preferable. Examples of the vinyl chloride resin include a homopolymer of vinyl chloride and other copolymerizable monomers of vinyl chloride, such as ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, and vinyl ether. And the copolymer with. The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is preferably 300 or more and 7,000 or less.
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、塩素化塩化ビニル系樹脂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 blending amount of the other resins is not particularly limited as long as the effects of the present invention are not impaired, but 0 to 99 parts by weight is used with respect to 100 parts by weight of the chlorinated vinyl chloride resin. preferable.
本発明の発泡性塩素化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、紡錘状などの丸みを帯びた小さい粒子）だけでなく、棒状（円柱状）、板状、扁平状の粒子も含まれるものとする。尚、本発明の発泡性塩素化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い。 The foamable chlorinated vinyl chloride-based resin particles of the present invention may be any general granular material, although the shape of the particles is not particularly limited as long as the particles have a shape capable of pre-foaming and foam-molding the foamable resin particles as described later. It is assumed that not only (for example, small rounded particles such as spherical, substantially spherical, convex lens-shaped, and spindle-shaped) but also rod-shaped (cylindrical), plate-shaped, and flat-shaped particles are included. The grain weight of the effervescent chlorinated vinyl chloride resin particles of the present invention is 0.5 from the viewpoint of ensuring the moldability such as the filling property of the effervescent particles into the molding die and the surface beauty of the effervescent molded product. It is preferably 10 mg / grain.
本発明の発泡性塩素化塩化ビニル系樹脂粒子は、発泡性塩素化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、真密度が１２００ｋｇ／ｍ３以上であることが好ましく、１３００ｋｇ／ｍ３以上がより好ましい。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。 The effervescent chlorinated vinyl chloride resin particles of the present invention have a true density of 1200 kg / kg from the viewpoint of reducing the diffusion rate of the foaming agent from the effervescent chlorinated vinyl chloride resin particles or further improving the foaming ratio. is preferably m 3 or more, 1300 kg / m 3 or more is more preferable. The true density referred to here can be obtained by a measuring method described later.
（発泡性塩素化塩化ビニル系樹脂粒子の製造方法）
本発明の発泡性塩素化塩化ビニル系樹脂粒子は、公知の製造方法で得ることができるが、例えば、以下の２つの製造方法が挙げられる。
(Manufacturing method of effervescent chlorinated vinyl chloride resin particles)
The effervescent chlorinated vinyl chloride resin particles of the present invention can be obtained by a known production method, and examples thereof include the following two production methods.
第１の発泡性塩素化塩化ビニル系樹脂粒子の製造方法（以下、「第１の製造方法」と称することがある。）としては、（Ａ）塩素化塩化ビニル系樹脂、及び（Ｂ）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、更に必要に応じて他の添加剤を押出機、ロール加工機、バンバリミキサーなどの公知の混練機にて加熱溶融混合した後、造粒し、得られた塩素化塩化ビニル系樹脂粒子をオートクレーブ中にて、発泡剤を含浸させることで、発泡性塩素化塩化ビニル系樹脂粒子を得る製造方法がある。 Examples of the method for producing the first foamable chlorinated vinyl chloride resin particles (hereinafter, may be referred to as “first production method”) include (A) chlorinated vinyl chloride resin and (B) fragrance. A copolymer having a group vinyl monomer and an unsaturated nitrile monomer as structural units, and if necessary, other additives are heated and melted in a known kneader such as an extruder, a roll processing machine, or a Bambari mixer. There is a manufacturing method for obtaining effervescent chlorinated vinyl chloride resin particles by impregnating the obtained chlorinated vinyl chloride resin particles with a foaming agent in an autoclave after mixing.
第２の発泡性塩素化塩化ビニル系樹脂粒子の製造方法（以下、「第２の製造方法」と称することがある。）としては、（Ａ）塩素化塩化ビニル系樹脂、及び（Ｂ）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、更に必要に応じて他の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スを通じて、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素化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、ダイス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、発泡性塩素化塩化ビニル系樹脂粒子を得る製造方法である。 Examples of the method for producing the second foamable chlorinated vinyl chloride resin particles (hereinafter, may be referred to as "second production method") include (A) chlorinated vinyl chloride resin and (B) fragrance. A copolymer having a group vinyl monomer and an unsaturated nitrile monomer as structural units, and if necessary, other additives are supplied to the extruder and melt-kneaded, and the foaming agent is supplied to the extruder or the extruder. A foaming agent-containing chlorinated vinyl chloride resin is placed in a cutter chamber filled with pressurized circulating water through a die with a large number of small holes attached to the extruder or later after being dissolved and dispersed in the melt-kneaded product by the subsequent dispersion equipment. A manufacturing method in which the melt-kneaded product of the composition is extruded, and immediately after the extrusion, the melt-kneaded product is cut by a rotary cutter in contact with a die and cooled and solidified by pressurized circulating water to obtain foamable chlorinated vinyl chloride resin particles. is there.
第２の製造方法によれば、本発明の効果の発現される程度が向上する傾向があり、より発泡倍率及び独立気泡率に優れる塩素化塩化ビニル発泡粒子を与えうる発泡性塩素化塩化ビニル系樹脂粒子が得られる。 According to the second production method, the degree to which the effect of the present invention is exhibited tends to be improved, and a foamable chlorinated vinyl chloride-based particle capable of giving chlorinated vinyl chloride foam particles having a higher foaming ratio and closed cell ratio can be provided. Resin particles are obtained.
尚、第１及び第２の製法方法に共通して、塩素化塩化ビニル系樹脂、必要に応じて併用される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。 It is preferable that the chlorinated vinyl chloride resin and, if necessary, the vinyl chloride resin used in combination are sufficiently gelled in common to the first and second production methods. If gelation is not sufficiently performed, the rate of dissipation of the foaming agent from the resin particles may increase when foaming resin particles are used, and the foaming agent tends to be difficult to contribute to foaming, resulting in high foaming agent. It may be difficult to obtain foamed particles and a foamed molded product having a foaming ratio or a high closed cell ratio.
樹脂溶融混練（混合）時の樹脂温度については、塩素化塩化ビニル系樹脂、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に影響を及ぼす可能性があることから、１６０℃以上２５０℃未満であることが好ましく、更に好ましくは１６０℃以上２４０℃未満である。樹脂温度が２５０℃を超えると塩素化塩化ビニル系樹脂、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の恐れがあり、結果として発泡性塩素化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。 Regarding the resin temperature during resin melt kneading (mixing), it may affect the decomposition of chlorinated vinyl chloride resin, vinyl chloride resin used in combination if necessary, and additives, so 160 ° C or higher and 250 ° C. It is preferably less than, more preferably 160 ° C. or higher and lower than 240 ° C. If the resin temperature exceeds 250 ° C, there is a risk of decomposition of the chlorinated vinyl chloride resin, the vinyl chloride resin used in combination if necessary, and the additives, and as a result, the deterioration of the foamable chlorinated vinyl chloride resin particles is induced. , May lead to deterioration of foaming performance.
（造粒工程の各条件）
第１及び第２の発泡性塩素化塩化ビニル系樹脂粒子の製造方法における塩素化塩化ビニル系樹脂粒子の造粒工程の条件について説明する。
(Each condition of granulation process)
The conditions of the granulation step of the chlorinated vinyl chloride resin particles in the first and second methods for producing the foamable chlorinated vinyl chloride resin particles will be described.
ダイスから溶融混練物を押出す実施形態においては、ダイス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 the embodiment of extruding the melt-kneaded product from the die, the die is not particularly limited, but for example, one having a small hole having a diameter of 0.3 mm to 2.0 mm, more preferably 0.4 mm to 1.5 mm. Can be mentioned.
ロール加工機等でシート状の溶融混練物を得る実施形態については、得られたシートを冷却した後、カッターやシュレッダーなどの裁断設備でシート状の塩素化塩化ビニル系樹脂粒子を造粒する例が挙げられる。尚、この際のシート状の塩素化塩化ビニル系樹脂粒子の厚みは、混練設備であるロール加工機のクリアランスの調整や、得られたシートを更にプレスすることで調整できる。 Regarding the embodiment of obtaining a sheet-shaped melt-kneaded product by a roll processing machine or the like, an example in which the obtained sheet is cooled and then the sheet-shaped chlorinated vinyl chloride resin particles are granulated by a cutting facility such as a cutter or a shredder. Can be mentioned. The thickness of the sheet-shaped chlorinated vinyl chloride resin particles at this time can be adjusted by adjusting the clearance of the roll processing machine, which is a kneading facility, or by further pressing the obtained sheet.
第２の発泡性塩素化塩化ビニル系樹脂粒子の製造方法において、ダイス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＋３０℃〜Ｔｇ＋１１０℃であることがより好ましく、Ｔｇ＋４０℃〜Ｔｇ＋９０℃であることがさらに好ましい。尚、塩素化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、使用する塩素化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、得られる発泡性塩素化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＋１１０℃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 second method for producing foamable chlorinated vinyl chloride resin particles, the temperature of the molten resin immediately before being extruded from the die is Tg + 20 ° C., where Tg is the glass transition temperature of the resin in a state where no foaming agent is contained. The above is preferable, Tg + 30 ° C. to Tg + 110 ° C. is more preferable, and Tg + 40 ° C. to Tg + 90 ° C. is further preferable. Since the glass transition temperature of the chlorinated vinyl chloride resin increases as the chlorine content increases, it is preferable to appropriately adjust the chlorinated vinyl chloride resin according to the chlorine content of the chlorinated vinyl chloride resin used. When Tg + 20 ° C. or higher, the viscosity of the extruded molten resin becomes low, small pore clogging is unlikely to occur, and the actual small pore opening ratio does not decrease. Therefore, the foamable chlorinated vinyl chloride resin particles obtained can be obtained. It is possible to avoid a situation where the shape is distorted or irregular. On the other hand, when the temperature is Tg + 110 ° C. or lower, the extruded molten resin is likely to solidify, is less likely to wrap around the rotary cutter, and can be cut stably.
第２の発泡性塩素化塩化ビニル系樹脂粒子の製造方法における循環加圧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、ダイス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 circulating pressurized cooling water in the second method for producing foamable chlorinated vinyl chloride resin particles is not particularly limited, but for example, it is cut with a rotary cutter in contact with a die. Examples thereof include a device in which the plastic is spheroidized and transferred to a centrifugal dehydrator to be dehydrated and aggregated without foaming in 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、含有量によって調整すべきであるが、ダイス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。圧力条件としては、得られる発泡性塩素化塩化ビニル系樹脂粒子の発泡倍率が１．０〜１．２倍となるよう、圧力を調整することが好ましい。尚、発泡性塩素化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）を発泡性塩素化塩化ビニル系樹脂粒子の真密度（ｋｇ／ｍ３）で除した値を指す。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０．７〜１．７ＭＰａ、更に好ましくは０．８〜１．５ＭＰａである。 The conditions of the pressurized circulating cooling water should be adjusted according to the resin, additives, foaming agent, and content used, but the foaming of the molten resin extruded from the die is suppressed and the water is stably cut with a cutter. The conditions are preferred. Specifically, the temperature condition of the pressurized circulating cooling water is preferably 40 ° C. to 99 ° C., more preferably 60 to 90 ° C. As the pressure condition, it is preferable to adjust the pressure so that the foaming ratio of the obtained foamable chlorinated vinyl chloride resin particles is 1.0 to 1.2 times. The foaming ratio of the foamable chlorinated vinyl chloride resin particles was obtained by dividing the true density (kg / m 3 ) of the base resin by the true density (kg / m 3 ) of the foamable chlorinated vinyl chloride resin particles. Point to a value. Although it depends on the type of foaming agent used, the pressure condition is preferably 0.6 to 2.0 MPa, more preferably 0.7 to 1.7 MPa, and further preferably 0.8 to 1.5 MPa.
本発明の発泡性塩素化塩化ビニル系樹脂粒子の製造方法において、上記第１の発泡性塩素化塩化ビニル系樹脂粒子での発泡剤の含浸条件等は、一般的に行なわれる条件と同様でよく、適宜設定すればよい。 In the method for producing foamable chlorinated vinyl chloride resin particles of the present invention, the conditions for impregnating the foaming agent with the first foamable chlorinated vinyl chloride resin particles may be the same as those generally performed. , It may be set appropriately.
（塩素化塩化ビニル系樹脂発泡粒子及びその製造方法）
本発明の発泡性塩素化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素化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。特に本発明においては、（Ｂ）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素化塩化ビニル系樹脂と併用させることにより、驚くべきことに水蒸気加熱条件での発泡性が著しく向上することを見出した。尚、ポリメチルメタクリレートを主成分とする塩化ビニル加工性改良剤についても塩素化塩化ビニル系樹脂の発泡倍率を向上させる効果はあるが、水蒸気加熱条件における発泡性については、（Ｂ）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使用する形態との違いが著しいことが本検討において明らかとなったのである。
(Chlorinated vinyl chloride resin foamed particles and their manufacturing method)
The foamable chlorinated vinyl chloride resin particles of the present invention are pre-foamed 2 to 110 times by a heating medium such as heated air or steam to form chlorinated vinyl chloride resin foam particles, and then formed into a foamed molded product. Can be used. In particular, in the present invention, by using (B) a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units in combination with a chlorinated vinyl chloride resin, surprisingly, steam heating conditions are used. It was found that the foamability in the water was remarkably improved. The vinyl chloride processability improver containing polymethylmethacrylate as a main component also has the effect of improving the foaming ratio of the chlorinated vinyl chloride resin, but regarding the foamability under steam heating conditions, (B) aromatic vinyl In this study, it was clarified that the difference from the form using a copolymer having a monomer and an unsaturated nitrile monomer as a structural unit is remarkable.
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。 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の点から１５０℃以下が好ましく、１３０℃以下がより好ましい。 The heating temperature at the time of foaming should be appropriately adjusted depending on the glass transition temperature and melting point of the resin and the content of the foaming agent, but 90 ° C. or higher is preferable, and 100 ° C. or higher is more preferable. On the other hand, from the viewpoint of suppressing variation in the expansion ratio between the expanded particles and preventing shrinkage of the expanded particles, the temperature is preferably 150 ° C. or lower, more preferably 130 ° C. or lower.
ここで特許文献２及び３に記載される押出発泡法により発泡体を得る技術と、本発明の発泡性樹脂粒子から発泡体を得る技術の相違点について詳細に説明する。
押出発泡法は、樹脂が溶融した状態で高圧状態から低圧状態へ圧力を開放させることによって樹脂に溶解・分散していた発泡剤を膨張させ、発泡体を得る技術である。対して、本発明の様に発泡性樹脂粒子から発泡粒子を得る方法では、上述の通り、発泡性樹脂粒子を空気や水蒸気等の加熱媒体を用いて加熱せしめることで発泡させる。
本発明者らは、この発泡性粒子の発泡プロセスにおいて、加熱媒体として空気あるいは水蒸気を用いることに着眼点を置き、鋭意検討を行った結果、驚くべきことに、（Ａ）塩素化塩化ビニル系樹脂と（Ｂ）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を組み合わせることが、（Ａ）塩素化塩化ビニル系樹脂の発泡性向上に好適であることを見出し、更に水蒸気加熱条件では、その効果が著しいことを見出したのである。
Here, the difference between the technique for obtaining a foam by the extrusion foaming method described in Patent Documents 2 and 3 and the technique for obtaining a foam from the foamable resin particles of the present invention will be described in detail.
The extrusion foaming method is a technique for obtaining a foam by expanding the foaming agent dissolved and dispersed in the resin by releasing the pressure from the high pressure state to the low pressure state in the molten state of the resin. On the other hand, in the method of obtaining foamed particles from foamable resin particles as in the present invention, as described above, the foamable resin particles are foamed by heating them with a heating medium such as air or steam.
The present inventors have focused on using air or water vapor as a heating medium in the foaming process of the foamable particles, and as a result of diligent studies, surprisingly, (A) chlorinated vinyl chloride-based Combining the resin with a copolymer having (B) an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units is suitable for improving the foamability of (A) a chlorinated vinyl chloride resin. Furthermore, it was found that the effect is remarkable under the steam heating condition.
以下に本発明者らが推察した発泡性が向上したメカニズムを記載する。（Ａ）塩素化塩化ビニル系樹脂と（Ｂ）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を組み合わせることにより、発泡性樹脂粒子の発泡プロセス中に、加熱媒体の空気あるいは水蒸気が、発泡粒子中へ進入しやすくなることで、発泡粒子セル内の圧力に寄与する作用が高まり高い発泡倍率が得られたものと推察される。特に加熱媒体が水蒸気である場合、発泡粒子セル内の圧力寄与が著しいと推察される。樹脂に含有されていない気体を発泡に寄与させるという着眼点は特許文献２、及び３に記載される押出発泡技術からは容易に類推できないものである。 The mechanism of improved foamability inferred by the present inventors is described below. By combining (A) a chlorinated vinyl chloride resin and (B) a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units, during the foaming process of the foamable resin particles, It is presumed that the air or water vapor of the heating medium easily enters the foamed particles, so that the action of contributing to the pressure in the foamed particle cells is enhanced and a high foaming ratio is obtained. In particular, when the heating medium is water vapor, it is presumed that the pressure contribution in the foamed particle cell is significant. The point of view that the gas not contained in the resin contributes to foaming cannot be easily inferred from the extrusion foaming techniques described in Patent Documents 2 and 3.
また本発明の様に、発泡性樹脂粒子から発泡体を得るためには、上述の様に空気や水蒸気などを加熱媒体として用いて、発泡性樹脂粒子を低温から高温へ温度上昇させ、ガラス状態からゴム状態へ変化させる過程で発泡が実施されるため、完全溶融したゴム状態で発泡させる押出発泡法と発泡時の樹脂粘度は必ずしも一致しないと推測される。以上の観点からも、押出発泡法の技術が発泡性樹脂粒子の発泡に適用可能かどうかは当業者にとっても容易に類推し難いものである。 Further, as in the present invention, in order to obtain a foam from the foamable resin particles, as described above, air or water vapor is used as a heating medium to raise the temperature of the foamable resin particles from a low temperature to a high temperature to obtain a glass state. Since foaming is carried out in the process of changing from to rubber state, it is presumed that the extrusion foaming method of foaming in a completely melted rubber state and the resin viscosity at the time of foaming do not always match. From the above viewpoint, it is difficult for those skilled in the art to easily infer whether the technique of the extrusion foaming method can be applied to the foaming of foamable resin particles.
（塩素化塩化ビニル系樹脂発泡成形体及びその製造方法）
得られた塩素化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）されて塩素化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。
(Chlorinated vinyl chloride resin foam molded article and its manufacturing method)
The obtained chlorinated vinyl chloride resin foam particles are molded by, for example, steam (for example, in-mold molding) using a conventionally known molding machine to produce a chlorinated vinyl chloride resin foam molded product. Depending on the shape of the mold used, it is possible to obtain a molded product having a complicated shape or a block-shaped molded product.
（セル径）
本発明に係る塩素化塩化ビニル系樹脂発泡粒子及びその塩素化塩化ビニル系樹脂発泡成形体は、平均セル径が好ましくは７０〜１０００μｍ、より好ましくは９０〜５００μｍ、さらに好ましくは１００〜４００μｍである。平均セル径が前述の範囲にあることによって、断熱性のより高い塩素化塩化ビニル系樹脂発泡成形体となる。平均セル径が７０μｍ以上であると、発泡倍率の高倍化が容易となる傾向にあり、また、１０００μｍ以下であると、熱伝導率が増加、即ち断熱性能が悪化するのを避けることができる。ここでいう、平均セル径は後述の測定方法により求められる。
(Cell diameter)
The chlorinated vinyl chloride resin foam particles and the chlorinated vinyl chloride resin foam molded product according to the present invention have an average cell diameter of preferably 70 to 1000 μm, more preferably 90 to 500 μm, and further preferably 100 to 400 μm. .. When the average cell diameter is in the above range, the chlorinated vinyl chloride resin foam molded product has higher heat insulating properties. When the average cell diameter is 70 μm or more, the expansion ratio tends to be easily increased, and when it is 1000 μm or less, it is possible to avoid an increase in thermal conductivity, that is, deterioration of heat insulating performance. The average cell diameter referred to here is obtained by the measurement method described later.
（独立気泡率）
本発明に係る塩素化塩化ビニル系樹脂発泡粒子及びその塩素化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 cell ratio)
The chlorinated vinyl chloride resin foam particles and the chlorinated vinyl chloride resin foam molded product according to the present invention have a closed cell ratio of preferably 70% or more, more preferably 80% or more, still more preferably 90% or more. .. When the closed cell ratio is within the above range, the foamed particles are likely to be secondarily foamed even during molding, the moldability of the foamed particles is improved, and the surface properties of the obtained foamed molded product are improved. Play. Further, when the closed cell ratio is in the above range, the strength such as the compressive strength of the foamed molded product tends to be increased.
（発泡成形体の用途）
本発明の発泡性塩素化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、高発泡倍率及び高独立気泡率であり、難燃性能に優れる。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のような各種用途に好適である。
(Use of foam molded product)
The foamed molded product formed by using the foamable chlorinated vinyl chloride resin particles of the present invention has a high foaming ratio and a high closed cell ratio, and is excellent in flame retardancy. Therefore, it is suitable for various applications such as building heat insulating materials, ceiling materials, metal sandwich panel core materials, food container boxes, cold storage boxes, cushioning materials, agricultural and fishery boxes, bathroom heat insulating materials and hot water storage tank heat insulating materials. is there.
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 each of the above-described embodiments, and various modifications can be made within the scope of the claims, and the technical means disclosed in the different embodiments may be appropriately combined. The obtained embodiments are also included in the technical scope of the 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。
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。
Hereinafter, one embodiment of the present invention will be specifically described based on Examples and Comparative Examples, but the present invention is not limited thereto.
The measurement method and evaluation method in the following Examples and Comparative Examples are as follows.
（発泡性塩素化塩化ビニル系樹脂粒子に含まれる発泡剤量の測定）
発泡性塩素化塩化ビニル系樹脂粒子の重量Ｗ１（ｇ）を測定し、１５０℃のオーブンで３０分加熱し、その後、デシケータ内にて室温で３０分冷却し、再度重量Ｗ２（ｇ）を測定した。この加熱前後の重量差（Ｗ１−Ｗ２）を発泡性塩素化塩化ビニル系樹脂粒子中の発泡剤含有量とした。
発泡剤含有量（重量％）＝（Ｗ１−Ｗ２）／Ｗ１×１００
(Measurement of the amount of foaming agent contained in effervescent chlorinated vinyl chloride resin particles)
The weight W 1 (g) of the effervescent chlorinated vinyl chloride resin particles is measured, heated in an oven at 150 ° C. for 30 minutes, then cooled in a desiccator at room temperature for 30 minutes, and again weighed W 2 (g). Was measured. The weight difference (W 1- W 2 ) before and after heating was defined as the content of the foaming agent in the foamable chlorinated vinyl chloride resin particles.
Foaming agent content (% by weight) = (W 1- W 2 ) / W 1 x 100
（塩素化塩化ビニル系樹脂粒子及び発泡性塩素化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塩素化塩化ビニル系樹脂粒子及び発泡性塩素化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
粒重量（ｍｇ）＝［粒子１００粒の重量（ｍｇ）］／１００
(Measurement of grain weight of chlorinated vinyl chloride resin particles and foamable chlorinated vinyl chloride resin particles)
Using an electronic balance capable of measuring up to 0.01 mg, the weights of randomly sampled chlorinated vinyl chloride resin particles and 100 foamable chlorinated vinyl chloride resin particles were measured, and the grain weight was calculated by the following formula. Grain weight (mg) = [Weight of 100 particles (mg)] / 100
（発泡性塩素化塩化ビニル系樹脂粒子の真密度）
重量Ｗ（ｋｇ）の発泡性塩素化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。
発泡性塩素化塩化ビニル系樹脂粒子の真密度＝Ｗ／Ｖ（ｋｇ／ｍ３）
(True density of effervescent chlorinated vinyl chloride resin particles)
Effervescent chlorinated vinyl chloride resin particles having a weight of W (kg) are submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) is obtained from the liquid level rise (submersion method) of the measuring cylinder. Calculated by the formula.
True density of effervescent chlorinated vinyl chloride resin particles = W / V (kg / m 3 )
（発泡性塩素化塩化ビニル系樹脂粒子の発泡性評価）
発泡粒子の最小真密度の評価を下記の３つの加熱雰囲気下で実施した。
(Evaluation of foamability of effervescent chlorinated vinyl chloride resin particles)
The evaluation of the minimum true density of the foamed particles was carried out under the following three heating atmospheres.
＜加熱空気雰囲気下での発泡評価＞
発泡性塩素化塩化ビニル系樹脂粒子を１３０℃に加熱したオーブン（アズワン株式会社製、強制対流定温乾燥器ＳＯＦＷ−６００）に投入し、温度１３０℃の加熱空気雰囲気下で加熱時間を変更して発泡させ、各加熱時間毎の発泡粒子を得た。加熱時間はオーブン投入後３０秒、６０秒、９０秒の様に３０秒間隔で変更し、加熱過多による発泡粒子の収縮（発泡粒子真密度の増加）が確認されるまで加熱した。得られた加熱時間毎の発泡粒子の真密度を測定し、このうちの最も低い密度を塩素化塩化ビニル系樹脂発泡粒子の最小真密度とした。
<Evaluation of foaming in a heated air atmosphere>
The effervescent chlorinated vinyl chloride resin particles were placed in an oven (manufactured by AS ONE Corporation, forced convection constant temperature dryer SOFW-600) heated to 130 ° C., and the heating time was changed in a heated air atmosphere at a temperature of 130 ° C. It was foamed to obtain foamed particles for each heating time. The heating time was changed at 30-second intervals such as 30 seconds, 60 seconds, and 90 seconds after being put into the oven, and heating was performed until shrinkage of the foamed particles (increase in the true density of the foamed particles) due to excessive heating was confirmed. The true density of the foamed particles for each heating time obtained was measured, and the lowest density was taken as the minimum true density of the chlorinated vinyl chloride resin foamed particles.
＜過熱水蒸気雰囲気下での発泡評価＞
発泡性塩素化塩化ビニル系樹脂粒子を１２０℃に加熱したウォーターオーブン（ＳＨＡＲＰ株式会社製、ヘルシオＡＸ−ＣＡ３００−Ｂ）に投入し、温度１２０℃の過熱水蒸気雰囲気下で加熱時間を変更して発泡させ、各加熱時間毎の発泡粒子を得た。加熱時間はウォーターオーブン投入後３０秒、６０秒、９０秒の様に３０秒間隔で変更し、加熱過多による発泡粒子の収縮（発泡粒子真密度の増加）が確認されるまで加熱した。得られた加熱時間毎の発泡粒子の真密度を測定し、このうちの最も低い密度を塩素化塩化ビニル系樹脂発泡粒子の最小真密度とした。
<Evaluation of foaming in a superheated steam atmosphere>
Foamable chlorinated vinyl chloride resin particles are placed in a water oven (Helsio AX-CA300-B manufactured by SHARP Co., Ltd.) heated to 120 ° C., and foamed by changing the heating time in a superheated steam atmosphere at a temperature of 120 ° C. To obtain foamed particles for each heating time. The heating time was changed at 30-second intervals such as 30 seconds, 60 seconds, and 90 seconds after the water was put into the water oven, and heating was performed until shrinkage of the foamed particles (increase in the true density of the foamed particles) due to excessive heating was confirmed. The true density of the foamed particles for each heating time obtained was measured, and the lowest density was taken as the minimum true density of the chlorinated vinyl chloride resin foamed particles.
＜水蒸気雰囲気下での発泡評価＞
発泡性塩素化塩化ビニル系樹脂粒子を予備発泡機（大開工業株式会社製）に投入し、０．２ＭＰａの水蒸気を予備発泡機に導入し、予備発泡機内部の温度９０〜１２０℃の条件で、発泡させ発泡粒子を得た。発泡性塩素化塩化ビニル系樹脂粒子の予備発泡機への投入量を１５００ｇ、１０００ｇ、７５０ｇ、６００ｇ、５００ｇ、４００ｇ、３５０ｇの条件で発泡させ、投入量毎の発泡粒子の真密度を測定し、このうちの最も低い真密度を塩素化塩化ビニル系樹脂発泡粒子の最小真密度とした。投入量の減量は発泡粒子の収縮（発泡粒子真密度の増加）が確認されるまで実施した。
<Evaluation of foaming in a water vapor atmosphere>
Effervescent chlorinated vinyl chloride resin particles were put into a pre-foaming machine (manufactured by Daikai Kogyo Co., Ltd.), 0.2 MPa of water vapor was introduced into the pre-foaming machine, and the temperature inside the pre-foaming machine was 90 to 120 ° C. , Foamed to obtain foamed particles. The amount of foamable chlorinated vinyl chloride resin particles charged into the pre-foaming machine was 1500 g, 1000 g, 750 g, 600 g, 500 g, 400 g, and 350 g, and the true density of the foamed particles was measured for each input amount. The lowest true density was defined as the minimum true density of the chlorinated vinyl chloride resin foamed particles. The input amount was reduced until the shrinkage of the foamed particles (increase in the true density of the foamed particles) was confirmed.
尚、発泡粒子の真密度は、重量Ｗ（ｋｇ）の発泡粒子を、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Ｖ（ｍ３）を求め、以下の式で算出した。
発泡粒子の真密度＝Ｗ／Ｖ（ｋｇ／ｍ３）
For the true density of the foamed particles, the foamed particles having a weight of W (kg) are submerged in a measuring cylinder containing ethanol, and the volume V (m 3 ) is obtained from the liquid level rise (submersion method) of the measuring cylinder. It was calculated by the following formula.
True density of foamed particles = W / V (kg / m 3 )
（塩素化塩化ビニル系樹脂発泡粒子及び塩素化塩化ビニル発泡成形体の独立気泡率の測定）
発泡粒子及び発泡成形体の試験片を、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、試験片の体積Ｖｃ（ｃｍ３）測定した。次に測定後の同じ試験片をエタノールの入ったメスシリンダー内に沈め、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。
独立気泡率（％）＝（Ｖｃ／Ｖａ）×１００
(Measurement of closed cell ratio of chlorinated vinyl chloride resin foam particles and chlorinated vinyl chloride foam molded product)
The volume Vc (cm 3 ) of the test piece of the foamed particles and the foamed molded product is measured by using an air pycnometer (air comparative hydrometer model 1000 manufactured by Tokyo Science Co., Ltd.) in accordance with the method described in ASTM D2856. )It was measured. Next, the same test piece after the measurement was submerged in a measuring cylinder containing ethanol, the volume Va (cm 3 ) was calculated from the liquid level rise (submersion method) of the measuring cylinder, and the closed cell ratio (%) was calculated according to the following formula. Was calculated.
Closed cell ratio (%) = (Vc / Va) x 100
（塩素化塩化ビニル系樹脂発泡粒子及び塩素化塩化ビニル発泡成形体の平均セル径の測定）
塩素化塩化ビニル系樹脂発泡粒子及び塩素化塩化ビニル発泡成形体の中心をカミソリで切削し、光学顕微鏡で断面を観察した。断面の１０００μｍ×１０００μｍ四方の範囲内に存在するセル数を計測し、下記式（面積平均径）で測定した値を平均セル径とした。各サンプル５個の平均セル径を測定し、その平均を水準の平均セル径とした。
平均セル径（μｍ）＝２×［１０００μｍ×１０００μｍ／（セル数×π）］１／２。
(Measurement of average cell diameter of chlorinated vinyl chloride resin foam particles and chlorinated vinyl chloride foam molded product)
The centers of the chlorinated vinyl chloride resin foam particles and the chlorinated vinyl chloride foam molded product were cut with a razor, and the cross section was observed with an optical microscope. The number of cells existing in the range of 1000 μm × 1000 μm square of the cross section was measured, and the value measured by the following formula (area average diameter) was taken as the average cell diameter. The average cell diameter of 5 samples was measured, and the average was taken as the average cell diameter of the level.
Average cell diameter (μm) = 2 × [1000 μm × 1000 μm / (number of cells × π)] 1/2 .
（発泡成形体の密度測定）
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、下記式から求めた。
発泡成形体の密度（ｋｇ／ｍ３） ＝ Ｗ ／（Ｘ×Ｙ×Ｚ）×１０６
(Measurement of density of foam molded product)
The vertical dimension X (mm), horizontal dimension Y (mm), and thickness dimension Z (mm) of the foamed molded product are measured with a caliper, and the weight W (g) of the foamed molded product is measured with an electronic balance. I asked for it.
Density of foam molded product (kg / m 3 ) = W / (X × Y × Z) × 10 6
（発泡成形体の表面性）
得られた発泡成形体の表面性を下記判断指標で評価した。
◎；成形体表面の発泡粒子間の隙間が殆ど無い
○；成形体表面の発泡粒子間の隙間がやや観察される
△；成形体表面の発泡粒子間の隙間がかなり観察される
(Surface property of foam molded product)
The surface property of the obtained foam molded product was evaluated by the following judgment index.
◎; There are almost no gaps between the foamed particles on the surface of the molded product ○; Gap between the foamed particles on the surface of the molded product is slightly observed △;
以下に、実施例及び比較例で用いた原材料を示す。
（塩素化塩化ビニル系樹脂）
（Ａ−１）塩素化塩化ビニル樹脂［（株）カネカ製、Ｈ７１６Ｓ、平均重合度６００、塩素含有量６７．６重量％］
（塩化ビニル系樹脂）
（Ａ−２）塩化ビニル樹脂［（株）カネカ製、平均重合度６００、塩素含有量５６．８重量％］
（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）
（Ｂ）スチレン−アクリロニトリル共重合体（Ｇａｌａｔａ製、Ｂｌｅｎｄｅｘ８６９、重量平均分子量２８６万、共重合体中のアクニロニトリル由来の成分比率；２０重量％）
（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］
（加工性改良剤）
（Ｄ）アクリル系樹脂［（株）カネカ製、カネエースＰＡ−４０］
The raw materials used in Examples and Comparative Examples are shown below.
(Chlorinated vinyl chloride resin)
(A-1) Chlorinated vinyl chloride resin [manufactured by Kaneka Corporation, H716S, average degree of polymerization 600, chlorine content 67.6% by weight]
(Vinyl chloride resin)
(A-2) Vinyl chloride resin [manufactured by Kaneka Corporation, average degree of polymerization 600, chlorine content 56.8% by weight]
(Copolymer having aromatic vinyl monomer and unsaturated nitrile monomer as structural units)
(B) Styrene-acrylonitrile copolymer (manufactured by Galata, Blendex 869, weight average molecular weight 2.86 million, component ratio derived from acnillonitrile in the copolymer; 20% by weight)
(Foaming agent)
(C-1) Normal pentane [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
(C-2) Acetone [manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.]
(Processability improver)
(D) Acrylic resin [Kaneka Corporation, Kaneka PA-40]
（実施例１）
［塩素化塩化ビニル系樹脂粒子の作製］
塩素化塩化ビニル樹脂（Ａ−１）１００重量部に対し、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を５重量部、更に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、塩素含有量３５重量％の塩素化ポリエチレン５重量部を加え、この配合物をハンドブレンドにてブレンドし均一な配合物を得た。
このブレンド配合物を、８インチのロールにより１９５℃で５分間混練し、得たシート状の組成物をカッターにて裁断し、粒重量６ｍｇの塩素化塩化ビニル系樹脂粒子を得た。
(Example 1)
[Preparation of chlorinated vinyl chloride resin particles]
5 parts by weight of the copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer with respect to 100 parts by weight of the chlorinated vinyl chloride resin (A-1). Further, 5 parts by weight of a butyltin mercapto-based stabilizer, 3 parts by weight of a lubricant (ester wax, polyethylene wax), and 5 parts by weight of chlorinated polyethylene having a chlorine content of 35% by weight are added, and this formulation is blended by hand blending to be uniform. Formulation was obtained.
This blend formulation was kneaded with an 8-inch roll at 195 ° C. for 5 minutes, and the obtained sheet-like composition was cut with a cutter to obtain chlorinated vinyl chloride resin particles having a grain weight of 6 mg.
［発泡性塩素化塩化ビニル系樹脂粒子の作製］
得られた塩素化塩化ビニル系樹脂粒子１００重量部に対して、発泡剤（Ｃ−１）１００重量部を容積１００ｃｃの耐圧容器に入れ密封した後、オイルバスにて１２０℃の条件で４時間加熱し、耐圧容器を冷却し、耐圧容器から発泡性塩素化塩化ビニル系樹脂粒子を取出した。発泡性塩素化塩化ビニル粒子の発泡剤含有量は１１重量％、真密度は１２７０ｋｇ／ｍ３であった。
[Preparation of effervescent chlorinated vinyl chloride resin particles]
100 parts by weight of the foaming agent (C-1) was placed in a pressure-resistant container having a volume of 100 cc with respect to 100 parts by weight of the obtained chlorinated vinyl chloride resin particles and sealed, and then in an oil bath at 120 ° C. for 4 hours. The pressure-resistant container was heated, and the foamable chlorinated vinyl chloride-based resin particles were taken out from the pressure-resistant container. The foaming agent content of the effervescent chlorinated vinyl chloride particles was 11% by weight, and the true density was 1270 kg / m 3 .
［塩素化塩化ビニル系樹脂発泡粒子の作製］
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、上述の＜加熱空気雰囲気下での発泡評価＞にて発泡評価を実施した結果、発泡粒子の最小真密度は７０ｋｇ／ｍ３、その際の発泡粒子の独立気泡率は１００％であった。
[Preparation of chlorinated vinyl chloride resin foam particles]
After storing the obtained foamable chlorinated vinyl chloride resin particles at 10 ° C. for 7 days, the foaming evaluation was performed by the above-mentioned <Expansion of foaming in a heated air atmosphere>. As a result, the minimum true density of the foamed particles was found. At 70 kg / m 3 , the closed cell ratio of the foamed particles was 100%.
（実施例２）
実施例１における［塩素化塩化ビニル系樹脂粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を１３重量部に変更した以外は実施例１と同様の操作を行い、発泡粒子を得た。結果を表１に示す。
(Example 2)
In [Preparation of Chlorinated Vinyl Chloride Resin Particles] in Example 1, 13 parts by weight of a copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was used. The same operation as in Example 1 was carried out except for the change to, to obtain foamed particles. The results are shown in Table 1.
（実施例３）
実施例１における［塩素化塩化ビニル系樹脂粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を２０重量部に変更した以外は実施例１と同様の操作を行い、発泡粒子を得た。結果を表１に示す。
(Example 3)
In [Preparation of Chlorinated Vinyl Chloride Resin Particles] in Example 1, 20 parts by weight of a copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was used. The same operation as in Example 1 was carried out except for the change to, to obtain foamed particles. The results are shown in Table 1.
（実施例４）
実施例１における［塩素化塩化ビニル系樹脂発泡粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を３０重量部に変更した以外は実施例１と同様の操作を行い、発泡粒子を得た。結果を表１に示す。
(Example 4)
In [Preparation of chlorinated vinyl chloride resin foamed particles] in Example 1, 30 weights of a copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was used. The same operation as in Example 1 was carried out except that the part was changed to a part, and foamed particles were obtained. The results are shown in Table 1.
（比較例１）
実施例１における［塩素化塩化ビニル系樹脂粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を添加しなかった以外は実施例１と同様の操作を行い、発泡粒子を得た。結果を表１に示す。
(Comparative Example 1)
In [Preparation of chlorinated vinyl chloride resin particles] in Example 1, the copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was not added. The same operation as in Example 1 was carried out except for the above, and foamed particles were obtained. The results are shown in Table 1.
（比較例２）
実施例１における［塩素化塩化ビニル系樹脂粒子の作製］において、塩素化塩化ビニル樹脂（Ａ−１）１００重量部の代わりに塩化ビニル系樹脂（Ａ−２）１００重量部を使用したこと以外は実施例２と同様の操作を行ったが、全く発泡せず、発泡粒子は得られなかった。結果を表１に示す。
(Comparative Example 2)
In [Preparation of chlorinated vinyl chloride resin particles] in Example 1, except that 100 parts by weight of vinyl chloride resin (A-2) was used instead of 100 parts by weight of chlorinated vinyl chloride resin (A-1). Performed the same operation as in Example 2, but did not foam at all, and foamed particles were not obtained. The results are shown in Table 1.
（実施例５）
［塩素化塩化ビニル系樹脂粒子の作製］
塩素化塩化ビニル樹脂（Ａ−１）１００重量部に対し、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を１３重量部、更に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、塩素含有量３５重量％の塩素化ポリエチレン５重量部を加え、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、φ２６ｍｍ同方向噛み合い二軸押出機にて吐出量８ｋｇ／ｈｒの条件で溶融混練し、押出機先端に取り付けられた直径１．７ｍｍの***が１３個設けられたダイスを通じてストランド状とし、水槽で冷却固化させた後、ストランドカッターで裁断し、塩素化塩化ビニル系樹脂粒子を得た。得られた塩化ビニル系樹脂粒子の粒重量は６ｍｇであった。
(Example 5)
[Preparation of chlorinated vinyl chloride resin particles]
13 parts by weight of the copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer with respect to 100 parts by weight of the chlorinated vinyl chloride resin (A-1). Further, 5 parts by weight of a butyl tin mercapto stabilizer, 3 parts by weight of a lubricant (ester wax, polyethylene wax), and 5 parts by weight of chlorinated polyethylene having a chlorine content of 35% by weight are added, and this formulation is blended to obtain a uniform formulation. After that, the pellets were melt-kneaded with a twin-screw extruder that meshed in the same direction to obtain pellets having the above compounding ratio.
The obtained pellets are melt-kneaded with a φ26 mm same-direction meshing twin-screw extruder under the condition of a discharge rate of 8 kg / hr, and strands are passed through a die provided with 13 small holes with a diameter of 1.7 mm attached to the tip of the extruder. After cooling and solidifying in a water tank, the particles were cut with a strand cutter to obtain chlorinated vinyl chloride resin particles. The grain weight of the obtained vinyl chloride resin particles was 6 mg.
[発泡性塩素化塩化ビニル系樹脂粒子の作製]
容積６Ｌの撹拌装置付きオートクレーブ内に、得られた塩素化塩化ビニル系樹脂粒子１００重量部に対して、発泡剤（Ｃ−１）１００重量部を投入し、オートクレーブを密閉した。その後、１時間３０分かけて１２０℃まで加温した後、そのまま２４時間保持した。
次いで、室温まで冷却し、オートクレーブから発泡剤が含浸された樹脂粒子を取り出し、発泡性塩素化塩化ビニル系樹脂粒子を得た。発泡性塩素化塩化ビニル粒子の発泡剤含有量は１３重量％、真密度は１２７０ｋｇ／ｍ３であった。
[Preparation of effervescent chlorinated vinyl chloride resin particles]
100 parts by weight of the foaming agent (C-1) was put into 100 parts by weight of the obtained chlorinated vinyl chloride resin particles in an autoclave with a stirring device having a volume of 6 L, and the autoclave was sealed. Then, after heating to 120 degreeC over 1 hour and 30 minutes, it was kept as it was for 24 hours.
Then, the mixture was cooled to room temperature, and the resin particles impregnated with the foaming agent were taken out from the autoclave to obtain foamable chlorinated vinyl chloride resin particles. The foaming agent content of the effervescent chlorinated vinyl chloride particles was 13% by weight, and the true density was 1270 kg / m 3 .
［塩素化塩化ビニル系樹脂発泡粒子の作製］
（加熱空気雰囲気下での発泡評価）
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、上述の＜加熱空気雰囲気下での発泡評価＞にて発泡評価を実施した結果、発泡粒子の最小真密度は４４ｋｇ／ｍ３、その際の発泡粒子の独立気泡率は９５％であった。
[Preparation of chlorinated vinyl chloride resin foam particles]
(Evaluation of foaming in a heated air atmosphere)
After storing the obtained foamable chlorinated vinyl chloride resin particles at 10 ° C. for 7 days, the foaming evaluation was performed by the above-mentioned <Expansion of foaming in a heated air atmosphere>. As a result, the minimum true density of the foamed particles was found. At 44 kg / m 3 , the closed cell ratio of the foamed particles was 95%.
（過熱水蒸気雰囲気下での発泡評価）
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、上述の＜過熱水蒸気雰囲気下での発泡評価＞にて発泡評価を実施した結果、発泡粒子の最小真密度は、３０ｋｇ／ｍ３、その際の発泡粒子の独立気泡率は７０％であった。
(Evaluation of foaming in a superheated steam atmosphere)
After storing the obtained foamable chlorinated vinyl chloride resin particles at 10 ° C. for 7 days, the foaming evaluation was carried out by the above-mentioned <Evaluation of foaming in a superheated steam atmosphere>. As a result, the minimum true density of the foamed particles was found. , 30 kg / m 3 , and the closed cell ratio of the foamed particles at that time was 70%.
（水蒸気雰囲気下での成形用発泡粒子の作製）
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、発泡性塩素化塩化ビニル系樹脂粒子１５００ｇを予備発泡機（大開工業株式会社製）に投入し、０．２ＭＰａ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、真密度９３ｋｇ／ｍ３、独立気泡率９９％、平均セル径２８０μｍの発泡粒子を得た。
(Preparation of foamed particles for molding in a steam atmosphere)
The obtained foamable chlorinated vinyl chloride resin particles were stored at 10 ° C. for 7 days, and then 1500 g of the foamable chlorinated vinyl chloride resin particles were put into a preliminary foaming machine (manufactured by Daikai Kogyo Co., Ltd.) and 0.2 MPa. steam is introduced into the pre-expanded machine, foamed at a temperature of 110 ° C. internal preliminary foaming machine, a true density of 93kg / m 3, 99% closed cell ratio, to obtain a foamed particle having an average cell diameter 280 .mu.m.
［塩素化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真密度９３ｋｇ／ｍ３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、０．１２ＭＰａ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。塩素化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）なるまで塩素化塩化ビニル系樹脂発泡成形体を金型内に保持した後に、塩素化塩化ビニル系樹脂発泡成形体を取り出して、直方体状の塩素化塩化ビニル系樹脂発泡成形体を得た。成形体の密度は、６０ｋｇ／ｍ３、独立気泡率は８８％、成形体表面性は○、平均セル径は３１０μｍであった。結果及び評価結果を表２に示す。
[Preparation of chlorinated vinyl chloride resin foam molded article]
Foamed particles having a true density of 93 kg / m 3 obtained under the above steam atmosphere are filled in an in-mold molding die having a length of 400 mm, a width of 400 mm, and a thickness of 25 mm attached to a styrofoam molding machine, and 0.12 MPa. After introducing the steam of the above and foaming in the mold, water was sprayed on the mold for 20 seconds to cool it. After holding the chlorinated vinyl chloride resin foam molded product in the mold until the pressure at which the chlorinated vinyl chloride resin foam molded product pushes the mold becomes 0.05 MPa (gauge pressure), the chlorinated vinyl chloride resin foamed product is foamed. The molded product was taken out to obtain a rectangular chlorinated vinyl chloride resin foam molded product. The density of the molded product was 60 kg / m 3 , the closed cell ratio was 88%, the surface texture of the molded product was ◯, and the average cell diameter was 310 μm. The results and evaluation results are shown in Table 2.
（比較例３）
実施例５における［塩素化塩化ビニル系樹脂粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を添加せず、代わりに加工性改良剤（Ｄ）を１３重量部添加した以外は、実施例５と同様の操作を行い、発泡成形体を得た。結果および評価結果を表２に示す。
(Comparative Example 3)
In [Preparation of chlorinated vinyl chloride resin particles] in Example 5, the copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was not added. The same operation as in Example 5 was carried out except that 13 parts by weight of the processability improving agent (D) was added instead, to obtain a foam molded product. The results and evaluation results are shown in Table 2.
（実施例６）
［発泡性塩素化塩化ビニル系樹脂粒子の作製］
塩素化塩化ビニル樹脂（Ａ−１）１００重量部に対し、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を１３重量部、更に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、塩素含有量３５重量％の塩素化ポリエチレン５重量部を加え、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。
二軸押出機の途中から、前記樹脂組成物１００重量部に対して、ノルマルペンタン（Ｃ−１）９重量部とアセトン（Ｃ−２）４重量部を圧入した。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１７０℃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℃に設定したダイスから、吐出量４５ｋｇ／ｈｒで、温度７０℃及び１．３ＭＰａの加圧循環水中に押出した。押出された溶融樹脂は、ダイス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６ｍｇの発泡性塩素化塩化ビニル系樹脂粒子を得た。得られた発泡性塩素化塩化ビニル系樹脂粒子の発泡剤含有量は１１重量％、真密度は１３１０ｋｇ／ｍ３であった。
(Example 6)
[Preparation of effervescent chlorinated vinyl chloride resin particles]
13 parts by weight of the copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer with respect to 100 parts by weight of the chlorinated vinyl chloride resin (A-1). Further, 5 parts by weight of a butyl tin mercapto stabilizer, 3 parts by weight of a lubricant (ester wax, polyethylene wax), and 5 parts by weight of chlorinated polyethylene having a chlorine content of 35% by weight are added, and this formulation is blended to obtain a uniform formulation. After that, the pellets were melt-kneaded with a twin-screw extruder that meshed in the same direction to obtain pellets having the above compounding ratio.
The obtained pellets were melt-kneaded in a φ40 mm co-directional meshing twin-screw extruder with a feed amount of 40 kg / hr.
From the middle of the twin-screw extruder, 9 parts by weight of normal pentane (C-1) and 4 parts by weight of acetone (C-2) were press-fitted into 100 parts by weight of the resin composition. After that, it was cooled to a resin temperature of 170 ° C. through a continuous pipe attached to the tip of the twin-screw extruder, a single-screw extruder, a gear pump, and a divertor valve, and was attached downstream of the divertor valve with a diameter of 1.0 mm and a land length of 3. A die set at 230 ° C. having 30 small holes of .5 mm was extruded into pressurized circulating water at a temperature of 70 ° C. and 1.3 MPa at a discharge rate of 45 kg / hr. The extruded molten resin was cut and granulated using a rotary cutter in contact with a die, and transferred to a centrifugal dehydrator to obtain foamable chlorinated vinyl chloride resin particles having a grain weight of 6 mg. The foaming agent content of the obtained foamable chlorinated vinyl chloride resin particles was 11% by weight, and the true density was 1310 kg / m 3 .
［塩素化塩化ビニル系樹脂発泡粒子の作製］
（水蒸気加熱雰囲気下での発泡評価）
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、上述の ＜水蒸気雰囲気下での発泡評価＞にて発泡評価を実施した結果、最小で真密度３４ｋｇ／ｍ３、独立気泡率９０％、平均セル径４００μｍの発泡粒子を得た。発泡性塩素化塩化ビニル系樹脂粒子の投入量と発泡粒子の真密度との関係性を図１に、発泡粒子の真密度と独立気泡率との関係性を図２に示す。
[Preparation of chlorinated vinyl chloride resin foam particles]
(Evaluation of foaming in a steam heating atmosphere)
The obtained effervescent chlorinated vinyl chloride resin particles were stored at 10 ° C. for 7 days, and then the effervescence evaluation was performed by the above-mentioned <effervescence evaluation in a water vapor atmosphere>. As a result, the minimum true density was 34 kg / m 3. , Foamed particles having a closed cell ratio of 90% and an average cell diameter of 400 μm were obtained. The relationship between the input amount of the foamable chlorinated vinyl chloride resin particles and the true density of the foamed particles is shown in FIG. 1, and the relationship between the true density of the foamed particles and the closed cell ratio is shown in FIG.
（水蒸気雰囲気下での成形用発泡粒子の作製）
得られた発泡性塩素化塩化ビニル系樹脂粒子を１０℃で７日保管した後、発泡性塩素化塩化ビニル系樹脂粒子１５００ｇを予備発泡機（大開工業株式会社製）に投入し、０．２ＭＰａ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、真密度１１０ｋｇ／ｍ３、独立気泡率９８％、平均セル径３２０μｍの発泡粒子を得た。
(Preparation of foamed particles for molding in a steam atmosphere)
The obtained foamable chlorinated vinyl chloride resin particles were stored at 10 ° C. for 7 days, and then 1500 g of the foamable chlorinated vinyl chloride resin particles were put into a preliminary foaming machine (manufactured by Daikai Kogyo Co., Ltd.) and 0.2 MPa. steam is introduced into the pre-expanded machine, foamed at a temperature of 110 ° C. internal preliminary foaming machine, a true density of 110kg / m 3, 98% closed cell ratio, to obtain a foamed particle having an average cell diameter 320 .mu.m.
［塩素化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真密度１１０ｋｇ／ｍ３の発泡粒子を、発泡スチロール用成形機に取り付けた型内成形用金型内に充填して、０．１２ＭＰａ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。塩素化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）なるまで塩素化塩化ビニル系樹脂発泡成形体を金型内に保持した後に、塩素化塩化ビニル系樹脂発泡成形体を取り出して、直方体状の塩素化塩化ビニル系樹脂発泡成形体を得た。成形体の密度は７３ｋｇ／ｍ３、独立気泡率は９６％、表面性は◎、平均セル径は３７０μｍであった。結果及び評価結果を表３に示す。
[Preparation of chlorinated vinyl chloride resin foam molded article]
Foamed particles having a true density of 110 kg / m 3 obtained under the above steam atmosphere are filled in an in-mold molding die attached to a styrofoam molding machine, and 0.12 MPa of steam is introduced to in-mold foam. After that, the mold was sprayed with water for 20 seconds to cool it. After holding the chlorinated vinyl chloride resin foam molded product in the mold until the pressure at which the chlorinated vinyl chloride resin foam molded product pushes the mold becomes 0.05 MPa (gauge pressure), the chlorinated vinyl chloride resin foamed product is foamed. The molded product was taken out to obtain a rectangular chlorinated vinyl chloride resin foam molded product. The density of the molded product was 73 kg / m 3 , the closed cell ratio was 96%, the surface property was ⊚, and the average cell diameter was 370 μm. The results and evaluation results are shown in Table 3.
（比較例４）
実施例６における［発泡性塩素化塩化ビニル系樹脂粒子の作製］において、芳香族ビニル単量体由来の構造単位及び不飽和ニトリル単量体由来の構造単位を有する共重合体（Ｂ）を添加せず、代わりに加工性改良剤（Ｄ）を１３重量部添加した以外は、実施例６と同様の操作を行い、発泡成形体を得た。尚、上述の＜水蒸気雰囲気下での発泡評価＞において、発泡性塩素化塩化ビニル系樹脂粒子の予備発泡機への投入量が４００ｇの際の発泡粒子の真密度が、投入量５００ｇの際の発泡粒子の真密度と比較して、増加（発泡粒子の収縮）が確認されたため、投入量３５０ｇの発泡評価は実施しなかった。結果および評価結果を表３、図１、図２に示す。
(Comparative Example 4)
In [Preparation of foamable chlorinated vinyl chloride resin particles] in Example 6, a copolymer (B) having a structural unit derived from an aromatic vinyl monomer and a structural unit derived from an unsaturated nitrile monomer was added. Instead, the same operation as in Example 6 was carried out except that 13 parts by weight of the processability improving agent (D) was added to obtain a foamed molded product. In the above-mentioned <evaluation of foaming in a steam atmosphere>, when the true density of the foamed particles when the amount of the foamable chlorinated vinyl chloride resin particles charged to the pre-foaming machine is 400 g is 500 g, the amount of the foamed particles is 500 g. Since an increase (shrinkage of the foamed particles) was confirmed as compared with the true density of the foamed particles, the foaming evaluation with an input amount of 350 g was not carried out. The results and evaluation results are shown in Table 3, FIG. 1 and FIG.
Claims (20)
（Ａ）塩素化塩化ビニル系樹脂、
（Ｂ）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、および、
（Ｃ）発泡剤。 Effervescent chlorinated vinyl chloride resin particles containing the following (A) to (C):
(A) Chlorinated vinyl chloride resin,
(B) A copolymer having an aromatic vinyl monomer and an unsaturated nitrile as structural units, and
(C) Foaming agent.
（Ｉ）塩素化塩化ビニル系樹脂、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、発泡剤を含有する溶融混練物を作製する工程
（ＩＩ）前記溶融混練物を、小孔を有するダイスを通じて、加圧循環水内に押し出す工程
（ＩＩＩ）前記押し出し直後の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する工程。 A method for producing effervescent chlorinated vinyl chloride resin particles, which comprises the following steps (I) to (III):
(I) Step of producing a melt-kneaded product containing a chlorinated vinyl chloride resin, a copolymer having an aromatic vinyl monomer and an unsaturated nitrile monomer as structural units, and a foaming agent (II). Step of extruding the melt-kneaded product into pressurized circulating water through a die having small holes (III) A step of cutting the melt-kneaded product immediately after the extrusion and cooling and solidifying it with pressurized circulating water.
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