JPWO2016098344A1 - Vinyl chloride resin composition and method for producing the same, vinyl chloride resin molded article and method for producing the same, and laminate - Google Patents
Vinyl chloride resin composition and method for producing the same, vinyl chloride resin molded article and method for producing the same, and laminate Download PDFInfo
- Publication number
- JPWO2016098344A1 JPWO2016098344A1 JP2016564687A JP2016564687A JPWO2016098344A1 JP WO2016098344 A1 JPWO2016098344 A1 JP WO2016098344A1 JP 2016564687 A JP2016564687 A JP 2016564687A JP 2016564687 A JP2016564687 A JP 2016564687A JP WO2016098344 A1 JPWO2016098344 A1 JP WO2016098344A1
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- Prior art keywords
- vinyl chloride
- chloride resin
- resin composition
- mass
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- Prior art date
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- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 263
- 229920005989 resin Polymers 0.000 title claims abstract description 180
- 239000011347 resin Substances 0.000 title claims abstract description 180
- 239000011342 resin composition Substances 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- -1 polyol compound Chemical class 0.000 claims abstract description 89
- 239000004014 plasticizer Substances 0.000 claims abstract description 46
- 239000000843 powder Substances 0.000 claims abstract description 41
- 229920005862 polyol Polymers 0.000 claims abstract description 40
- 239000004814 polyurethane Substances 0.000 claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 claims abstract description 33
- 238000005187 foaming Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 62
- 239000010419 fine particle Substances 0.000 claims description 45
- 238000000465 moulding Methods 0.000 claims description 42
- 229920005906 polyester polyol Polymers 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 12
- 150000003077 polyols Chemical class 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 46
- 229910052751 metal Inorganic materials 0.000 description 21
- 239000002184 metal Substances 0.000 description 21
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 21
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 20
- 239000000049 pigment Substances 0.000 description 19
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 18
- 229960001545 hydrotalcite Drugs 0.000 description 18
- 229910001701 hydrotalcite Inorganic materials 0.000 description 18
- 235000014113 dietary fatty acids Nutrition 0.000 description 17
- 239000000194 fatty acid Substances 0.000 description 17
- 229930195729 fatty acid Natural products 0.000 description 17
- 150000004665 fatty acids Chemical class 0.000 description 14
- 150000003839 salts Chemical class 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 13
- 238000010410 dusting Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 10
- 229920001610 polycaprolactone Polymers 0.000 description 9
- 239000004632 polycaprolactone Substances 0.000 description 9
- 229920000728 polyester Polymers 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 150000002148 esters Chemical class 0.000 description 7
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000000417 fungicide Substances 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920005830 Polyurethane Foam Polymers 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 239000002216 antistatic agent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 239000011496 polyurethane foam Substances 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N allylamine Natural products NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- PXZQEOJJUGGUIB-UHFFFAOYSA-N isoindolin-1-one Chemical compound C1=CC=C2C(=O)NCC2=C1 PXZQEOJJUGGUIB-UHFFFAOYSA-N 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- JQCXWCOOWVGKMT-UHFFFAOYSA-N phthalic acid diheptyl ester Natural products CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- KMZHZAAOEWVPSE-UHFFFAOYSA-N 2,3-dihydroxypropyl acetate Chemical class CC(=O)OCC(O)CO KMZHZAAOEWVPSE-UHFFFAOYSA-N 0.000 description 2
- NXQMCAOPTPLPRL-UHFFFAOYSA-N 2-(2-benzoyloxyethoxy)ethyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCCOCCOC(=O)C1=CC=CC=C1 NXQMCAOPTPLPRL-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Chemical class 0.000 description 2
- 239000004609 Impact Modifier Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- UYXTWWCETRIEDR-UHFFFAOYSA-N Tributyrin Chemical class CCCC(=O)OCC(OC(=O)CCC)COC(=O)CCC UYXTWWCETRIEDR-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000007561 laser diffraction method Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- 125000001477 organic nitrogen group Chemical group 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- PJQYNUFEEZFYIS-UHFFFAOYSA-N perylene maroon Chemical compound C=12C3=CC=C(C(N(C)C4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)N(C)C(=O)C4=CC=C3C1=C42 PJQYNUFEEZFYIS-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical class CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical compound FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- LRQGFQDEQPZDQC-UHFFFAOYSA-N 1-Phenyl-1,3-eicosanedione Chemical compound CCCCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 LRQGFQDEQPZDQC-UHFFFAOYSA-N 0.000 description 1
- BKUAQOCVPRDREL-UHFFFAOYSA-N 1-Phenyl-1,3-octadecanedione Chemical compound CCCCCCCCCCCCCCCC(=O)CC(=O)C1=CC=CC=C1 BKUAQOCVPRDREL-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000000263 2,3-dihydroxypropyl (Z)-octadec-9-enoate Substances 0.000 description 1
- HDIFHQMREAYYJW-FMIVXFBMSA-N 2,3-dihydroxypropyl (e)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C\CCCCCCCC(=O)OCC(O)CO HDIFHQMREAYYJW-FMIVXFBMSA-N 0.000 description 1
- 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 1
- PHDVPEOLXYBNJY-KTKRTIGZSA-N 2-(2-hydroxyethoxy)ethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCOCCO PHDVPEOLXYBNJY-KTKRTIGZSA-N 0.000 description 1
- QUYITUXSUUKIRL-ZDKIGPTLSA-N 2-(2-hydroxyethoxy)ethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCCOCCO QUYITUXSUUKIRL-ZDKIGPTLSA-N 0.000 description 1
- WGIMXKDCVCTHGW-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCOCCO WGIMXKDCVCTHGW-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
- RTGQGAXEHFZMBG-UHFFFAOYSA-N 2-(2-nonanoyloxyethoxy)ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCCOCCOC(=O)CCCCCCCC RTGQGAXEHFZMBG-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-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
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- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 1
- DWNAQMUDCDVSLT-UHFFFAOYSA-N diphenyl phthalate Chemical compound C=1C=CC=C(C(=O)OC=2C=CC=CC=2)C=1C(=O)OC1=CC=CC=C1 DWNAQMUDCDVSLT-UHFFFAOYSA-N 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- YCZJVRCZIPDYHH-UHFFFAOYSA-N ditridecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCCC YCZJVRCZIPDYHH-UHFFFAOYSA-N 0.000 description 1
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229920006244 ethylene-ethyl acrylate Polymers 0.000 description 1
- 229920005680 ethylene-methyl methacrylate copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010097 foam moulding Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002237 fumaric acid derivatives Chemical class 0.000 description 1
- NKHAVTQWNUWKEO-UHFFFAOYSA-N fumaric acid monomethyl ester Natural products COC(=O)C=CC(O)=O NKHAVTQWNUWKEO-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002531 isophthalic acids Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- NKHAVTQWNUWKEO-IHWYPQMZSA-N methyl hydrogen fumarate Chemical compound COC(=O)\C=C/C(O)=O NKHAVTQWNUWKEO-IHWYPQMZSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- RZRNAYUHWVFMIP-UHFFFAOYSA-N monoelaidin Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC(O)CO RZRNAYUHWVFMIP-UHFFFAOYSA-N 0.000 description 1
- WIBFFTLQMKKBLZ-SEYXRHQNSA-N n-butyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCCC WIBFFTLQMKKBLZ-SEYXRHQNSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- QTDSLDJPJJBBLE-PFONDFGASA-N octyl (z)-octadec-9-enoate Chemical compound CCCCCCCCOC(=O)CCCCCCC\C=C/CCCCCCCC QTDSLDJPJJBBLE-PFONDFGASA-N 0.000 description 1
- 150000002888 oleic acid derivatives Chemical class 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- ZZSIDSMUTXFKNS-UHFFFAOYSA-N perylene red Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N(C(=O)C=1C2=C3C4=C(OC=5C=CC=CC=5)C=1)C(=O)C2=CC(OC=1C=CC=CC=1)=C3C(C(OC=1C=CC=CC=1)=CC1=C2C(C(N(C=3C(=CC=CC=3C(C)C)C(C)C)C1=O)=O)=C1)=C2C4=C1OC1=CC=CC=C1 ZZSIDSMUTXFKNS-UHFFFAOYSA-N 0.000 description 1
- ODFKDYBAQKFTOU-KTKRTIGZSA-N phenyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC1=CC=CC=C1 ODFKDYBAQKFTOU-KTKRTIGZSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003021 phthalic acid derivatives Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920006350 polyacrylonitrile resin Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920005903 polyol mixture Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- QYUMESOEHIJKHV-UHFFFAOYSA-M prop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].NC(=O)C=C.CCC[N+](C)(C)C QYUMESOEHIJKHV-UHFFFAOYSA-M 0.000 description 1
- BPJZKLBPJBMLQG-KWRJMZDGSA-N propanoyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OC(=O)CC BPJZKLBPJBMLQG-KWRJMZDGSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001054 red pigment Substances 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical class CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 150000003329 sebacic acid derivatives Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FRKHZXHEZFADLA-UHFFFAOYSA-L strontium;octadecanoate Chemical compound [Sr+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O FRKHZXHEZFADLA-UHFFFAOYSA-L 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- PZTAGFCBNDBBFZ-UHFFFAOYSA-N tert-butyl 2-(hydroxymethyl)piperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCCCC1CO PZTAGFCBNDBBFZ-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- 239000001069 triethyl citrate Substances 0.000 description 1
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 description 1
- 235000013769 triethyl citrate Nutrition 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- HQUQLFOMPYWACS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl HQUQLFOMPYWACS-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 239000001052 yellow pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GAWWVVGZMLGEIW-GNNYBVKZSA-L zinc ricinoleate Chemical compound [Zn+2].CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O.CCCCCC[C@@H](O)C\C=C/CCCCCCCC([O-])=O GAWWVVGZMLGEIW-GNNYBVKZSA-L 0.000 description 1
- 229940100530 zinc ricinoleate Drugs 0.000 description 1
- IFNXAMCERSVZCV-UHFFFAOYSA-L zinc;2-ethylhexanoate Chemical compound [Zn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O IFNXAMCERSVZCV-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/18—Slush casting, i.e. pouring moulding material into a hollow mould with excess material being poured off
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60K—ARRANGEMENT OR MOUNTING OF PROPULSION UNITS OR OF TRANSMISSIONS IN VEHICLES; ARRANGEMENT OR MOUNTING OF PLURAL DIVERSE PRIME-MOVERS IN VEHICLES; AUXILIARY DRIVES FOR VEHICLES; INSTRUMENTATION OR DASHBOARDS FOR VEHICLES; ARRANGEMENTS IN CONNECTION WITH COOLING, AIR INTAKE, GAS EXHAUST OR FUEL SUPPLY OF PROPULSION UNITS IN VEHICLES
- B60K37/00—Dashboards
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Combustion & Propulsion (AREA)
- Transportation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Moulding By Coating Moulds (AREA)
- Vehicle Interior And Exterior Ornaments, Soundproofing, And Insulation (AREA)
- Instrument Panels (AREA)
Abstract
本発明は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物を提供することを目的とする。本発明の塩化ビニル樹脂組成物は、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である。An object of this invention is to provide the vinyl chloride resin composition which gives the powder molded object with high adhesiveness to a foaming polyurethane molded object. The vinyl chloride resin composition of the present invention includes (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less. At least one of the ether polyols.
Description
本発明は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体、上記塩化ビニル樹脂成形体と発泡ポリウレタン成形体とを有する積層体、上記塩化ビニル樹脂組成物の製造方法、及び上記塩化ビニル樹脂成形体の製造方法に関する。 The present invention relates to a vinyl chloride resin composition that gives a powder molded article having high adhesion to a foamed polyurethane molded article, a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and the vinyl chloride resin molded article. The present invention relates to a laminate having a body and a polyurethane foam molded body, a method for producing the vinyl chloride resin composition, and a method for producing the vinyl chloride resin molded body.
自動車インスツルメントパネルは、発泡ポリウレタン層が、樹脂からなる表皮と基材との間に設けられた構造を有している。ここで樹脂からなる表皮は、主として塩化ビニル樹脂組成物が粉体成形されて製造される。しかし、塩化ビニル樹脂組成物の粉体成形体よりなる表皮と発泡ポリウレタン層との接着性は低く、これら2つは剥離しやすかった。
そこで、発泡ポリウレタン層への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物を得るため、塩化ビニル樹脂、可塑剤、過塩素酸処理ハイドロタルサイト、及びホワイトカーボンを含有する粉体成形用塩化ビニル樹脂組成物が検討された(例えば、特許文献1参照)。
更に、粒状塩化ビニル系樹脂、微粒塩化ビニル系樹脂、糖質類、可塑剤、安定剤、及び顔料等を含む粉体成形用塩化ビニル系樹脂組成物が検討された(例えば、特許文献2参照)。The automobile instrument panel has a structure in which a polyurethane foam layer is provided between a skin made of resin and a base material. Here, the skin made of resin is produced mainly by powder molding a vinyl chloride resin composition. However, the adhesiveness between the skin made of the powder molded body of the vinyl chloride resin composition and the polyurethane foam layer was low, and these two were easy to peel off.
Therefore, in order to obtain a vinyl chloride resin composition that gives a powder molded body having high adhesion to the foamed polyurethane layer, powder molding containing vinyl chloride resin, plasticizer, perchloric acid-treated hydrotalcite, and white carbon A vinyl chloride resin composition for use has been studied (for example, see Patent Document 1).
Furthermore, a vinyl chloride resin composition for powder molding containing a granular vinyl chloride resin, a fine vinyl chloride resin, a saccharide, a plasticizer, a stabilizer, a pigment, and the like has been studied (for example, see Patent Document 2). ).
近年、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える、従来の塩化ビニル樹脂組成物とは異なる組成の塩化ビニル樹脂組成物が要求されていた。しかし、そのような塩化ビニル樹脂組成物は得られていなかった。
そこで、本発明が解決しようとする課題は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える塩化ビニル樹脂組成物の提供である。また、本発明が解決しようとする別の課題は、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体、及び、上記塩化ビニル樹脂成形体と発泡ポリウレタン成形体を有する積層体の提供である。更に、本発明が解決しようとする別の課題は、上記塩化ビニル樹脂組成物の製造方法、及び、上記塩化ビニル樹脂成形体の製造方法の提供である。In recent years, there has been a demand for a vinyl chloride resin composition having a composition different from that of a conventional vinyl chloride resin composition, which gives a powder molded article having high adhesion to a foamed polyurethane molded article. However, such a vinyl chloride resin composition has not been obtained.
Accordingly, the problem to be solved by the present invention is to provide a vinyl chloride resin composition that provides a powder molded body having high adhesion to a foamed polyurethane molded body. Another problem to be solved by the present invention is a vinyl chloride resin molded article obtained by powder molding the vinyl chloride resin composition, and a laminate having the vinyl chloride resin molded article and a foamed polyurethane molded article. Is an offer. Furthermore, another subject which this invention tends to solve is provision of the manufacturing method of the said vinyl chloride resin composition, and the manufacturing method of the said vinyl chloride resin molded object.
本発明の発明者は、上記課題を解決するために鋭意検討した結果、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)特定範囲の分子量のポリオール系化合物を含む塩化ビニル樹脂組成物が、発泡ポリウレタン成形体への接着性が高い粉体成形体を与えることを見出し、本発明を完成させるに至った。 The inventor of the present invention has intensively studied to solve the above problems, and as a result, a vinyl chloride resin composition comprising (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight within a specific range. The product has been found to give a powder molded product having high adhesion to the foamed polyurethane molded product, and the present invention has been completed.
本発明は、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、塩化ビニル樹脂組成物である。 The present invention includes (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 to 4000, and the polyol compound is at least one of a polyester polyol and a polyether polyol. It is a certain vinyl chloride resin composition.
ここで、本発明の塩化ビニル樹脂組成物において、前記(b)可塑剤の好ましい配合量は、前記(a)塩化ビニル樹脂100質量部に対し30質量部以上190質量部以下である。 Here, in the vinyl chloride resin composition of the present invention, a preferable blending amount of the (b) plasticizer is 30 parts by mass or more and 190 parts by mass or less with respect to 100 parts by mass of the (a) vinyl chloride resin.
そして、本発明の塩化ビニル樹脂組成物において、前記(c)分子量が900以上4000以下のポリオール系化合物の好ましい配合量は、上記(a)塩化ビニル樹脂100質量部に対し0.1質量部以上30質量部以下である。 And in the vinyl chloride resin composition of the present invention, the preferred compounding amount of the (c) polyol compound having a molecular weight of 900 or more and 4000 or less is 0.1 parts by mass or more with respect to 100 parts by mass of the (a) vinyl chloride resin. 30 parts by mass or less.
更に、本発明の塩化ビニル樹脂組成物は、70質量%以上100質量%以下の(a1)塩化ビニル樹脂粒子、及び0質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが好ましい。なお、本発明において、「樹脂粒子」とは、粒子径が30μm以上の粒子を指し、「樹脂微粒子」とは、粒子径が30μm未満の粒子を指す。 Furthermore, the vinyl chloride resin composition of the present invention comprises only 70% by mass to 100% by mass of (a1) vinyl chloride resin particles and 0% by mass to 30% by mass of (a2) vinyl chloride resin fine particles. Is preferred. In the present invention, “resin particles” refers to particles having a particle size of 30 μm or more, and “resin particles” refers to particles having a particle size of less than 30 μm.
加えて、本発明の塩化ビニル樹脂組成物において、上記(a1)塩化ビニル樹脂粒子の好ましい平均粒子径は50μm以上500μm以下であり、上記(a2)塩化ビニル樹脂微粒子の好ましい平均粒子径は0.1μm以上10μm以下である。 In addition, in the vinyl chloride resin composition of the present invention, a preferable average particle size of the (a1) vinyl chloride resin particles is 50 μm or more and 500 μm or less, and a preferable average particle size of the (a2) vinyl chloride resin fine particles is 0.00. 1 μm or more and 10 μm or less.
そして、本発明の塩化ビニル樹脂組成物の好ましい用途は粉体成形であり、更に好ましい用途はパウダースラッシュ成形である。 A preferred use of the vinyl chloride resin composition of the present invention is powder molding, and a more preferred use is powder slush molding.
また、本発明は、前記いずれかの塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体である。 Moreover, this invention is a vinyl chloride resin molded object formed by powder-molding one of the said vinyl chloride resin compositions.
ここで、本発明の塩化ビニル樹脂成形体は、好ましくは前記いずれかの塩化ビニル樹脂組成物をパウダースラッシュ成形してなる。 Here, the vinyl chloride resin molded article of the present invention is preferably formed by powder slush molding of any of the vinyl chloride resin compositions described above.
そして、本発明の塩化ビニル樹脂成形体は、好ましくは自動車インスツルメントパネル表皮用である。 The vinyl chloride resin molded article of the present invention is preferably for an automotive instrument panel skin.
また、本発明は、発泡ポリウレタン成形体と、前記いずれかの塩化ビニル樹脂成形体とを有する積層体である。 Moreover, this invention is a laminated body which has a foaming polyurethane molding and one of the said vinyl chloride resin moldings.
ここで、本発明の積層体は、好ましくは自動車インスツルメントパネル用である。 Here, the laminate of the present invention is preferably for an automotive instrument panel.
また、本発明は、(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物を混合することを含み、前記ポリオール系化合物が、ポリエステルポリオールおよびポリエーテルポリオールの少なくとも一方である、前記いずれかの塩化ビニル樹脂組成物の製造方法である。 The present invention also includes mixing (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less. The method for producing any one of the vinyl chloride resin compositions, which is at least one of ether polyols.
また、本発明は、前記いずれかの塩化ビニル樹脂組成物、または、前記製造方法に従って製造した塩化ビニル樹脂組成物を粉体成形することを特徴とする、塩化ビニル樹脂成形体の製造方法である。 In addition, the present invention is a method for producing a vinyl chloride resin molded article, which comprises powder molding any one of the vinyl chloride resin compositions or the vinyl chloride resin composition produced according to the production method. .
本発明の塩化ビニル樹脂組成物は、発泡ポリウレタン成形体への接着性が高い粉体成形体を与える。 The vinyl chloride resin composition of the present invention provides a powder molded body having high adhesion to a foamed polyurethane molded body.
(塩化ビニル樹脂組成物)
本発明の塩化ビニル樹脂組成物は(a)塩化ビニル樹脂と、(b)可塑剤と、(c)分子量が900以上4000以下のポリオール系化合物とを含み、任意に添加剤を更に含有する。(Vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention contains (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less, and optionally further contains an additive.
<(a)塩化ビニル樹脂>
ここで本発明において、(a)塩化ビニル樹脂としては、樹脂粒子である(a1)塩化ビニル樹脂粒子と、樹脂微粒子である(a2)塩化ビニル樹脂微粒子とが挙げられる。
(a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂は、塩化ビニルの単独重合体の他、塩化ビニル単位を好ましくは50質量%以上、より好ましくは70質量%以上含有する共重合体を含む。塩化ビニル共重合体の共単量体の具体例は、エチレン、プロピレンなどのオレフィン類;塩化アリル、塩化ビニリデン、フッ化ビニル、三フッ化塩化エチレンなどのハロゲン化オレフィン類;酢酸ビニル、プロピオン酸ビニルなどのカルボン酸ビニルエステル類;イソブチルビニルエーテル、セチルビニルエーテルなどのビニルエーテル類;アリル−3−クロロ−2−オキシプロピルエーテル、アリルグリシジルエーテルなどのアリルエーテル類;アクリル酸、マレイン酸、イタコン酸、アクリル酸−2−ヒドロキシエチル、メタクリル酸メチル、マレイン酸モノメチル、マレイン酸ジエチル、無水マレイン酸などの不飽和カルボン酸、そのエステルまたはその酸無水物類;アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル類;アクリルアミド、N−メチロールアクリルアミド、アクリルアミド−2−メチルプロパンスルホン酸、(メタ)アクリルアミドプロピルトリメチルアンモニウムクロライドなどのアクリルアミド類;アリルアミン安息香酸塩、ジアリルジメチルアンモニウムクロライドなどのアリルアミンおよびその誘導体類;などである。以上に例示される単量体は、塩化ビニルと共重合可能な単量体(共単量体)の一部に過ぎず、共単量体としては、近畿化学協会ビニル部会編「ポリ塩化ビニル」日刊工業新聞社(1988年)第75〜104頁に例示されている各種単量体が使用され得る。これらの単量体の1種又は2種以上が使用され得る。上記(a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂には、エチレン−酢酸ビニル共重合体、エチレン−メタクリル酸メチル共重合体、エチレン−アクリル酸エチル共重合体、塩素化ポリエチレンなどの樹脂に、(1)塩化ビニルまたは(2)塩化ビニルと前記共単量体とがグラフト重合された樹脂も含まれる。
ここで、本明細書において、「(メタ)アクリル」とは、アクリル及び/又はメタクリルを意味する。<(A) Vinyl chloride resin>
In the present invention, examples of (a) vinyl chloride resin include (a1) vinyl chloride resin particles that are resin particles and (a2) vinyl chloride resin particles that are resin fine particles.
The vinyl chloride resin constituting the (a1) vinyl chloride resin particles and the (a2) vinyl chloride resin fine particles, in addition to the vinyl chloride homopolymer, preferably has a vinyl chloride unit of 50% by mass or more, more preferably 70% by mass or more. Contains the containing copolymer. Specific examples of comonomers of the vinyl chloride copolymer include olefins such as ethylene and propylene; halogenated olefins such as allyl chloride, vinylidene chloride, vinyl fluoride, and ethylene trifluoride; vinyl acetate and propionic acid. Carboxylic acid vinyl esters such as vinyl; vinyl ethers such as isobutyl vinyl ether and cetyl vinyl ether; allyl ethers such as allyl-3-chloro-2-oxypropyl ether and allyl glycidyl ether; acrylic acid, maleic acid, itaconic acid, acrylic 2-hydroxyethyl acid, methyl methacrylate, monomethyl maleate, diethyl maleate, maleic anhydride and other unsaturated carboxylic acids, their esters or acid anhydrides; acrylonitrile, methacrylonitrile and other unsaturated nitriles; Acrylamide, N- methylol acrylamide, acrylamido-2-methylpropanesulfonic acid, (meth) acrylamides such as acrylamide propyl trimethyl ammonium chloride; allyl amine benzoates, allylamine and its derivatives such as diallyl dimethyl ammonium chloride; and the like. The monomer exemplified above is only a part of the monomer (comonomer) copolymerizable with vinyl chloride. As the comonomer, “polyvinyl chloride” edited by Kinki Chemical Association Vinyl Division The various monomers illustrated in Nikkan Kogyo Shimbun (1988), pages 75-104 may be used. One or more of these monomers can be used. The vinyl chloride resin constituting the above (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles include ethylene-vinyl acetate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl acrylate copolymer. Also included are resins obtained by graft polymerization of (1) vinyl chloride or (2) vinyl chloride and the above-mentioned comonomer to a resin such as chlorinated polyethylene.
Here, in this specification, “(meth) acryl” means acryl and / or methacryl.
上記(a1)塩化ビニル樹脂粒子および(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂は、懸濁重合法、乳化重合法、溶液重合法、塊状重合法など、従来から知られているいずれの製造法によっても製造され得る。 The vinyl chloride resin constituting the above (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles may be any of conventionally known methods such as suspension polymerization, emulsion polymerization, solution polymerization, and bulk polymerization. It can also be manufactured by a manufacturing method.
なお、塩化ビニル樹脂組成物において、(a1)塩化ビニル樹脂粒子は、マトリックス樹脂として機能する。また、(a2)塩化ビニル樹脂微粒子は、マトリックス樹脂として機能しつつ、後述するダスティング剤(粉体流動性改良剤)として機能する。 In the vinyl chloride resin composition, (a1) vinyl chloride resin particles function as a matrix resin. Moreover, (a2) vinyl chloride resin fine particles function as a dusting agent (powder fluidity improver) described later while functioning as a matrix resin.
[(a1)塩化ビニル樹脂粒子]
ここで、(a1)塩化ビニル樹脂粒子の平均粒子径は、好ましくは50μm以上500μm以下、より好ましくは50μm以上250μm以下、更に好ましくは100μm以上200μm以下である。(a1)塩化ビニル樹脂粒子の平均粒子径が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。
なお、「平均粒子径」は、JIS Z8825に準拠し、例えばレーザー回折法により測定される体積平均粒子径を指す。[(A1) Vinyl chloride resin particles]
Here, the average particle diameter of the (a1) vinyl chloride resin particles is preferably 50 μm to 500 μm, more preferably 50 μm to 250 μm, and still more preferably 100 μm to 200 μm. (A1) When the average particle diameter of the vinyl chloride resin particles is within the above range, the powder flowability of the vinyl chloride resin composition is good and the vinyl chloride resin composition is obtained by powder molding the vinyl chloride resin composition. Adhesiveness of the resin molded body to the foamed polyurethane molded body is improved.
The “average particle diameter” refers to the volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
上記(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度は、好ましくは800以上5000以下であり、より好ましくは800以上3000以下である。上記(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂の平均重合度が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。
なお、「平均重合度」は、JIS K 6720−2に準拠して測定される。The average degree of polymerization of the vinyl chloride resin constituting the (a1) vinyl chloride resin particles is preferably 800 or more and 5000 or less, and more preferably 800 or more and 3000 or less. When the average degree of polymerization of the vinyl chloride resin constituting the (a1) vinyl chloride resin particles is in the above range, the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is converted into a foamed polyurethane molded product. High adhesion can be imparted.
The “average degree of polymerization” is measured according to JIS K 6720-2.
また、(a1)塩化ビニル樹脂粒子を構成する塩化ビニル樹脂としては、懸濁重合法により製造された塩化ビニル樹脂を用いることが好ましい。 Moreover, it is preferable to use the vinyl chloride resin manufactured by the suspension polymerization method as (a1) vinyl chloride resin which comprises a vinyl chloride resin particle.
[(a2)塩化ビニル樹脂微粒子]
本発明の塩化ビニル樹脂組成物は、上記(a)塩化ビニル樹脂として、(a2)塩化ビニル樹脂微粒子を使用することもできる。上記(a2)塩化ビニル樹脂微粒子は、マトリックス樹脂として機能しつつ、塩化ビニル樹脂組成物の粉体流動性を向上させるダスティング剤として機能する。[(A2) Vinyl chloride resin fine particles]
In the vinyl chloride resin composition of the present invention, (a2) vinyl chloride resin fine particles can also be used as the (a) vinyl chloride resin. The (a2) vinyl chloride resin fine particles function as a dusting agent that improves the powder fluidity of the vinyl chloride resin composition while functioning as a matrix resin.
ここで、上記(a2)塩化ビニル樹脂微粒子の好ましい平均粒子径は0.1μm以上10μm以下である。(a2)塩化ビニル樹脂微粒子の平均粒子径が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が向上するからである。
なお、「平均粒子径」は、JIS Z8825に準拠し、例えば、レーザー回折法により測定される体積平均粒子径を指す。Here, the preferable average particle diameter of the (a2) vinyl chloride resin fine particles is 0.1 μm or more and 10 μm or less. (A2) It is because the powder fluidity | liquidity of a vinyl chloride resin composition will improve that the average particle diameter of vinyl chloride resin fine particle is the said range.
The “average particle diameter” refers to a volume average particle diameter measured by, for example, a laser diffraction method in accordance with JIS Z8825.
上記(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の好ましい平均重合度は、好ましくは500以上5000以下であり、より好ましくは600以上3000以下であり、更に好ましくは700以上2500以下である。上記(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂の平均重合度が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。 The average polymerization degree of the vinyl chloride resin constituting the (a2) vinyl chloride resin fine particles is preferably 500 or more and 5000 or less, more preferably 600 or more and 3000 or less, and further preferably 700 or more and 2500 or less. (A2) If the average degree of polymerization of the vinyl chloride resin constituting the vinyl chloride resin fine particles is in the above range, the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is powdered. The adhesion of the molded body of the vinyl chloride resin to the foamed polyurethane molded body is improved.
また、(a2)塩化ビニル樹脂微粒子を構成する塩化ビニル樹脂としては、乳化重合法により製造された塩化ビニル樹脂を用いることが好ましい。 Moreover, it is preferable to use the vinyl chloride resin manufactured by the emulsion polymerization method as (a2) vinyl chloride resin which comprises vinyl chloride resin fine particles.
[(a)塩化ビニル樹脂中における(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の配合割合]
ここで(a)塩化ビニル樹脂は、好適には、少なくとも(a1)塩化ビニル樹脂粒子を含み、任意に、(a2)塩化ビニル樹脂微粒子を含む。例えば、(a)塩化ビニル樹脂100質量%が、70質量%以上100質量%以下の(a1)塩化ビニル樹脂粒子、及び0質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが好ましい。このような組成の(a)塩化ビニル樹脂を使用すれば、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。
そして(a)塩化ビニル樹脂100質量%は、70質量%以上99質量%以下の(a1)塩化ビニル樹脂粒子、及び1質量%以上30質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることがより好ましく、75質量%以上95質量%以下の(a1)塩化ビニル樹脂粒子、及び5質量%以上25質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが更に好ましく、80質量%以上92質量%以下の(a1)塩化ビニル樹脂粒子、及び8質量%以上20質量%以下の(a2)塩化ビニル樹脂微粒子のみからなることが特に好ましい。上記(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の配合割合が上記範囲であると、塩化ビニル樹脂組成物の粉体流動性が良好であり、かつ、上記塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の、発泡ポリウレタン成形体への接着性が向上する。[(A) Mixing ratio of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles in vinyl chloride resin]
Here, the (a) vinyl chloride resin preferably contains at least (a1) vinyl chloride resin particles, and optionally (a2) vinyl chloride resin fine particles. For example, (a) 100% by mass of the vinyl chloride resin consists only of (a1) vinyl chloride resin particles of 70% by mass to 100% by mass and (a2) vinyl chloride resin fine particles of 0% by mass to 30% by mass. It is preferable. If (a) vinyl chloride resin of such a composition is used, the adhesiveness to the foaming polyurethane molding of the vinyl chloride resin molding formed by carrying out powder molding of the vinyl chloride resin composition will improve.
And (a) 100% by mass of the vinyl chloride resin consists only of 70% to 99% by mass of (a1) vinyl chloride resin particles and 1% to 30% by mass of (a2) vinyl chloride resin fine particles. More preferably, it is composed of only 75% by mass to 95% by mass of (a1) vinyl chloride resin particles and 5% by mass to 25% by mass of (a2) vinyl chloride resin fine particles, and more preferably 80% by mass or more. It is particularly preferable that the composition consists of 92% by mass or less of (a1) vinyl chloride resin particles and 8% by mass or more and 20% by mass or less of (a2) vinyl chloride resin fine particles. When the blending ratio of the (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles is within the above range, the powder flowability of the vinyl chloride resin composition is good, and the vinyl chloride resin composition is The adhesiveness of the vinyl chloride resin molded article formed by powder molding to the foamed polyurethane molded article is improved.
<可塑剤>
本発明の塩化ビニル樹脂組成物が含有する(b)可塑剤は、好ましくは、トリメリット酸エステル可塑剤である。トリメリット酸エステル可塑剤は、トリメリット酸と一価アルコールとのエステル化合物である。<Plasticizer>
The plasticizer (b) contained in the vinyl chloride resin composition of the present invention is preferably a trimellitic acid ester plasticizer. The trimellitic acid ester plasticizer is an ester compound of trimellitic acid and a monohydric alcohol.
上記一価アルコールの具体例としては、特に限定されることなく、1−ヘキサノール、1−ヘプタノール、1−オクタノール、2−エチルヘキサノール、1−ノナノール、1−デカノール、1−ウンデカノール、1−ドデカノール等が挙げられる。 Specific examples of the monohydric alcohol are not particularly limited, and include 1-hexanol, 1-heptanol, 1-octanol, 2-ethylhexanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, and the like. Is mentioned.
中でも、(b)可塑剤として好ましいトリメリット酸エステル可塑剤は、上述した一価アルコールによりトリメリット酸のカルボキシ基を実質的に全てエステル化したトリエステル化物である。トリエステル化物におけるアルコール残基部分は、同一のアルコール由来であってもよく、それぞれ異なるアルコール由来のものであってもよい。
上記トリメリット酸エステル可塑剤は、単一の化合物からなるものであってもよいし、異なる化合物の混合物であってもよい。Among them, the trimellitic acid ester plasticizer that is preferable as the plasticizer (b) is a triesterized product obtained by esterifying substantially all the carboxy groups of trimellitic acid with the above-described monohydric alcohol. The alcohol residue part in the triesterized product may be derived from the same alcohol or may be derived from different alcohols.
The trimellitic acid ester plasticizer may be composed of a single compound or a mixture of different compounds.
好適なトリメリット酸エステル可塑剤の具体例は、トリメリット酸トリ−n−ヘキシル、トリメリット酸トリ−n−ヘプチル、トリメリット酸トリ−n−オクチル、トリメリット酸トリ−(2−エチルヘキシル)、トリメリット酸トリ−n−ノニル、トリメリット酸トリ−n−デシル、トリメリット酸トリイソデシル、トリメリット酸トリ−n−ウンデシル、トリメリット酸トリ−n−ドデシル、トリメリット酸トリ−n−アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6〜12である。〕を分子内に2種以上有するエステル)、トリメリット酸トリアルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は8〜10である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。
より好ましいトリメリット酸エステル可塑剤の具体例は、トリメリット酸トリ−n−オクチル、トリメリット酸トリ−(2−エチルヘキシル)、トリメリット酸トリ−n−ノニル、トリメリット酸トリ−n−デシル、トリメリット酸トリ−n−アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は8〜10である。〕を分子内に2種以上有するエステル)、及びこれらの混合物等である。Specific examples of suitable trimellitic acid ester plasticizers are trimellitic acid tri-n-hexyl, trimellitic acid tri-n-heptyl, trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl) , Trimellitic acid tri-n-nonyl, trimellitic acid tri-n-decyl, trimellitic acid triisodecyl, trimellitic acid tri-n-undecyl, trimellitic acid tri-n-dodecyl, trimellitic acid tri-n-alkyl Esters (esters having two or more alkyl groups having different carbon numbers [provided that the number of carbon atoms is 6 to 12]), trimellitic acid trialkyl esters (alkyl groups having different carbon numbers [however, carbon number Is an ester having 2 or more types in the molecule), and mixtures thereof.
Specific examples of more preferable trimellitic acid ester plasticizers are trimellitic acid tri-n-octyl, trimellitic acid tri- (2-ethylhexyl), trimellitic acid tri-n-nonyl, trimellitic acid tri-n-decyl , Trimellitic acid tri-n-alkyl esters (esters having two or more types of alkyl groups having different carbon numbers [wherein the number of carbon atoms is 8 to 10]), and mixtures thereof.
本発明の塩化ビニル樹脂組成物が含有する(b)可塑剤として用い得るトリメリット酸エステル可塑剤以外の可塑剤としては、例えば、以下の一次可塑剤及び二次可塑剤などが挙げられる。 Examples of the plasticizer other than the trimellitic acid ester plasticizer that can be used as the plasticizer (b) contained in the vinyl chloride resin composition of the present invention include the following primary plasticizers and secondary plasticizers.
いわゆる一次可塑剤としては、
ピロメリット酸テトラ−n−ヘキシル、ピロメリット酸テトラ−n−ヘプチル、ピロメリット酸テトラ−n−オクチル、ピロメリット酸テトラ−(2−エチルヘキシル)、ピロメリット酸テトラ−n−ノニル、ピロメリット酸テトラ−n−デシル、ピロメリット酸テトライソデシル、ピロメリット酸テトラ−n−ウンデシル、ピロメリット酸テトラ−n−ドデシル、ピロメリット酸テトラ−n−アルキルエステル(炭素数が異なるアルキル基〔但し、炭素数は6〜12である。〕を分子内に2種以上有するエステル)等のピロメリット酸エステル可塑剤;
ジメチルフタレート、ジエチルフタレート、ジブチルフタレート、ジ−(2−エチルヘキシル)フタレート、ジ−n−オクチルフタレート、ジイソブチルフタレート、ジヘプチルフタレート、ジフェニルフタレート、ジイソデシルフタレート、ジトリデシルフタレート、ジウンデシルフタレート、ジベンジルフタレート、ブチルベンジルフタレート、ジノニルフタレート、ジシクロヘキシルフタレート等のフタル酸誘導体;
ジメチルイソフタレート、ジ−(2−エチルヘキシル)イソフタレート、ジイソオクチルイソフタレート等のイソフタル酸誘導体;
ジ−(2−エチルヘキシル)テトラヒドロフタレート、ジ−n−オクチルテトラヒドロフタレート、ジイソデシルテトラヒドロフタレート等のテトラヒドロフタル酸誘導体;
ジ−n−ブチルアジペート、ジ(2−エチルヘキシル)アジペート、ジイソデシルアジペート、ジイソノニルアジペート等のアジピン酸誘導体;
ジ−(2−エチルヘキシル)アゼレート、ジイソオクチルアゼレート、ジ−n−ヘキシルアゼレート等のアゼライン酸誘導体;
ジ−n−ブチルセバケート、ジ−(2−エチルヘキシル)セバケート、ジイソデシルセバケート、ジ−(2−ブチルオクチル)セバケート等のセバシン酸誘導体;
ジ−n−ブチルマレエート、ジメチルマレエート、ジエチルマレエート、ジ−(2−エチルヘキシル)マレエート等のマレイン酸誘導体;
ジ−n−ブチルフマレート、ジ−(2−エチルヘキシル)フマレート等のフマル酸誘導体;
トリエチルシトレート、トリ−n−ブチルシトレート、アセチルトリエチルシトレート、アセチルトリ−(2−エチルヘキシル)シトレート等のクエン酸誘導体;
モノメチルイタコネート、モノブチルイタコネート、ジメチルイタコネート、ジエチルイタコネート、ジブチルイタコネート、ジ−(2−エチルヘキシル)イタコネート等のイタコン酸誘導体;
ブチルオレエート、グリセリルモノオレエート、ジエチレングリコールモノオレエート等のオレイン酸誘導体;
メチルアセチルリシノレート、ブチルアセチルリシノレート、グリセリルモノリシノレート、ジエチレングリコールモノリシノレート等のリシノール酸誘導体;
n−ブチルステアレート、ジエチレングリコールジステアレート等のステアリン酸誘導体;
ジエチレングリコールモノラウレート、ジエチレングリコールジペラルゴネート、ペンタエリスリトール脂肪酸エステル等のその他の脂肪酸誘導体;
トリエチルホスフェート、トリブチルホスフェート、トリ−(2−エチルヘキシル)ホスフェート、トリブトキシエチルホスフェート、トリフェニルホスフェート、クレジルジフェニルホスフェート、トリクレジルホスフェート、トリキシレニルホスフェート、トリス(クロロエチル)ホスフェート等のリン酸誘導体;
ジエチレングリコールジベンゾエート、ジプロピレングリコールジベンゾエート、トリエチレングリコールジベンゾエート、トリエチレングリコールジ−(2−エチルブチレート)、トリエチレングリコールジ−(2−エチルヘキソエート)、ジブチルメチレンビスチオグリコレート等のグリコール誘導体;
グリセロールモノアセテート、グリセロールトリアセテート、グリセロールトリブチレート等のグリセリン誘導体;
エポキシヘキサヒドロフタル酸ジイソデシル、エポキシトリグリセライド、エポキシ化オレイン酸オクチル、エポキシ化オレイン酸デシル等のエポキシ誘導体;
アジピン酸系ポリエステル、セバシン酸系ポリエステル、フタル酸系ポリエステル等のポリエステル系可塑剤
等が挙げられる。As so-called primary plasticizers,
Pyromellitic acid tetra-n-hexyl, pyromellitic acid tetra-n-heptyl, pyromellitic acid tetra-n-octyl, pyromellitic acid tetra- (2-ethylhexyl), pyromellitic acid tetra-n-nonyl, pyromellitic acid Tetra-n-decyl, pyromellitic acid tetraisodecyl, pyromellitic acid tetra-n-undecyl, pyromellitic acid tetra-n-dodecyl, pyromellitic acid tetra-n-alkyl ester (an alkyl group having a different carbon number [however, Pyromellitic ester plasticizer such as ester having 2 or more carbon atoms in the molecule].
Dimethyl phthalate, diethyl phthalate, dibutyl phthalate, di- (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisobutyl phthalate, diheptyl phthalate, diphenyl phthalate, diisodecyl phthalate, ditridecyl phthalate, diundecyl phthalate, dibenzyl phthalate, Phthalic acid derivatives such as butylbenzyl phthalate, dinonyl phthalate, dicyclohexyl phthalate;
Isophthalic acid derivatives such as dimethyl isophthalate, di- (2-ethylhexyl) isophthalate, diisooctyl isophthalate;
Tetrahydrophthalic acid derivatives such as di- (2-ethylhexyl) tetrahydrophthalate, di-n-octyltetrahydrophthalate, diisodecyltetrahydrophthalate;
Adipic acid derivatives such as di-n-butyl adipate, di (2-ethylhexyl) adipate, diisodecyl adipate, diisononyl adipate;
Azelaic acid derivatives such as di- (2-ethylhexyl) azelate, diisooctylazelate, di-n-hexylazelate;
Sebacic acid derivatives such as di-n-butyl sebacate, di- (2-ethylhexyl) sebacate, diisodecyl sebacate, di- (2-butyloctyl) sebacate;
Maleic acid derivatives such as di-n-butyl maleate, dimethyl maleate, diethyl maleate, di- (2-ethylhexyl) maleate;
Fumaric acid derivatives such as di-n-butyl fumarate and di- (2-ethylhexyl) fumarate;
Citric acid derivatives such as triethyl citrate, tri-n-butyl citrate, acetyl triethyl citrate, acetyl tri- (2-ethylhexyl) citrate;
Itaconic acid derivatives such as monomethyl itaconate, monobutyl itaconate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, di- (2-ethylhexyl) itaconate;
Oleic acid derivatives such as butyl oleate, glyceryl monooleate, diethylene glycol monooleate;
Ricinoleic acid derivatives such as methylacetylricinoleate, butylacetylricinoleate, glycerylmonoricinoleate, diethylene glycol monoricinoleate;
stearic acid derivatives such as n-butyl stearate and diethylene glycol distearate;
Other fatty acid derivatives such as diethylene glycol monolaurate, diethylene glycol dipelargonate, pentaerythritol fatty acid ester;
Phosphoric acid derivatives such as triethyl phosphate, tributyl phosphate, tri- (2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris (chloroethyl) phosphate;
Diethylene glycol dibenzoate, dipropylene glycol dibenzoate, triethylene glycol dibenzoate, triethylene glycol di- (2-ethylbutyrate), triethylene glycol di- (2-ethylhexoate), dibutylmethylene bisthioglycolate, etc. A glycol derivative of
Glycerol derivatives such as glycerol monoacetate, glycerol triacetate, glycerol tributyrate;
Epoxy derivatives such as epoxyhexahydrophthalate diisodecyl, epoxy triglyceride, epoxidized octyl oleate, epoxidized decyl oleate;
Examples thereof include polyester plasticizers such as adipic acid-based polyester, sebacic acid-based polyester, and phthalic acid-based polyester.
また、いわゆる二次可塑剤としては、エポキシ化大豆油、エポキシ化亜麻仁油等のエポキシ化植物油;塩素化パラフィン、トリエチレングリコールジカプリレート等のグリコールの脂肪酸エステル、ブチルエポキシステアレート、フェニルオレエート、ジヒドロアビエチン酸メチル等が挙げられる。 In addition, so-called secondary plasticizers include epoxidized vegetable oils such as epoxidized soybean oil and epoxidized linseed oil; fatty acid esters of glycols such as chlorinated paraffin and triethylene glycol dicaprylate, butyl epoxy stearate, phenyl oleate And methyl dihydroabietic acid.
そして、上記トリメリット酸エステル可塑剤以外の可塑剤の中でも、エポキシ化植物油が好ましい。
なお、本発明の塩化ビニル樹脂組成物では、1種又は2種以上の、上記トリメリット酸エステル可塑剤以外の可塑剤を使用しうる。また、二次可塑剤を用いる場合、当該二次可塑剤と等質量以上の一次可塑剤を併用することが好ましい。Among the plasticizers other than the trimellitic acid ester plasticizer, epoxidized vegetable oil is preferable.
In the vinyl chloride resin composition of the present invention, one or more plasticizers other than the trimellitic acid ester plasticizer can be used. Moreover, when using a secondary plasticizer, it is preferable to use together the said secondary plasticizer and the primary plasticizer of equal mass or more.
そして、上記(b)可塑剤の合計含有量は、上記(a)塩化ビニル樹脂100質量部に対して、好ましくは30質量部以上190質量部以下であり、より好ましくは60質量部以上170質量部以下であり、更に好ましくは90質量部以上160質量部以下である。上記(b)可塑剤の含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 The total content of the (b) plasticizer is preferably 30 parts by weight or more and 190 parts by weight or less, and more preferably 60 parts by weight or more and 170 parts by weight, with respect to 100 parts by weight of the (a) vinyl chloride resin. Part or less, more preferably 90 parts by mass or more and 160 parts by mass or less. When the content of the plasticizer (b) is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
<(c)分子量が900以上4000以下のポリオール系化合物>
本発明の塩化ビニル樹脂組成物が含有する(c)分子量が900以上4000以下のポリオール系化合物は、分子量が900以上4000以下であれば特定のポリオール系化合物に限定されない。そして本発明においてポリオール系化合物としては、例えば、アルキレングリコール系ポリエステルポリオール、ポリカプロラクトン系ポリエステルポリオール等のポリエステルポリオール;ポリエーテルポリオ―ルが挙げられる。<(C) Polyol compound having a molecular weight of 900 to 4000>
The (c) polyol compound having a molecular weight of 900 or more and 4000 or less contained in the vinyl chloride resin composition of the present invention is not limited to a specific polyol compound if the molecular weight is 900 or more and 4000 or less. In the present invention, examples of the polyol compound include polyester polyols such as alkylene glycol polyester polyols and polycaprolactone polyester polyols; and polyether polyols.
[ポリエステルポリオール]
アルキレングリコール系ポリエステルポリオールとしては、アルキレングリコールと脂肪族二塩基酸との縮合体が挙げられる。そしてアルキレングリコール系ポリエステルポリオールは、例えば、アルキレングリコールと脂肪族二塩基としてのアジピン酸との縮合体であるポリエステルポリオールであり、エチレンアジペートエステルポリオール、ブチレンアジペートエステルポリオール、ヘキシレンアジペートエステルポリオール、エチレンプロピレンアジペートエステルポリオール、エチレンブチレンアジペートエステルポリオール、及びエチレンネオペンチレンアジペートエステルポリオール等が挙げられる。[Polyester polyol]
Examples of the alkylene glycol polyester polyol include condensates of alkylene glycol and aliphatic dibasic acid. The alkylene glycol-based polyester polyol is, for example, a polyester polyol that is a condensate of alkylene glycol and adipic acid as an aliphatic dibase, such as ethylene adipate ester polyol, butylene adipate ester polyol, hexylene adipate ester polyol, ethylene propylene. Examples include adipate ester polyol, ethylene butylene adipate ester polyol, and ethylene neopentylene adipate ester polyol.
ポリカプロラクトン系ポリエステルポリオールとしては、カプロラクトンを開環重合して得られるポリカプロラクトンをポリオールに結合して得られるポリエステルポリオールが挙げられる。そしてポリカプロラクトン系ポリエステルポリオールの具体例として、以下の式(1)、式(2)で示される化合物が挙げられる。 Examples of the polycaprolactone-based polyester polyol include polyester polyols obtained by bonding polycaprolactone obtained by ring-opening polymerization of caprolactone to the polyol. Specific examples of the polycaprolactone-based polyester polyol include compounds represented by the following formulas (1) and (2).
式(1)及び(2)中、a、b、cは、それぞれ独立して、好ましくは3以上8以下の整数であり、より好ましくは4以上7以下の整数であり、更に好ましくは5以上6以下の整数であり、特に好ましくは5である。l、m、nはそれぞれ独立して同一の又は異なる整数である。そして、l、m、nの各々の範囲は、式(1)、式(2)で示されるポリカプロラクトン系ポリエステルポリオールの分子量が900以上4000以下となる範囲であれば特に限定されない。なおl、m、nの各々の範囲は、好ましくは、当該分子量が900以上3000以下となる範囲であり、より好ましくは当該分子量が900以上2000以下となる範囲である。例えばl、m、nは、それぞれ独立して1以上80以下の整数である。Rはトリオール又はジオール由来の構造であり、特定の構造に限定されない。例えばRは、C、O、H、及びNからなる群から選択される2種以上の原子で構成される有機基である。
なお、式(1)及び(2)で示されるポリカプロラクトン系ポリエステルポリオールは市販されている。式(1)のポリカプロラクトン系ポリエステルポリオール(ポリエステルトリオール)の市販品としては、プラクセル(登録商標)312、プラクセル320(何れも(株)ダイセル製)が挙げられ、式(2)のポリカプロラクトン系ポリエステルポリオール(ポリエステルジオール)の市販品としては、プラクセル210((株)ダイセル製)が挙げられる。In the formulas (1) and (2), a, b, and c are each independently preferably an integer of 3 or more and 8 or less, more preferably an integer of 4 or more and 7 or less, and still more preferably 5 or more. It is an integer of 6 or less, particularly preferably 5. l, m, and n are each independently the same or different integers. The ranges of l, m, and n are not particularly limited as long as the molecular weight of the polycaprolactone-based polyester polyol represented by the formulas (1) and (2) is in the range of 900 to 4000. Each range of l, m, and n is preferably a range in which the molecular weight is 900 or more and 3000 or less, and more preferably a range in which the molecular weight is 900 or more and 2000 or less. For example, l, m, and n are each independently an integer of 1 to 80. R is a structure derived from triol or diol, and is not limited to a specific structure. For example, R is an organic group composed of two or more atoms selected from the group consisting of C, O, H, and N.
In addition, the polycaprolactone type | system | group polyester polyol shown by Formula (1) and (2) is marketed. Examples of commercially available products of the polycaprolactone-based polyester polyol (polyester triol) of the formula (1) include Plaxel (registered trademark) 312 and Plaxel 320 (both manufactured by Daicel Corporation), and the polycaprolactone type of the formula (2) As a commercially available product of polyester polyol (polyester diol), Plaxel 210 (manufactured by Daicel Corporation) can be mentioned.
[ポリエーテルポリオール]
ポリエーテルポリオールとしては、ポリ(オキシテトラメチレン)グリコール、ポリ(オキシプロピレン)グリコール等が挙げられる。[Polyether polyol]
Examples of the polyether polyol include poly (oxytetramethylene) glycol and poly (oxypropylene) glycol.
これらのポリオール系化合物は、1種単独で使用してもよく2種以上を併用してもよい。そして、これらの中でも、ポリオール系化合物としては、ポリエステルポリオールが好ましく、ポリカプロラクトン系ポリエステルポリオールがより好ましい。 These polyol compounds may be used alone or in combination of two or more. Among these, as the polyol-based compound, a polyester polyol is preferable, and a polycaprolactone-based polyester polyol is more preferable.
ここで、上記(c)ポリオール系化合物の分子量は900以上4000以下であり、好ましくは900以上3000以下であり、より好ましくは900以上2000以下である。上記(c)ポリオール系化合物の分子量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 Here, the molecular weight of the (c) polyol compound is 900 or more and 4000 or less, preferably 900 or more and 3000 or less, and more preferably 900 or more and 2000 or less. When the molecular weight of the (c) polyol compound is in the above range, high adhesion to the foamed polyurethane molded product can be imparted to the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition.
また上記(c)分子量が900以上4000以下のポリオール系化合物の含有量は、上記(a)塩化ビニル樹脂100質量部に対して好ましくは0.1質量部以上30質量部以下であり、より好ましくは0.1質量部以上20質量部以下であり、更に好ましくは0.2質量部以上10質量部以下である。上記(c)分子量が900以上4000以下のポリオール系化合物の含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、発泡ポリウレタン成形体への高い接着性を付与できる。 The content of the polyol compound (c) having a molecular weight of 900 or more and 4000 or less is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 100 parts by mass of the vinyl chloride resin (a). Is 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass. When the content of the polyol compound (c) having a molecular weight of 900 or more and 4000 or less is within the above range, a vinyl chloride resin molded product obtained by powder molding a vinyl chloride resin composition is highly suitable for a foamed polyurethane molded product. Adhesiveness can be imparted.
<添加剤>
[過塩素酸処理ハイドロタルサイト]
本発明の塩化ビニル樹脂組成物は、過塩素酸処理ハイドロタルサイトを含有していてもよい。過塩素酸処理ハイドロタルサイトは、例えば、ハイドロタルサイトを過塩素酸の希薄水溶液中に加えて撹拌し、その後必要に応じて、ろ過、脱水または乾燥することによって、ハイドロタルサイト中の炭酸アニオン(CO3 2−)の少なくとも一部を過塩素酸アニオン(ClO4 −)で置換して(炭酸アニオン1モルにつき過塩素酸アニオン2モルが置換する)、容易に製造することができる。上記ハイドロタルサイトと上記過塩素酸とのモル比は任意に設定できるが、一般には、ハイドロタルサイト1モルに対し、過塩素酸0.1〜2モルとする。<Additives>
[Perchloric acid-treated hydrotalcite]
The vinyl chloride resin composition of the present invention may contain perchloric acid-treated hydrotalcite. Perchloric acid-treated hydrotalcite, for example, by adding hydrotalcite to a dilute aqueous solution of perchloric acid, stirring, and then filtering, dehydrating or drying as necessary, thereby allowing carbonate anions in hydrotalcite It can be easily produced by substituting at least a part of (CO 3 2− ) with a perchlorate anion (ClO 4 − ) (2 mol of perchlorate anion per 1 mol of carbonate anion). Although the molar ratio of the hydrotalcite and the perchloric acid can be arbitrarily set, it is generally 0.1 to 2 mol of perchloric acid with respect to 1 mol of hydrotalcite.
未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率は、好ましくは50モル%以上、より好ましくは70モル%以上、更に好ましくは85モル%以上である。また、未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率は、好ましくは95モル%以下である。未処理(未置換)のハイドロタルサイト中の炭酸アニオンの過塩素酸アニオンへの置換率が上記の範囲内にあることにより、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、良好な低温での柔軟性を付与できる。 The substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 50 mol% or more, more preferably 70 mol% or more, still more preferably 85 mol% or more. Further, the substitution rate of the carbonate anion to the perchlorate anion in the untreated (unsubstituted) hydrotalcite is preferably 95 mol% or less. A vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition when the substitution rate of the carbonate anion in the untreated (unsubstituted) hydrotalcite is within the above range. In addition, good flexibility at low temperatures can be imparted.
ハイドロタルサイトは、一般式:[Mg1−xAlx(OH)2]x+[(CO3)x/2・mH2O]x−で表される不定比化合物で、プラスに荷電した基本層[Mg1−xAlx(OH)2]x+と、マイナスに荷電した中間層[(CO3)x/2・mH2O]x−とからなる層状の結晶構造を有する無機物質である。ここで、上記一般式中、xは0より大きく0.33以下の範囲の数である。天然のハイドロタルサイトは、Mg6Al2(OH)16CO3・4H2Oである。合成されたハイドロタルサイトとしては、Mg4.5Al2(OH)13CO3・3.5H2Oが市販されている。合成ハイドロタルサイトの合成方法は、例えば特公昭61−174270号公報に記載されている。Hydrotalcite is a non - stoichiometric compound represented by the general formula: [Mg 1-x Al x (OH) 2 ] x + [(CO 3 ) x / 2 · mH 2 O] x- It is an inorganic substance having a layered crystal structure composed of a layer [Mg 1-x Al x (OH) 2 ] x + and a negatively charged intermediate layer [(CO 3 ) x / 2 · mH 2 O] x− . Here, in the above general formula, x is a number in the range of greater than 0 and less than or equal to 0.33. The natural hydrotalcite is Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O. The synthetic hydrotalcite, Mg 4.5 Al 2 (OH) 13 CO 3 · 3.5H 2 O are commercially available. A method for synthesizing synthetic hydrotalcite is described in, for example, Japanese Patent Publication No. 61-174270.
過塩素酸処理ハイドロタルサイトの、上記(a)塩化ビニル樹脂100質量部に対する好ましい含有量は0.5質量部以上7質量部以下であり、より好ましい含有量は1質量部以上6質量部以下であり、更に好ましい含有量は1.5質量部以上5.5質量部以下である。過塩素酸処理ハイドロタルサイトの含有量が上記範囲であると、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体に、良好な低温での柔軟性を付与できる。 The content of perchloric acid-treated hydrotalcite is preferably 0.5 parts by mass or more and 7 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less with respect to 100 parts by mass of the vinyl chloride resin (a). The more preferable content is 1.5 parts by mass or more and 5.5 parts by mass or less. When the content of the perchloric acid-treated hydrotalcite is within the above range, good flexibility at a low temperature can be imparted to a vinyl chloride resin molded article obtained by powder molding a vinyl chloride resin composition.
[ゼオライト]
本発明の塩化ビニル樹脂組成物は、ゼオライトを安定剤として含有し得る。ゼオライトは、一般式:Mx/n・[(AlO2)x・(SiO2)y]・zH2O(一般式中、Mは原子価nの金属イオン、x+yは単位格子当たりの四面体数、zは水のモル数である)で表される化合物である。当該一般式中のMの種類としてはNa、Li、Ca、Mg、Znなどの一価又は二価の金属及びこれらの混合型が挙げられる。[Zeolite]
The vinyl chloride resin composition of the present invention may contain zeolite as a stabilizer. Zeolite has the general formula: M x / n · [(AlO 2 ) x · (SiO 2 ) y ] · zH 2 O (wherein M is a metal ion of valence n, and x + y is a tetrahedron per unit cell) Number, z is the number of moles of water). Examples of M in the general formula include monovalent or divalent metals such as Na, Li, Ca, Mg, and Zn, and mixed types thereof.
ゼオライトの含有量は特定の範囲に限定されない。ゼオライトの好ましい含有量は、(a)塩化ビニル樹脂100質量部に対して0.1質量部以上5質量部以下である。 The content of zeolite is not limited to a specific range. A preferable content of zeolite is 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.
[脂肪酸金属塩]
本発明の塩化ビニル樹脂組成物は、脂肪酸金属塩を含有していてもよい。好ましい脂肪酸金属塩は、一価脂肪酸金属塩であり、より好ましい脂肪酸金属塩は、炭素数12〜24の一価脂肪酸金属塩であり、更に好ましい脂肪酸金属塩は、炭素数15〜21の一価脂肪酸金属塩である。脂肪酸金属塩の具体例は、ステアリン酸リチウム、ステアリン酸マグネシウム、ステアリン酸アルミニウム、ステアリン酸カルシウム、ステアリン酸ストロンチウム、ステアリン酸バリウム、ステアリン酸亜鉛、ラウリン酸カルシウム、ラウリン酸バリウム、ラウリン酸亜鉛、2−エチルヘキサン酸バリウム、2−エチルヘキサン酸亜鉛、リシノール酸バリウム、リシノール酸亜鉛等である。脂肪酸金属塩を構成する金属としては、多価陽イオンを生成しうる金属が好ましく、2価陽イオンを生成しうる金属がより好ましく、周期表第3周期〜第6周期の、2価陽イオンを生成しうる金属が更に好ましく、周期表第4周期の、2価陽イオンを生成しうる金属が特に好ましい。最も好ましい脂肪酸金属塩はステアリン酸亜鉛である。[Fatty acid metal salt]
The vinyl chloride resin composition of the present invention may contain a fatty acid metal salt. A preferable fatty acid metal salt is a monovalent fatty acid metal salt, a more preferable fatty acid metal salt is a monovalent fatty acid metal salt having 12 to 24 carbon atoms, and a more preferable fatty acid metal salt is a monovalent fatty acid metal salt having 15 to 21 carbon atoms. It is a fatty acid metal salt. Specific examples of the fatty acid metal salt include lithium stearate, magnesium stearate, aluminum stearate, calcium stearate, strontium stearate, barium stearate, zinc stearate, calcium laurate, barium laurate, zinc laurate, 2-ethylhexane Barium acid, zinc 2-ethylhexanoate, barium ricinoleate, zinc ricinoleate and the like. The metal constituting the fatty acid metal salt is preferably a metal capable of generating a polyvalent cation, more preferably a metal capable of generating a divalent cation, and a divalent cation of the third to sixth periods of the periodic table. Is more preferable, and a metal capable of generating a divalent cation in the fourth period of the periodic table is particularly preferable. The most preferred fatty acid metal salt is zinc stearate.
上記脂肪酸金属塩の、上記(a)塩化ビニル樹脂100質量部に対する好ましい含有量は0.05質量部以上5質量部以下であり、より好ましくは0.1質量部以上1質量部以下であり、更に好ましくは0.1質量部以上0.5質量部以下である。脂肪酸金属塩の含有量が上記範囲であると、塩化ビニル樹脂組成物の加熱成形後の色差の値を小さくできる。 The preferred content of the fatty acid metal salt with respect to 100 parts by mass of the (a) vinyl chloride resin is 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 1 part by mass or less. More preferably, they are 0.1 mass part or more and 0.5 mass part or less. When the content of the fatty acid metal salt is within the above range, the value of the color difference after the thermoforming of the vinyl chloride resin composition can be reduced.
[その他のダスティング剤]
本発明の塩化ビニル樹脂組成物は、上記(a2)塩化ビニル樹脂微粒子以外のダスティング剤(以下、「その他のダスティング剤」ということがある。)を含有し得る。その他のダスティング剤としては、炭酸カルシウム、タルク、酸化アルミニウム等の無機微粒子;ポリアクリロニトリル樹脂微粒子、ポリ(メタ)アクリレート樹脂微粒子、ポリスチレン樹脂微粒子、ポリエチレン樹脂微粒子、ポリプロピレン樹脂微粒子、ポリエステル樹脂微粒子、ポリアミド樹脂微粒子等の有機微粒子が挙げられる。中でも、平均粒子径が10nm以上100nm以下の無機微粒子が好ましい。[Other dusting agents]
The vinyl chloride resin composition of the present invention may contain a dusting agent other than the above (a2) vinyl chloride resin fine particles (hereinafter sometimes referred to as “other dusting agents”). Other dusting agents include inorganic fine particles such as calcium carbonate, talc, and aluminum oxide; polyacrylonitrile resin fine particles, poly (meth) acrylate resin fine particles, polystyrene resin fine particles, polyethylene resin fine particles, polypropylene resin fine particles, polyester resin fine particles, polyamide Organic fine particles such as resin fine particles may be mentioned. Among these, inorganic fine particles having an average particle size of 10 nm to 100 nm are preferable.
その他のダスティング剤の含有量は特定の範囲に限定されない。その他のダスティング剤の含有量は、(a)塩化ビニル樹脂100質量部に対して、好ましくは20質量部以下であり、更に好ましくは10質量部以下である。 The content of other dusting agents is not limited to a specific range. The content of the other dusting agent is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, with respect to 100 parts by mass of the (a) vinyl chloride resin.
[その他の添加剤]
本発明の塩化ビニル樹脂組成物は、着色剤、耐衝撃性改良剤、過塩素酸処理ハイドロタルサイト以外の過塩素酸化合物(過塩素酸ナトリウム、過塩素酸カリウム等)、酸化防止剤、防カビ剤、難燃剤、帯電防止剤、充填剤、紫外線吸収剤、光安定剤、発泡剤、β−ジケトン類、滑剤等の、その他の添加剤を含有し得る。[Other additives]
The vinyl chloride resin composition of the present invention comprises a colorant, impact modifier, perchloric acid compound other than perchloric acid-treated hydrotalcite (sodium perchlorate, potassium perchlorate, etc.), antioxidant, Other additives such as fungicides, flame retardants, antistatic agents, fillers, ultraviolet absorbers, light stabilizers, foaming agents, β-diketones, lubricants and the like may be contained.
着色剤の具体例は、キナクリドン系顔料、ペリレン系顔料、ポリアゾ縮合顔料、イソインドリノン系顔料、銅フタロシアニン系顔料、チタンホワイト、カーボンブラックである。本発明の塩化ビニル樹脂組成物では、1種又は2種以上の顔料が使用される。キナクリドン系顔料は、p−フェニレンジアントラニル酸類が濃硫酸で処理されて得られ、黄みの赤から赤みの紫の色相を示す。キナクリドン系顔料の具体例は、キナクリドンレッド、キナクリドンマゼンタ、キナクリドンバイオレットである。
ペリレン系顔料は、ペリレン−3,4,9,10−テトラカルボン酸無水物と芳香族第一級アミンの縮合反応により得られ、赤から赤紫、茶色の色相を示す。ペリレン系顔料の具体例は、ペリレンレッド、ペリレンオレンジ、ペリレンマルーン、ペリレンバーミリオン、ペリレンボルドーである。
ポリアゾ縮合顔料は、アゾ色素が溶剤中で縮合されて高分子量化されて得られ、黄、赤系顔料の色相を示す。ポリアゾ縮合顔料の具体例は、ポリアゾレッド、ポリアゾイエロー、クロモフタルオレンジ、クロモフタルレッド、クロモフタルスカーレットである。
イソインドリノン系顔料は、4,5,6,7−テトラクロロイソインドリノンと芳香族第一級ジアミンの縮合反応により得られ、緑みの黄色から、赤、褐色の色相を示す。イソインドリノン系顔料の具体例は、イソインドリノンイエローである。
銅フタロシアニン系顔料は、フタロシアニン類に銅を配位した顔料で、黄みの緑から鮮やかな青の色相を示す。銅フタロシアニン系顔料の具体例は、フタロシアニングリーン、フタロシアニンブルーである。
チタンホワイトは、二酸化チタンからなる白色顔料で、隠蔽力が大きく、アナタース型とルチル型がある。
カーボンブラックは、炭素を主成分とし、酸素、水素、窒素を含む黒色顔料である。カーボンブラックの具体例は、サーマルブラック、アセチレンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、ボーンブラックである。Specific examples of the colorant are quinacridone pigments, perylene pigments, polyazo condensation pigments, isoindolinone pigments, copper phthalocyanine pigments, titanium white, and carbon black. In the vinyl chloride resin composition of the present invention, one or more pigments are used. The quinacridone pigment is obtained by treating p-phenylene dianthranilic acid with concentrated sulfuric acid, and exhibits a yellowish red to reddish purple hue. Specific examples of the quinacridone pigment are quinacridone red, quinacridone magenta, and quinacridone violet.
The perylene pigment is obtained by a condensation reaction of perylene-3,4,9,10-tetracarboxylic anhydride and an aromatic primary amine, and exhibits a hue from red to magenta and brown. Specific examples of the perylene pigment are perylene red, perylene orange, perylene maroon, perylene vermilion, and perylene bordeaux.
The polyazo condensation pigment is obtained by condensing an azo dye in a solvent to obtain a high molecular weight, and exhibits a hue of a yellow or red pigment. Specific examples of the polyazo condensation pigment are polyazo red, polyazo yellow, chromophthal orange, chromophthal red, and chromophthal scarlet.
The isoindolinone pigment is obtained by a condensation reaction of 4,5,6,7-tetrachloroisoindolinone and an aromatic primary diamine, and exhibits a hue of greenish yellow to red and brown. A specific example of the isoindolinone pigment is isoindolinone yellow.
The copper phthalocyanine pigment is a pigment in which copper is coordinated to phthalocyanines, and exhibits a hue of yellowish green to vivid blue. Specific examples of the copper phthalocyanine pigment are phthalocyanine green and phthalocyanine blue.
Titanium white is a white pigment made of titanium dioxide and has a large hiding power, and there are anatase type and rutile type.
Carbon black is a black pigment containing carbon as a main component and containing oxygen, hydrogen, and nitrogen. Specific examples of carbon black are thermal black, acetylene black, channel black, furnace black, lamp black, and bone black.
耐衝撃性改良剤の具体例は、アクリロニトリル−ブタジエン−スチレン共重合体、メタクリル酸メチル−ブタジエン−スチレン共重合体、塩素化ポリエチレン、エチレン−酢酸ビニル共重合体、クロロスルホン化ポリエチレン等である。本発明の塩化ビニル樹脂組成物では、1種又は2種以上の耐衝撃性改良剤を使用できる。なお、耐衝撃性改良剤は、塩化ビニル樹脂組成物中で微細な弾性粒子の不均一相となって分散する。当該弾性粒子にグラフト重合した鎖及び極性基が(a1)塩化ビニル樹脂粒子と相溶し、塩化ビニル樹脂組成物を粉体成形してなる塩化ビニル樹脂成形体の耐衝撃性が向上する。 Specific examples of the impact modifier include acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene copolymer, chlorinated polyethylene, ethylene-vinyl acetate copolymer, chlorosulfonated polyethylene and the like. In the vinyl chloride resin composition of the present invention, one or more impact resistance improvers can be used. The impact resistance improver is dispersed as a heterogeneous phase of fine elastic particles in the vinyl chloride resin composition. The chain and the polar group graft-polymerized on the elastic particles are compatible with the (a1) vinyl chloride resin particles, and the impact resistance of the vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition is improved.
酸化防止剤の具体例は、フェノール系酸化防止剤、硫黄系酸化防止剤、リン系酸化防止剤等である。
防カビ剤の具体例は、脂肪族エステル系防カビ剤、炭化水素系防カビ剤、有機窒素系防カビ剤、有機窒素硫黄系防カビ剤等である。Specific examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant.
Specific examples of the fungicide include aliphatic ester fungicides, hydrocarbon fungicides, organic nitrogen fungicides, organic nitrogen sulfur fungicides and the like.
難燃剤の具体例は、塩素化パラフィン等のハロゲン系難燃剤;リン酸エステル等のリン系難燃剤;水酸化マグネシウム、水酸化アルミニウム等の無機水酸化物;等である。 Specific examples of the flame retardant include halogen-based flame retardants such as chlorinated paraffins; phosphorus-based flame retardants such as phosphate esters; inorganic hydroxides such as magnesium hydroxide and aluminum hydroxide;
帯電防止剤の具体例は、脂肪酸塩類、高級アルコール硫酸エステル類、スルホン酸塩類等のアニオン系帯電防止剤;脂肪族アミン塩類、第四級アンモニウム塩類のカチオン系帯電防止剤;ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェノールエーテル類等のノニオン系帯電防止剤等である。 Specific examples of the antistatic agent include anionic antistatic agents such as fatty acid salts, higher alcohol sulfates and sulfonates; cationic antistatic agents such as aliphatic amine salts and quaternary ammonium salts; polyoxyethylene alkyl ethers And nonionic antistatic agents such as polyoxyethylene alkylphenol ethers.
充填剤の具体例は、シリカ、タルク、マイカ、炭酸カルシウム、クレー等である。 Specific examples of the filler are silica, talc, mica, calcium carbonate, clay and the like.
光安定剤の具体例は、ベンゾトリアゾール系、ベンゾフェノン系、ニッケルキレート系等の紫外線吸収剤、ヒンダートアミン系光安定剤等である。 Specific examples of the light stabilizer include benzotriazole-based, benzophenone-based, nickel chelate-based ultraviolet absorbers, hindered amine-based light stabilizers, and the like.
発泡剤の具体例は、アゾジカルボンアミド、アゾビスイソブチロニトリル等のアゾ化合物、N,N′−ジニトロソペンタメチレンテトラミン等のニトロソ化合物、p−トルエンスルホニルヒドラジド、p,p−オキシビス(ベンゼンスルホニルヒドラジド)等のスルホニルヒドラジド化合物等の有機発泡剤;フロンガス、炭酸ガス、水、ペンタン等の揮発性炭化水素化合物;これらを内包したマイクロカプセル等のガス系の発泡剤等である。 Specific examples of the blowing agent include azo compounds such as azodicarbonamide and azobisisobutyronitrile, nitroso compounds such as N, N'-dinitrosopentamethylenetetramine, p-toluenesulfonyl hydrazide, p, p-oxybis (benzene). Organic foaming agents such as sulfonyl hydrazide compounds such as sulfonyl hydrazide; volatile hydrocarbon compounds such as chlorofluorocarbon gas, carbon dioxide gas, water and pentane; gas-based foaming agents such as microcapsules enclosing these.
β−ジケトン類は、本発明の塩化ビニル樹脂組成物を粉体成形して得られる塩化ビニル樹脂成形体の初期色調の変動をより効果的に抑えるために用いられる。β−ジケトン類の具体例は、ジベンゾイルメタン、ステアロイルベンゾイルメタン、パルミトイルベンゾイルメタン等である。これらのβ−ジケトン類は1種を単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
なお、β−ジケトン類の含有量は特定の範囲に限定されない。β−ジケトン類の好ましい含有量は、(a)塩化ビニル樹脂100質量部に対して0.1質量部以上5質量部以下である。The β-diketones are used for more effectively suppressing fluctuations in the initial color tone of a vinyl chloride resin molded product obtained by powder molding the vinyl chloride resin composition of the present invention. Specific examples of β-diketones are dibenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, and the like. These β-diketones may be used singly or in combination of two or more.
In addition, content of (beta) -diketone is not limited to a specific range. The preferable content of β-diketones is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of (a) vinyl chloride resin.
滑剤の具体例は、12−ヒドロキシステアリン酸オリゴマーなどである。 Specific examples of the lubricant include 12-hydroxystearic acid oligomer.
(塩化ビニル樹脂組成物の製造方法)
本発明の塩化ビニル樹脂組成物は、上述した成分を混合して製造することができる。即ち、本発明の塩化ビニル樹脂組成物の製造方法は、少なくとも、上記(a)塩化ビニル樹脂、(b)可塑剤、及び(c)分子量が900以上4000以下のポリオール系化合物(ポリエステルポリオールおよび/またはポリエーテルポリオール)を混合することを含む。そして、本発明の塩化ビニル樹脂組成物の製造方法では、上記成分に加え任意に添加剤が混合されてもよい。
ここで、上記(a)塩化ビニル樹脂、上記(b)可塑剤、上記(c)分子量が900以上4000以下のポリオール系化合物、及び必要に応じて添加される添加剤の混合方法は限定されない。好ましい混合方法は、可塑剤及びダスティング剤(上記(a2)塩化ビニル樹脂微粒子と、必要に応じて添加されるその他のダスティング剤とを含む)を除く成分をドライブレンドにより混合し、その後、可塑剤、ダスティング剤を順次、混合する方法である。ドライブレンドには、ヘンシェルミキサーの使用が好ましい。また、ドライブレンド時の温度は、好ましくは50℃以上100℃以下、より好ましくは70℃以上80℃以下である。(Method for producing vinyl chloride resin composition)
The vinyl chloride resin composition of the present invention can be produced by mixing the components described above. That is, the method for producing a vinyl chloride resin composition of the present invention comprises at least (a) a vinyl chloride resin, (b) a plasticizer, and (c) a polyol compound having a molecular weight of 900 or more and 4000 or less (polyester polyol and / or Or mixing a polyether polyol). And in the manufacturing method of the vinyl chloride resin composition of this invention, in addition to the said component, an additive may be mixed arbitrarily.
Here, the mixing method of the (a) vinyl chloride resin, the (b) plasticizer, the (c) polyol compound having a molecular weight of 900 or more and 4000 or less, and an additive added as necessary is not limited. A preferred mixing method is to dry dry blend the components except for the plasticizer and the dusting agent (including the above (a2) vinyl chloride resin fine particles and other dusting agent added if necessary), and then In this method, a plasticizer and a dusting agent are sequentially mixed. The Henschel mixer is preferably used for dry blending. The temperature during dry blending is preferably 50 ° C. or higher and 100 ° C. or lower, more preferably 70 ° C. or higher and 80 ° C. or lower.
(塩化ビニル樹脂成形体)
本発明の塩化ビニル樹脂成形体は、上述した本発明の塩化ビニル樹脂組成物を粉体成形、好ましくはパウダースラッシュ成形して得る。
そして、本発明の塩化ビニル樹脂成形体は、自動車内装材、例えばインスツルメントパネル、ドアトリム等の表皮として好適に用いられる。(Vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention is obtained by powder molding, preferably powder slush molding, of the above-described vinyl chloride resin composition of the present invention.
The vinyl chloride resin molded article of the present invention is suitably used as an automobile interior material, for example, as a skin for instrument panels, door trims, and the like.
(塩化ビニル樹脂成形体の製造方法)
本発明の塩化ビニル樹脂成形体は、上述した塩化ビニル樹脂組成物を用いて製造することができる。即ち、本発明の塩化ビニル樹脂成形体の製造方法は、少なくとも、上述したいずれかの塩化ビニル樹脂組成物、または、上述した製造方法に従って製造した塩化ビニル樹脂組成物を粉体成形、好ましくはパウダースラッシュ成形することを特徴とする。(Method for producing vinyl chloride resin molding)
The vinyl chloride resin molded article of the present invention can be produced using the above-described vinyl chloride resin composition. That is, the method for producing a vinyl chloride resin molded article of the present invention is at least one of the above-described vinyl chloride resin compositions or a vinyl chloride resin composition produced according to the above-described production method. It is characterized by slush molding.
ここで、パウダースラッシュ成形時の金型温度は、好ましくは200℃以上300℃以下、より好ましくは220℃以上280℃以下である。 Here, the mold temperature at the time of powder slush molding is preferably 200 ° C. or higher and 300 ° C. or lower, more preferably 220 ° C. or higher and 280 ° C. or lower.
本発明の塩化ビニル樹脂成形体を製造する際には、上記温度範囲の金型に本発明の塩化ビニル樹脂組成物を振りかけて5秒以上30秒以下の間放置し、その後、余剰の塩化ビニル樹脂組成物を振り落とし、さらに30秒以上3分以下の間放置した後、金型を10℃以上60℃以下に冷却し、得られた本発明の塩化ビニル樹脂成形体を金型から脱型する。 In producing the vinyl chloride resin molded article of the present invention, the vinyl chloride resin composition of the present invention is sprinkled on a mold in the above temperature range and left for 5 seconds to 30 seconds, and then excess vinyl chloride is used. The resin composition is shaken off and allowed to stand for 30 seconds or more and 3 minutes or less, and then the mold is cooled to 10 ° C. or more and 60 ° C. or less, and the obtained vinyl chloride resin molded article of the present invention is removed from the mold. To do.
(積層体)
本発明の積層体は、本発明の塩化ビニル樹脂成形体と発泡ポリウレタン成形体とを積層して得ることができる。積層方法は、塩化ビニル樹脂成形体と、発泡ポリウレタン成形体とを別途製造した後に、熱融着あるいは熱接着又は公知の接着剤などを用いることにより貼り合わせる方法;塩化ビニル樹脂成形体上で、発泡ポリウレタン成形体の原料となるイソシアネート類とポリオール類などとを反応させて重合を行うと共に、公知の方法によりポリウレタンの発泡を行い、塩化ビニル樹脂成形体上に発泡ポリウレタン成形体を直接形成する方法等が挙げられる。後者の方が、工程が簡素であり、かつ、種々の形状の積層体を得る場合においても、塩化ビニル樹脂成形体と発泡ポリウレタン成形体との接着を確実に行うことができるのでより好適である。(Laminate)
The laminate of the present invention can be obtained by laminating the vinyl chloride resin molded product of the present invention and the foamed polyurethane molded product. The lamination method is a method in which a vinyl chloride resin molded body and a foamed polyurethane molded body are separately manufactured, and then bonded together by using heat fusion or thermal bonding or a known adhesive; on the vinyl chloride resin molded body, Polymerization by reacting isocyanates, which are raw materials for foamed polyurethane moldings, polyols, etc., and foaming polyurethane by a known method to directly form a foamed polyurethane molding on a vinyl chloride resin molding Etc. The latter is more preferable because the process is simple and the vinyl chloride resin molded body and the polyurethane foam molded body can be securely bonded even when obtaining laminates of various shapes. .
そして、本発明の積層体は、自動車内装材、例えばインスツルメントパネル、ドアトリム等として好適に用いられる。 And the laminated body of this invention is used suitably as a vehicle interior material, for example, an instrument panel, a door trim, etc.
以下、実施例により本発明が詳細に説明されるが、本発明はこれらの実施例に限定されない。なお、各種物性の測定方法、接着性の評価方法は次の通りである。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. In addition, the measuring method of various physical properties and the evaluation method of adhesiveness are as follows.
<(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均粒子径>
実施例及び比較例において、塩化ビニル樹脂組成物に用いられる(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均粒子径(体積平均粒子径)は、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子を、それぞれ水槽内に分散させ、以下に示す装置を用いて、光の回折・散乱強度分布を測定・解析し、粒子径及び体積基準の粒子径分布を測定することにより、算出した。
・装置:レーザー回折式粒度分布測定機(島津製作所製、型番「SALD−2300」)
・測定方式:レーザー回折及び散乱
・測定範囲:0.017μm〜2500μm
・光源:半導体レーザー(波長680nm、出力3mW)<Average particle diameter of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles>
In Examples and Comparative Examples, the average particle diameter (volume average particle diameter) of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride resin composition is as follows: vinyl chloride resin particles and vinyl chloride resin The fine particles were dispersed in a water tank, and the light diffraction / scattering intensity distribution was measured and analyzed using the apparatus shown below, and the particle diameter and volume-based particle diameter distribution were measured.
・ Apparatus: Laser diffraction particle size distribution analyzer (manufactured by Shimadzu Corporation, model number “SALD-2300”)
Measurement method: Laser diffraction and scattering Measurement range: 0.017 μm to 2500 μm
Light source: Semiconductor laser (wavelength 680 nm, output 3 mW)
<(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均重合度>
実施例及び比較例において、塩化ビニル樹脂組成物に用いられる(a1)塩化ビニル樹脂粒子及び(a2)塩化ビニル樹脂微粒子の平均重合度は、JIS K6720−2に準拠し、塩化ビニル樹脂粒子及び塩化ビニル樹脂微粒子のそれぞれを、シクロヘキサノンに溶解させて粘度を測定することにより、算出した。<Average polymerization degree of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin particles>
In Examples and Comparative Examples, the average degree of polymerization of (a1) vinyl chloride resin particles and (a2) vinyl chloride resin fine particles used in the vinyl chloride resin composition is in accordance with JIS K6720-2. Each of the vinyl resin fine particles was calculated by dissolving each of the vinyl resin fine particles in cyclohexanone and measuring the viscosity.
<塩化ビニル樹脂成形体のポリウレタン接着性>
実施例および比較例で得られた積層体において、塩化ビニル樹脂成形シートからなる表皮を発泡ポリウレタン成形体から剥離した。その後、剥離表面(塩化ビニル樹脂成形シート裏面及び発泡ポリウレタン成形体表面)の状態を目視で観察し、塩化ビニル樹脂成形体(シート)のポリウレタン接着性を以下の3段階の基準で判定した。
A:凝集破壊が剥離表面の90%以上の面積で起きている。
B:凝集破壊が剥離表面の60%以上90%未満の面積で起きている。
C:凝集破壊が剥離表面の60%未満の面積で起きている。
なお「凝集破壊」とは、発泡ポリウレタン成形体が塩化ビニル樹脂成形シートの剥離時に材料破壊され、発泡ポリウレタン成形体の一部が塩化ビニル樹脂成形シート側に残存する現象である。<Polyurethane adhesion of vinyl chloride resin molding>
In the laminates obtained in Examples and Comparative Examples, the skin made of a vinyl chloride resin molded sheet was peeled from the foamed polyurethane molded product. Thereafter, the state of the release surface (the back surface of the vinyl chloride resin molded sheet and the surface of the foamed polyurethane molded body) was visually observed, and the polyurethane adhesiveness of the vinyl chloride resin molded body (sheet) was determined based on the following three levels.
A: Cohesive failure occurs in an area of 90% or more of the peeled surface.
B: Cohesive failure occurs in an area of 60% or more and less than 90% of the peeled surface.
C: Cohesive failure occurs in an area of less than 60% of the peeled surface.
The “cohesive failure” is a phenomenon in which the foamed polyurethane molded product is destroyed when the vinyl chloride resin molded sheet is peeled off, and a part of the foamed polyurethane molded product remains on the vinyl chloride resin molded sheet side.
(実施例1〜3及び比較例1〜2)
表1に示す配合成分のうち可塑剤(トリメリット酸エステル可塑剤、及びエポキシ化大豆油)とダスティング剤である塩化ビニル樹脂微粒子を除く成分をヘンシェルミキサーに入れて混合した。そして、混合物の温度が80℃に上昇した時点で上記可塑剤を添加し、ドライアップ(可塑剤が塩化ビニル樹脂粒子に吸収されて、上記混合物がさらさらになった状態をいう。)させた。その後、ドライアップさせた混合物が70℃以下に冷却された時点でダスティング剤である塩化ビニル樹脂微粒子を添加し、塩化ビニル樹脂組成物を製造した。
次に、得られた塩化ビニル樹脂組成物を250℃に加熱したシボ付き金型に振りかけ、塩化ビニル樹脂成形シートの厚みが1mmになるよう調整した時間(具体的には12〜14秒間)放置して溶融させた後、余剰の塩化ビニル樹脂組成物を振り落とした。その後、200℃に設定したオーブンに静置し、静置後60秒経過した時点で金型を冷却水により冷却し、金型温度が40℃まで冷却された時点で145mm×175mm×1mmの塩化ビニル樹脂成形シートを金型から脱型した。
得られた塩化ビニル樹脂成形シートを100mm×100mmに切り取り、切り取られた塩化ビニル樹脂成形シート2枚を、200mm×300mm×10mmの金型中に重ならないように敷き、シボ付き面を下にして置いた。
別途、プロピレングリコールのプロピレンオキサイド・エチレンオキサイド(PO・EO)ブロック付加物(水酸基価28、末端EO単位の含有量=10%、内部EO単位の含有量4%)50質量部、グリセリンのPO・EOブロック付加物(水酸基価21、末端EO単位の含有量=14%)50質量部、水2.5質量部、トリエチレンジアミンのエチレングリコ−ル溶液(東ソー(株)製、商品名:「TEDA−L33」)0.2質量部、トリエタノールアミン1.2質量部、トリエチルアミン0.5質量部及び整泡剤(信越化学工業(株)製、商品名:「F−122」)0.5質量部からなるポリオール混合物と、ポリメチレンポリフェニレンポリイソシアネート(ポリメリックMDI))とを、インデックスが98になる比率で混合して混合液を調製した。そして、調製した混合液を、上述の通り金型中に敷かれた塩化ビニル樹脂成形シート2枚の上にそれぞれ注いだ。その後、348mm×255mm×10mmのアルミ板で金型に蓋をすることで金型を密閉した。密閉してから5分後、1mm厚の塩化ビニル樹脂成形シートからなる表皮に発泡ポリウレタン成形体が裏打ちされた積層体を金型から取り出した直後、上記に示す方法で塩化ビニル樹脂成形体のポリウレタン接着性を測定した。結果を表1に示す。(Examples 1-3 and Comparative Examples 1-2)
Among the blending components shown in Table 1, components other than plasticizers (trimellitic acid ester plasticizer and epoxidized soybean oil) and vinyl chloride resin fine particles as a dusting agent were placed in a Henschel mixer and mixed. Then, when the temperature of the mixture rose to 80 ° C., the plasticizer was added and dried up (referred to a state in which the plasticizer was absorbed into the vinyl chloride resin particles and the mixture was further improved). Thereafter, when the dried-up mixture was cooled to 70 ° C. or lower, vinyl chloride resin fine particles as a dusting agent were added to produce a vinyl chloride resin composition.
Next, the obtained vinyl chloride resin composition is sprinkled on a metal mold with a texture heated to 250 ° C., and left for a time (specifically, 12 to 14 seconds) adjusted so that the thickness of the vinyl chloride resin molded sheet becomes 1 mm. Then, the excess vinyl chloride resin composition was shaken off. Then, it is left still in an oven set at 200 ° C., and when 60 seconds have passed after standing, the mold is cooled with cooling water, and when the mold temperature is cooled to 40 ° C., 145 mm × 175 mm × 1 mm The vinyl resin molded sheet was removed from the mold.
Cut the obtained vinyl chloride resin molded sheet to 100 mm x 100 mm, lay the two cut vinyl chloride resin molded sheets so that they do not overlap in a 200 mm x 300 mm x 10 mm mold, and place the wrinkled face down placed.
Separately, propylene oxide / propylene oxide / ethylene oxide (PO / EO) block adduct (hydroxyl value 28, content of terminal EO unit = 10%, content of internal EO unit 4%), 50 parts by mass of glycerin PO. EO block adduct (hydroxyl value 21, terminal EO unit content = 14%) 50 parts by mass, water 2.5 parts by mass, ethylene glycol solution of triethylenediamine (manufactured by Tosoh Corporation, trade name: “TEDA -L33 ") 0.2 parts by mass, 1.2 parts by mass of triethanolamine, 0.5 parts by mass of triethylamine and a foam stabilizer (manufactured by Shin-Etsu Chemical Co., Ltd., trade name:" F-122 ") 0.5 A polyol mixture composed of parts by mass and a polymethylene polyphenylene polyisocyanate (polymeric MDI)) are mixed in a ratio such that the index is 98. The mixture was prepared. And the prepared liquid mixture was each poured on 2 sheets of vinyl chloride resin molding sheets spread | laid in the metal mold | die as above-mentioned. Thereafter, the mold was sealed by covering the mold with an aluminum plate of 348 mm × 255 mm × 10 mm. 5 minutes after sealing, immediately after taking out the laminated body in which the foamed polyurethane molded product is lined on the skin made of a 1 mm-thick vinyl chloride resin molded sheet from the mold, the polyurethane of the vinyl chloride resin molded product by the method described above is used. Adhesion was measured. The results are shown in Table 1.
1)新第一塩ビ(株)製、ZEST 1000Z(懸濁重合で得られた塩化ビニル樹脂粒子、平均重合度1000、平均粒子径145μm)
2)花王(株)製、トリメックスN−08
3)(株)ADEKA製、アデカサイザーO−130S
4)協和化学工業(株)製、アルカマイザー5
5)水澤化学工業(株)製、MIZUKALIZER DS
6)昭和電工(株)製、カレンズ DK−1
7)堺化学工業(株)製、SAKAI SZ2000
8)(株)ADEKA製、アデカスタブ LS−12
9)(株)ダイセル製、プラクセル 210
10)(株)ダイセル製、プラクセル 312
11)(株)ダイセル製、プラクセル 320
12)(株)ダイセル製、プラクセル 308
13)新第一塩ビ(株)製、ZEST PQLTX(乳化重合で得られた塩化ビニル樹脂微粒子、平均重合度800、平均粒子径2μm)
14)大日精化工業(株)製、DA PX−1720ブラック(A)1) ZEST 1000Z (Vinyl chloride resin particles obtained by suspension polymerization, average degree of polymerization 1000, average particle size 145 μm), manufactured by Shin Daiichi PVC Co., Ltd.
2) manufactured by Kao Corporation, Trimex N-08
3) Adeka Sizer O-130S manufactured by ADEKA Corporation
4) Alkamizer 5 manufactured by Kyowa Chemical Industry Co., Ltd.
5) MIZUKALIZER DS, manufactured by Mizusawa Chemical Co., Ltd.
6) Karenz DK-1, manufactured by Showa Denko K.K.
7) SAKAI SZ2000, manufactured by Sakai Chemical Industry Co., Ltd.
8) Made by ADEKA, ADK STAB LS-12
9) Placel 210 manufactured by Daicel Corporation
10) Made by Daicel Corporation, Plaxel 312
11) Made by Daicel Corporation, Plaxel 320
12) Placel 308, manufactured by Daicel Corporation
13) New Daiichi PVC Co., Ltd., ZEST PQLTX (vinyl chloride resin fine particles obtained by emulsion polymerization, average degree of polymerization 800, average particle diameter 2 μm)
14) DAPX-1720 Black (A), manufactured by Dainichi Seika Kogyo Co., Ltd.
なお、上記実施例および比較例で使用したポリエステルポリオール(ポリエステルジオールおよびポリエステルトリオール)の分子量は、(株)ダイセルがカタログで開示する値である。そしてポリエステルポリオール等のポリオール系化合物の分子量は、JIS K1557に準拠して測定される水酸基価に基づき、数平均分子量として算出することができる。 In addition, the molecular weight of the polyester polyol (polyester diol and polyester triol) used by the said Example and comparative example is a value which Daicel Corporation discloses by a catalog. And the molecular weight of polyol-type compounds, such as polyester polyol, can be computed as a number average molecular weight based on the hydroxyl value measured based on JISK1557.
表1より、実施例1〜3の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体は、発泡ポリウレタン成形体への接着性に優れていることがわかる。一方、ポリエステルポリオールを含まない比較例1の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体の発泡ポリウレタン成形体、また分子量が900に満たないポリエステルポリオールを含む比較例2の塩化ビニル樹脂組成物から得られた塩化ビニル樹脂成形体は、いずれも発泡ポリウレタン成形体への接着性が低いことがわかる。 From Table 1, it can be seen that the vinyl chloride resin molded bodies obtained from the vinyl chloride resin compositions of Examples 1 to 3 are excellent in adhesiveness to the foamed polyurethane molded bodies. On the other hand, a foamed polyurethane molded article of a vinyl chloride resin molded article obtained from the vinyl chloride resin composition of Comparative Example 1 containing no polyester polyol, and a vinyl chloride resin composition of Comparative Example 2 containing a polyester polyol having a molecular weight of less than 900 It can be seen that any of the vinyl chloride resin moldings obtained from the products has low adhesion to the polyurethane foam molding.
本発明の塩化ビニル樹脂組成物は、例えば、インスツルメントパネル、ドアトリム等の自動車内装材の表皮の成形材料として好適に用いられる。
The vinyl chloride resin composition of the present invention is suitably used as a molding material for the skin of automobile interior materials such as instrument panels and door trims.
Claims (15)
A vinyl chloride resin composition according to any one of claims 1 to 8, or a vinyl chloride resin composition produced according to the production method according to claim 14, which is powder-molded. Manufacturing method of resin molding.
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EP3705522B1 (en) | 2017-11-02 | 2023-10-25 | Kaneka Corporation | Vinyl chloride-based resin composition for powder molding, and vinyl chloride-based resin-molded body and laminate |
US20200354560A1 (en) * | 2018-01-16 | 2020-11-12 | Arkema Inc. | Polyol polyester and polyhydroxy alkane blends with polar polymers |
US20210017373A1 (en) | 2018-03-28 | 2021-01-21 | Zeon Corporation | Surface skin, method of producing surface skin, and laminate |
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