JP6121927B2 - Recycled thermoplastic resin composition - Google Patents
Recycled thermoplastic resin composition Download PDFInfo
- Publication number
- JP6121927B2 JP6121927B2 JP2014036920A JP2014036920A JP6121927B2 JP 6121927 B2 JP6121927 B2 JP 6121927B2 JP 2014036920 A JP2014036920 A JP 2014036920A JP 2014036920 A JP2014036920 A JP 2014036920A JP 6121927 B2 JP6121927 B2 JP 6121927B2
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- weight
- resin composition
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- 239000011342 resin composition Substances 0.000 title claims description 235
- 229920005992 thermoplastic resin Polymers 0.000 title claims description 63
- 239000002245 particle Substances 0.000 claims description 158
- 238000010521 absorption reaction Methods 0.000 claims description 155
- 238000000465 moulding Methods 0.000 claims description 129
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 117
- -1 polypropylene Polymers 0.000 claims description 107
- 150000002484 inorganic compounds Chemical class 0.000 claims description 69
- 229910010272 inorganic material Inorganic materials 0.000 claims description 69
- 239000004743 Polypropylene Substances 0.000 claims description 68
- 229920001155 polypropylene Polymers 0.000 claims description 67
- 239000000203 mixture Substances 0.000 claims description 58
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 239000012760 heat stabilizer Substances 0.000 claims description 36
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical group OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 claims description 34
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 32
- 239000000378 calcium silicate Substances 0.000 claims description 29
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 29
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 29
- 229920005990 polystyrene resin Polymers 0.000 claims description 28
- 230000008929 regeneration Effects 0.000 claims description 28
- 238000011069 regeneration method Methods 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 229920013716 polyethylene resin Polymers 0.000 claims description 27
- 229910001593 boehmite Inorganic materials 0.000 claims description 25
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 25
- 239000003607 modifier Substances 0.000 claims description 25
- 239000012188 paraffin wax Substances 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 22
- 229920005668 polycarbonate resin Polymers 0.000 claims description 21
- 239000004431 polycarbonate resin Substances 0.000 claims description 21
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 18
- 239000000194 fatty acid Substances 0.000 claims description 18
- 229930195729 fatty acid Natural products 0.000 claims description 18
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 150000004665 fatty acids Chemical class 0.000 claims description 16
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005498 polishing Methods 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006078 metal deactivator Substances 0.000 claims description 7
- 239000011593 sulfur Substances 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- 239000001993 wax Substances 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 4
- 239000000344 soap Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 description 188
- 239000003921 oil Substances 0.000 description 158
- 235000019198 oils Nutrition 0.000 description 158
- 238000012360 testing method Methods 0.000 description 99
- 229920005989 resin Polymers 0.000 description 91
- 239000011347 resin Substances 0.000 description 91
- 239000008188 pellet Substances 0.000 description 73
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 71
- 230000000052 comparative effect Effects 0.000 description 58
- 238000001746 injection moulding Methods 0.000 description 58
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 58
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 42
- 238000013461 design Methods 0.000 description 39
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 36
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 36
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 229910052622 kaolinite Inorganic materials 0.000 description 34
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 34
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 32
- 229910052623 talc Inorganic materials 0.000 description 30
- 238000010438 heat treatment Methods 0.000 description 29
- 238000002844 melting Methods 0.000 description 29
- 230000008018 melting Effects 0.000 description 29
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 27
- 239000000126 substance Substances 0.000 description 25
- 239000000047 product Substances 0.000 description 24
- 238000000034 method Methods 0.000 description 23
- 239000000454 talc Substances 0.000 description 22
- 229940088594 vitamin Drugs 0.000 description 22
- 229930003231 vitamin Natural products 0.000 description 22
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 19
- MKTRXTLKNXLULX-UHFFFAOYSA-P pentacalcium;dioxido(oxo)silane;hydron;tetrahydrate Chemical compound [H+].[H+].O.O.O.O.[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O.[O-][Si]([O-])=O MKTRXTLKNXLULX-UHFFFAOYSA-P 0.000 description 19
- 235000019359 magnesium stearate Nutrition 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- 239000004793 Polystyrene Substances 0.000 description 15
- 239000003795 chemical substances by application Substances 0.000 description 15
- 229920002223 polystyrene Polymers 0.000 description 14
- 239000000377 silicon dioxide Substances 0.000 description 14
- VBICKXHEKHSIBG-UHFFFAOYSA-N beta-monoglyceryl stearate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 13
- 239000007983 Tris buffer Substances 0.000 description 12
- 229910052791 calcium Inorganic materials 0.000 description 12
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 12
- GWFGDXZQZYMSMJ-UHFFFAOYSA-N Octadecansaeure-heptadecylester Natural products CCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC GWFGDXZQZYMSMJ-UHFFFAOYSA-N 0.000 description 11
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 11
- 239000003063 flame retardant Substances 0.000 description 11
- NKBWPOSQERPBFI-UHFFFAOYSA-N octadecyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCCCCCCCCCCCCCCCC NKBWPOSQERPBFI-UHFFFAOYSA-N 0.000 description 11
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 10
- 239000004417 polycarbonate Substances 0.000 description 10
- 239000004408 titanium dioxide Substances 0.000 description 10
- 101000610557 Homo sapiens U4/U6 small nuclear ribonucleoprotein Prp31 Proteins 0.000 description 9
- 101001109965 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L7-A Proteins 0.000 description 9
- 101001109960 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L7-B Proteins 0.000 description 9
- 102100040118 U4/U6 small nuclear ribonucleoprotein Prp31 Human genes 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 229920000515 polycarbonate Polymers 0.000 description 9
- 229920005672 polyolefin resin Polymers 0.000 description 9
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 8
- 229920001971 elastomer Polymers 0.000 description 8
- 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 7
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 7
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 7
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 230000005484 gravity Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 235000021314 Palmitic acid Nutrition 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 229920000098 polyolefin Polymers 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000008186 active pharmaceutical agent Substances 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 229920005669 high impact polystyrene Polymers 0.000 description 5
- 239000004797 high-impact polystyrene Substances 0.000 description 5
- 239000011256 inorganic filler Substances 0.000 description 5
- 229910003475 inorganic filler Inorganic materials 0.000 description 5
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000005909 Kieselgur Substances 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229920001893 acrylonitrile styrene Polymers 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010425 asbestos Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- 235000012216 bentonite Nutrition 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 3
- 235000010261 calcium sulphite Nutrition 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229910052570 clay Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000001095 magnesium carbonate Substances 0.000 description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 3
- 229910052895 riebeckite Inorganic materials 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010456 wollastonite Substances 0.000 description 3
- 229910052882 wollastonite Inorganic materials 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 2
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
この発明は、熱可塑性樹脂組成物の再生と製造方法に関するものであり、特に使用済みポリオレフィン系、ポリスチレン系、ポリアクリロニトリル系およびポリカーボネート系樹脂組成物の再生に関するものである。 The present invention relates to a method for regenerating and producing a thermoplastic resin composition, and more particularly to regenerating a used polyolefin-based, polystyrene-based, polyacrylonitrile-based, and polycarbonate-based resin composition.
現在、家電製品、複写機などのＯＡ機器、コンピュータの筐体、部品として、オレフィン系、スチレン系、アクリロニトリル系およびポリカーボネート系樹脂などの熱可塑性樹脂組成物が一般的に用いられている。これらの製品は、役目を終えて捨てられる段になると、廃棄物として取り扱われ、その多くは焼却、埋め立て、燃料として処理されてきた。しかしながら、近年、焼却、埋め立てによる環境汚染、埋め立ての処分場の不足が社会的問題となっている状況を受けて、家電業界、ＯＡ機器業界では、環境負荷低減、資源の有効活用の観点から、そのまま粉砕して再溶融して各種成形品に加工するマテリアルリサイクルが推進されて、マテリアルリサイクル材の製品への適用が進められている。 At present, thermoplastic resin compositions such as olefin-based, styrene-based, acrylonitrile-based, and polycarbonate-based resins are generally used as home appliances, office automation equipment such as copying machines, computer casings, and parts. These products are handled as waste when they are finished and discarded, and many of them have been incinerated, landfilled and processed as fuel. However, in recent years, in response to the situation where incineration, environmental pollution due to landfill, and shortage of landfill disposal sites have become a social problem, the home appliance industry and OA equipment industry have a view to reducing environmental impact and effectively using resources. Material recycling, which is crushed as it is, remelted and processed into various molded products, is being promoted, and application of material recycled materials to products is being promoted.
なお、使用済み家電製品を構成する樹脂組成物の大半は、ポリオレフィン系であるポリプロピレン（Polypropylene；略してＰＰ）樹脂、ポリエチレン（Polyethylene；略してＰＥ）樹脂、ポリスチレン系である耐衝撃性ポリスチレン（High Impact Polystyrene；略してＨＩＰＳ）樹脂、透明ポリスチレン（General Purpose Polystyrene；略してＧＰＰＳ）樹脂、アクリロニトリル系であるアクリロニトリル−ブタジエン−スチレン（Acrylonitrile-Butadiene-Styrene；略してＡＢＳ）樹脂、アクリロニトリル−スチレン（Acrylonitrile-Styrene；略してＡＳ）樹脂組成物であり、使用済みＯＡ機器、コンピュータを構成する樹脂組成物の大半は、アクリロニトリル系（ＡＢＳ、ＡＳ）樹脂、ポリカーボネート（Polycarbonate；略してＰＣ）系樹脂、ポリカーボネート／アクリロニトリル系樹脂などの難燃系の樹脂組成物である。 Most of the resin compositions constituting used home appliances are polyolefin-based polypropylene (Polypropylene; abbreviated PP) resin, polyethylene (Polyethylene; abbreviated PE) resin, and polystyrene-based impact-resistant polystyrene (High Impact Polystyrene (abbreviated as HIPS) resin, transparent polystyrene (General Purpose Polystyrene; abbreviated as GPPS) resin, acrylonitrile-based acrylonitrile-Butadiene-Styrene (abbreviated as ABS) resin, acrylonitrile-styrene (Acrylonitrile-styrene) Styrene (abbreviated as AS) resin composition, and most of resin compositions constituting used OA equipment and computers are acrylonitrile (ABS, AS) resin, polycarbonate (abbreviated as PC) resin, polycarbonate / Acrylonitrile Resin is a resin composition flame retardant, such as.
使用済み家電製品、ＯＡ機器から回収される廃プラスチックの中で、手解体により回収できないプラスチック残渣（シュレッダーダスト）は、ゴム、金属類の異物、異種樹脂の混合物であり、物性、ゴミなどの異物の問題により、そのまま使用することはできない。これらプラスチック残渣は、比重差による分別回収が進められており、比重が１．０以下で水に浮くポリオレフィン系（ポリエチレン、ポリプロピレン）樹脂組成物は、他の樹脂組成物に比べて、分別回収しやすい。また、水に沈んだプラスチック残渣の中から、熱可塑性樹脂組成物を選別する場合は、ポリスチレン系およびアクリロニトリル系樹脂組成物（比重：１．０５〜１．１０）、ポリカーボネート系樹脂組成物（比重：１．２０）のように比重が異なる場合には、溶液中で比重差を用いて選別するジグ選別を用いることにより選別が可能となる。さらに、同じ比重（１．０５〜１．１０）を有するポリスチレン系樹脂組成物およびアクリロニトリル系樹脂組成物については、お互いを擦り合せて、帯電させ、静電力により選別する静電選別を用いることにより、選別が可能となる。以上の結果、プラスチック残渣に含まれるポリオレフィン系、ポリスチレン系、アクリロニトリル系、ポリカーボネート系の樹脂組成物は、それぞれ樹脂種毎に高純度に選別され、マテリアルリサイクル可能な再生樹脂材料として、扱うことできる。 Among waste plastics collected from used home appliances and OA equipment, plastic residue (shredder dust) that cannot be recovered by manual dismantling is a mixture of rubber, metal foreign matter, and different types of resin. Because of this problem, it cannot be used as it is. These plastic residues are being collected separately by specific gravity difference. Polyolefin-based (polyethylene, polypropylene) resin compositions that float in water with a specific gravity of 1.0 or less are separated and recovered compared to other resin compositions. Cheap. When a thermoplastic resin composition is selected from plastic residues that have been submerged in water, a polystyrene-based and acrylonitrile-based resin composition (specific gravity: 1.05 to 1.10), a polycarbonate-based resin composition (specific gravity) : 1.20), when the specific gravity is different, it is possible to sort by using jig sorting which sorts using the specific gravity difference in the solution. Furthermore, for polystyrene-based resin compositions and acrylonitrile-based resin compositions having the same specific gravity (1.05 to 1.10), by electrostatically sorting by rubbing each other, charging, and selecting by electrostatic force Sorting becomes possible. As a result, the polyolefin-based, polystyrene-based, acrylonitrile-based, and polycarbonate-based resin compositions contained in the plastic residue can be handled as recycled resin materials that are sorted with high purity for each resin type and can be recycled.
再生樹脂材料は、完全に除去しきれない異物により、新材に比べて、衝撃特性（たとえば、シャルピー衝撃強度）、伸び特性（たとえば、引張破断伸び率）などの靭性面の物性低下が著しいことが分かっている。これら異物の除去方法としては、洗浄することが有効であるが、製品破砕時にこびり付いた異物は、洗浄で取りきるのは困難である。そこで、樹脂を溶融状態にして異物を除去する方法として、押出機のスクリーンメッシュによる異物を除去する方法が挙げられる。この方法では、スクリーンメッシュを細かくすることにより、異物除去効果が高く、樹脂組成物の衝撃特性、伸び特性などの靭性面の物性が大幅に改善される。しかし、この場合、異物がメッシュに目詰まりすることにより、押出機がベンドアップし、生産性が大きく低下することがあり、異物除去レベルと生産性がトレードオフの関係にある。さらに、これらの異物は、樹脂の溶融温度領域（１５０〜３００℃）では、固形分であり、押出機のスクリーンメッシュによる異物を除去する方法でも完全に取りきることが困難であるが、意匠性部品適用においては、顔料、無機成分による異物の隠蔽や構造部品適用においては、耐衝撃性改善剤などの添加剤の添加により、物性改善が検討されてきた。 Recycled resin materials have significantly reduced physical properties on toughness such as impact characteristics (for example, Charpy impact strength) and elongation characteristics (for example, tensile breaking elongation) due to foreign materials that cannot be completely removed. I know. As a method for removing these foreign substances, it is effective to wash them. However, it is difficult to remove the foreign substances stuck during product crushing by washing. Therefore, as a method for removing foreign matters by melting the resin, there is a method for removing foreign matters by a screen mesh of an extruder. In this method, by making the screen mesh fine, the foreign matter removal effect is high, and the physical properties of the toughness such as the impact properties and elongation properties of the resin composition are greatly improved. However, in this case, the foreign matter clogs the mesh, the extruder may bend up, and the productivity may be greatly reduced, and the foreign matter removal level and the productivity are in a trade-off relationship. Furthermore, these foreign matters are solids in the melting temperature region (150 to 300 ° C.) of the resin, and it is difficult to completely remove them by the method of removing foreign matters using a screen mesh of an extruder. In the application of parts, the improvement of physical properties has been studied by the addition of additives such as impact resistance improvers in the hiding of foreign matters by pigments and inorganic components and the application of structural parts.
ここでは、これまで再生樹脂材料で検討されてきていない課題を取り上げる。それは、再生樹脂材料を成形した時に、微量のガスが発生することであり、発生したガスにより、直ぐに、成形用金型が汚染されることはない。しかし、再生樹脂材料の成形を１，０００回以上繰り返すことにより、金型にヤニ成分が付着し、そのヤニが原因で、金型の転写性が悪くなり、いずれは成形品の外観意匠性が損なわれることが問題である。このヤニ成分を拭き取り、ガスクロマトグラフィー質量分析（ＧＣ／ＭＳ）を行った結果、ステアリン酸、パルミチン酸などの脂肪酸、ステアリン酸アミド、オレイン酸アミドなどの脂肪酸アミドが主成分であることがわかった。これらヤニ成分の主成分は、樹脂の流動性改善のための滑剤、押出機出口ダイに発生するメヤニ防止、金型の離型抵抗を最小限にするための内部離型剤として、添加されるものであり、樹脂組成物に悪い影響を及ぼす添加剤ではない。しかし、成形時に過度に添加したことにより、再生樹脂材料では、余分な滑剤や内部離型剤が、成形時に蒸発し、金型に付着することにより、ヤニとなり、成形品の外観意匠性を悪化させるため、金型に付着したヤニを除去する方法が必要となる。 Here, problems that have not been studied for recycled resin materials will be taken up. That is, when a recycled resin material is molded, a small amount of gas is generated, and the generated gas does not immediately contaminate the molding die. However, by repeating the molding of the recycled resin material more than 1,000 times, the spear component adheres to the mold, and due to the spear, the transferability of the mold is deteriorated. It is a problem that it is damaged. As a result of wiping this spear component and performing gas chromatography mass spectrometry (GC / MS), it was found that fatty acids such as stearic acid and palmitic acid, and fatty acid amides such as stearic acid amide and oleic acid amide were the main components. . The main component of these resin components is added as a lubricant for improving the fluidity of the resin, as an anti-mold agent for preventing die from the die at the exit of the extruder, and as an internal mold release agent for minimizing the mold release resistance. It is not an additive that adversely affects the resin composition. However, due to excessive addition at the time of molding, in the recycled resin material, excess lubricant and internal mold release agent evaporate at the time of molding and adhere to the mold, resulting in a spear, which deteriorates the appearance design of the molded product. Therefore, there is a need for a method for removing the dirt adhering to the mold.
樹脂組成物に含まれるガス成分を吸着する方法として、特開２００１−２９６６３９号公報（特許文献１）では、写真性に悪影響を及ぼすガス（硫黄、シアン、ホルムアルデヒド、塩素、塩化水素など）を吸着するガス吸着物質（ゼオライト、シリカ、タルク）、滑剤（ステアリン酸アミドなど）、ハイドロタルサイト類化合物、遮光性物質（無機フィラー）を含有する遮光性ポリオレフィン樹脂フィルム層を具備しているポリオレフィン系樹脂が提案されている。ここでは、フィルムから発生する硫黄、シアン、塩素ガス等を吸着するために、ゼオライトを用いている。今回の問題となるヤニ成分は、前述のように、ステアリン酸やパルミチン酸などの脂肪酸、ステアリン酸アミド、オレイン酸アミドなどの脂肪酸アミドが主成分である。特許文献１のゼオライトの吸油量は４０ｍｌ／１００ｇであり、吸油性能が足りず、充分に、ヤニ成分を除去できないことが考えられる。 As a method for adsorbing a gas component contained in a resin composition, Japanese Patent Application Laid-Open No. 2001-296639 (Patent Document 1) adsorbs gas (sulfur, cyan, formaldehyde, chlorine, hydrogen chloride, etc.) that adversely affects photographic properties. Polyolefin resin comprising a light shielding polyolefin resin film layer containing a gas adsorbing material (zeolite, silica, talc), a lubricant (such as stearamide), a hydrotalcite compound, and a light shielding material (inorganic filler) Has been proposed. Here, zeolite is used to adsorb sulfur, cyan, chlorine gas, etc. generated from the film. As described above, the main component of the spear component of this time is a fatty acid such as stearic acid or palmitic acid, or a fatty acid amide such as stearic acid amide or oleic acid amide. The oil absorption amount of the zeolite of Patent Document 1 is 40 ml / 100 g, and the oil absorption performance is insufficient, and it is considered that the spider component cannot be removed sufficiently.
また、特開２００７−３３２２９６号公報（特許文献２）では、ヒドロキシ脂肪酸アミドの誘導体と二酸化珪素を添加して、メヤニの原因物質となる低分子量樹脂が押出機出口のダイ先端において滞留することを抑制できる架橋構造を有するポリオレフィン系樹脂組成物が提案されている。ここでは、押出機出口ダイに発生するメヤニ原因物質を抑制するために、ヒドロキシ脂肪酸アミドの誘導体および二酸化珪素を用いており、前述のヤニ成分と同種のものを添加するために、ヤニ成分の抑制は困難であると考える。 In addition, JP 2007-332296 A (Patent Document 2) adds a hydroxy fatty acid amide derivative and silicon dioxide so that a low-molecular-weight resin that becomes a causative agent of stagnation stays at the die tip at the exit of the extruder. A polyolefin-based resin composition having a crosslinked structure that can be suppressed has been proposed. Here, hydroxy fatty acid amide derivatives and silicon dioxide are used to suppress the cause-causing substances generated at the exit die of the extruder. Is considered difficult.
さらに、特開平８−１５７６４９号公報（特許文献３）では、ＢＥＴ比表面積が０．５〜１５ｍ２／ｇ、固体酸量が１５μｍｏｌ／ｇ以下である炭酸カルシウムを添加することで、押出成形時にダイリップ汚れが改善できるポリオレフィン系樹脂組成物が提案されている。また、特開２０１２−２１４７０９号公報（特許文献４）では、平均粒子径１．０〜４．０μｍ、比表面積が２６０〜１０００ｍ２／ｇであり、吸油量が１００〜４００ｍｌ／ｇである球状シリカ微粉末を１〜１０重量部を添加することで、フィルム製膜時のメヤニの発生は抑制できるポリプロピレン系樹脂組成物が提案されている。特許文献３、４では、主目的が押出機出口ダイに発生するメヤニ原因物質の抑制であり、用途が異なる。特許文献３で使用される炭酸カルシウムは、ＢＥＴ比表面積は規定されているが、吸油量の規定がなく、たとえば、炭酸カルシウムには、比表面積３．０ｍ２／ｇで吸油量が３７ｍｌ／１００ｇのものや比表面積２．５ｍ２／ｇで吸油量６５ｍｌ／１００ｇのものがあり、比表面積と吸油量に相関のないものがあるため、吸油性能を規定するとは言えないのである。これらの課題を解決するためには、リサイクル材成形時のガス発生量を抑えたリサイクル材を提供する。 Furthermore, in JP-A-8-157649 (Patent Document 3), by adding calcium carbonate having a BET specific surface area of 0.5 to 15 m 2 / g and a solid acid amount of 15 μmol / g or less, at the time of extrusion molding A polyolefin resin composition capable of improving die lip contamination has been proposed. In JP 2012-214709 A (Patent Document 4), an average particle diameter of 1.0 to 4.0 μm, a specific surface area of 260 to 1000 m 2 / g, and an oil absorption of 100 to 400 ml / g. By adding 1 to 10 parts by weight of silica fine powder, there has been proposed a polypropylene resin composition capable of suppressing the occurrence of scouring during film formation. In Patent Documents 3 and 4, the main purpose is to suppress the cause-causing substance generated in the extruder exit die, and the uses are different. Calcium carbonate used in Patent Document 3 has a BET specific surface area, but no oil absorption amount. For example, calcium carbonate has a specific surface area of 3.0 m 2 / g and an oil absorption amount of 37 ml / 100 g. And the specific surface area is 2.5 m 2 / g and the oil absorption amount is 65 ml / 100 g, and there is no correlation between the specific surface area and the oil absorption amount, so the oil absorption performance cannot be defined. In order to solve these problems, the present invention provides a recycled material that suppresses the amount of gas generated during molding of the recycled material.
本発明は、使用済み熱可塑性樹脂組成物を成形時に、発生する微量のガスにより、金型にヤニ成分が付着し、そのヤニが原因で、金型の転写性が悪くなり、いずれは成形品の外観意匠性が損なわれるという問題に対し、成形時の微量のガス発生を抑制し、金型へのヤニ付着を抑制することができる、再生熱可塑性樹脂組成物を得ることを目的とする。 In the present invention, when a used thermoplastic resin composition is molded, a small amount of gas generated causes a component of the resin to adhere to the mold, which causes the transferability of the mold to deteriorate. An object of the present invention is to obtain a recycled thermoplastic resin composition capable of suppressing the generation of a small amount of gas during molding and suppressing the adhesion of the resin to the mold.
本発明の再生熱可塑性樹脂組成物は、使用済み熱可塑性樹脂組成物１００重量部と、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の吸油性無機化合物０．５〜５重量部と、流動性調整剤０．１〜５重量部と、耐熱安定剤０．０５〜１０重量部とを含有し、前記吸油性無機化合物が、粒子径０．１〜１．０μｍのアルミナ、粒子径０．１〜５．０μｍのベーマイト、粒子径１〜５０μｍのケイ酸カルシウム、粒子径０．１〜１０μｍの炭酸カルシウムから選ばれる少なくともいずれかであることを特徴とする。 The recycled thermoplastic resin composition of the present invention comprises 100 parts by weight of a used thermoplastic resin composition, 0.5 to 5 parts by weight of an oil-absorbing inorganic compound having an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more. And 0.1 to 5 parts by weight of a fluidity modifier and 0.05 to 10 parts by weight of a heat stabilizer, and the oil-absorbing inorganic compound is alumina having a particle size of 0.1 to 1.0 μm, a particle size boehmite 0.1 to 5.0 [mu] m, wherein at least either of silicic acid calcium particle size 1 to 50 [mu] m, is selected from calcium carbonate particle child size 0.1 to 10 [mu] m.
本発明の再生熱可塑性樹脂組成物において、前記使用済み熱可塑性樹脂組成物は、ポリプロピレン樹脂組成物、ポリエチレン樹脂組成物、ポリスチレン樹脂組成物、ＡＢＳ樹脂組成物、ポリカーボネート樹脂組成物から選ばれる少なくともいずれかであることが好ましい。 In the recycled thermoplastic resin composition of the present invention, the used thermoplastic resin composition is at least any selected from a polypropylene resin composition, a polyethylene resin composition, a polystyrene resin composition, an ABS resin composition, and a polycarbonate resin composition. It is preferable that
本発明の再生熱可塑性樹脂組成物において、前記流動性調整剤は、炭化水素系の流動パラフィン、パラフィンワックス、合成ポリエチレンワックス、ならびに、使用済み熱可塑性樹脂組成物の成形温度付近で揮発しない脂肪酸系、高級アルコール系、脂肪酸アミド系、金属石鹸系、エステル系の流動性調整剤から選ばれる少なくともいずれかであることが好ましい。 In the regenerated thermoplastic resin composition of the present invention, the fluidity adjusting agent includes hydrocarbon liquid paraffin, paraffin wax, synthetic polyethylene wax, and fatty acid system that does not volatilize around the molding temperature of the used thermoplastic resin composition. It is preferably at least one selected from higher alcohol type, fatty acid amide type, metal soap type and ester type fluidity modifiers.
本発明の再生熱可塑性樹脂組成物において、前記耐熱安定剤は、金属不活性剤およびヒンダードフェノール系の酸化防止剤を含み、前記ヒンダードフェノール系の酸化防止剤と同量のリン系の酸化防止剤またはイオウ系の酸化防止剤をさらに含むことが好ましい。また、本発明の再生熱可塑性樹脂組成物において、前記金属不活性剤はデカメチレンジカルボン酸ジサリチロイルヒドラジドであることが好ましい。 In the recycled thermoplastic resin composition of the present invention, the heat-resistant stabilizer includes a metal deactivator and a hindered phenol-based antioxidant, and the same amount of phosphorus-based oxidation as the hindered phenol-based antioxidant. It is preferable to further contain an inhibitor or a sulfur-based antioxidant. In the regenerated thermoplastic resin composition of the present invention, the metal deactivator is preferably decamethylene dicarboxylic acid disalicyloyl hydrazide .
本発明の再生熱可塑性樹脂組成物における使用済み熱可塑性樹脂組成物は、表面色の濃淡選別および表面研磨の少なくともいずれかが施されたものであることが好ましい。 The used thermoplastic resin composition in the recycled thermoplastic resin composition of the present invention is preferably subjected to at least one of surface color density selection and surface polishing.
本発明の再生熱可塑性樹脂組成物は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の吸油性無機化合物、流動性調整剤および耐熱安定剤をそれぞれ所定量含有することにより、成形時の発生するヤニ成分であるステアリン酸、パルミチン酸などの脂肪酸、ステアリン酸アミド、オレイン酸アミドなどの脂肪酸アミドを５０％以上吸着し、金型へのヤニ付着を抑制でき、外観意匠性が優れた成形品を得ることができる。 The regenerated thermoplastic resin composition of the present invention contains predetermined amounts of an oil-absorbing inorganic compound, a fluidity adjusting agent and a heat stabilizer having an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more. 50% or more of fatty acid amides such as stearic acid and palmitic acid, stearic acid amide, oleic acid amide, etc., which are the spear components that generate odor, can suppress the adhesion of spears to the mold and has excellent appearance design A molded product can be obtained.
また、本発明に用いられる吸油性無機化合物は、効率よく成形時のガス成分を吸収することができるため、少量の添加により、吸油性能を発揮するため、再生樹脂組成物およびそれを用いた成形品の物性低下を生じにくい。 In addition, the oil-absorbing inorganic compound used in the present invention can efficiently absorb the gas component at the time of molding, so that the oil-absorbing performance is exhibited by the addition of a small amount. Therefore, the recycled resin composition and the molding using the same It is difficult to cause deterioration of physical properties of products.
本発明の再生熱可塑性樹脂組成物は、使用済み熱可塑性樹脂組成物１００重量部と、０．５〜５重量部の吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の吸油性無機化合物と、０．１〜５重量部の流動性調整剤と、０．０５〜１０重量部の耐熱安定剤とを含有することを特徴とする。このような本発明の再生熱可塑性樹脂組成物により、成形時の発生するヤニ成分を５０％以上吸着し、金型へのヤニ付着を抑制でき、外観意匠性が優れた成形品を得ることができる。なお、ここで、発生を抑制したいヤニ成分とは、金型に付着したヤニ成分を拭き取り、ガスクロマトグラフィー質量分析（ＧＣ／ＭＳ）にて、加熱温度２００〜２５０℃、３０分間の測定条件で行ったときに発生したガス成分であり、列挙すると、ヘキサン、ヘプテン、ヘプタン、オクタン、ノナン、デカン、ウンデカン、ドデカン、トリデカン、テトラデカン、ペンタデカン、ヘキサデカン、ヘプタデカン、オクタデカン、ノナデカンなどの炭化水素、ラウリル酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、パルミトレイン酸などの脂肪酸、セチルアルコール、ステアリルアルコール、オレイルアルコールなどの高級アルコール、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、ヘキサデカンアミドなどの脂肪酸アミド、スクワレン、ビスフェノールＡなどである。 The recycled thermoplastic resin composition of the present invention comprises 100 parts by weight of a used thermoplastic resin composition, 0.5 to 5 parts by weight of an oil absorption amount of 50 ml / 100 g or more, and a specific surface area of 1 m 2 / g or more. And 0.1 to 5 parts by weight of a fluidity modifier and 0.05 to 10 parts by weight of a heat-resistant stabilizer. With such a recycled thermoplastic resin composition of the present invention, it is possible to adsorb 50% or more of the spear component generated at the time of molding, to suppress the spear adherence to the mold, and to obtain a molded product with excellent appearance design. it can. In addition, the spear component which wants to suppress generation | occurrence | production here wipes off the spear component adhering to a metal mold | die, and is the measurement conditions of heating temperature 200-250 degreeC and 30 minutes by gas chromatography mass spectrometry (GC / MS). These are gas components generated at the time of the enumeration. , Fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, palmitoleic acid, higher alcohols such as cetyl alcohol, stearyl alcohol, oleyl alcohol, fats such as stearic acid amide, oleic acid amide, erucic acid amide, hexadecanamide Amides, squalene, and the like bisphenol A.
［使用済み熱可塑性樹脂組成物］
本発明における使用済み熱可塑性樹脂組成物は、使用済みの家電製品、使用済みのＯＡ機器から回収される廃プラスチックに含まれている熱可塑性樹脂組成物であれば、特に限定されないが、使用済みの家電製品、使用済みのＯＡ機器から回収される廃プラスチックであるポリオレフィン系（ポリプロピレン、ポリエチレン）、ポリスチレン系（ＨＩＰＳ、ＧＰＰＳ）、アクリロニトリル系（ＡＢＳ、ＡＳ）、ポリカーボネート系、ポリカーボネート／アクリロニトリル系、または、アクリル酸系樹脂組成物であることが好ましい。
[Used thermoplastic resin composition]
The used thermoplastic resin composition in the present invention is not particularly limited as long as it is a thermoplastic resin composition contained in waste plastics collected from used home appliances and used OA equipment. Home appliances, polyolefins (polypropylene, polyethylene), polystyrenes (HIPS, GPPS), acrylonitriles (ABS, AS), polycarbonates, polycarbonate / acrylonitriles, which are waste plastics collected from used OA equipment, or An acrylic resin composition is preferred.
ポリオレフィン系樹脂組成物を構成するポリオレフィン系樹脂としては、ポリエチレン、ホモポリプロピレン、プロピレン−エチレンブロック共重合体、プロピレン−ブテンブロック共重合体、プロピレン−α−オレフィンブロック共重合体、プロピレン−エチレンランダム共重合体、プロピレン−ブテンランダム共重合体、プロピレン−α−オレフィンランダム共重合体、プロピレン−α−オレフィングラフト共重合体などが挙げられる。 Examples of the polyolefin resin constituting the polyolefin resin composition include polyethylene, homopolypropylene, propylene-ethylene block copolymer, propylene-butene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer. Examples thereof include a polymer, a propylene-butene random copolymer, a propylene-α-olefin random copolymer, and a propylene-α-olefin graft copolymer.
ポリオレフィン系樹脂組成物は、これら以外に、エチレン−α−オレフィン共重合体、スチレン系エラストマーなどの公知の樹脂、タルク、マイカ、ワラストナイト、炭酸カルシウム、硫酸バリウム、炭酸マグネシウム、クレー、アルミナ、シリカ、硫酸カルシウム、炭素繊維、ガラス繊維、金属繊維、けい砂、けし石、カーボンブラック、二酸化チタン、酸化亜鉛、三酸化アンチモン、水酸化マグネシウム、アスベスト、ゼオライト、モリブデン、珪藻土、セリサイト、シラス、水酸化カルシウム、亜硫酸カルシウム、硫酸ソーダ、ベントナイト、カオリナイト、黒鉛などの無機充填材を含有していてもよい。 Polyolefin resin composition, to these other than ethylene -α- olefin copolymer, known resins such as styrene-based elastomers, talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay, Alumina, silica, calcium sulfate, carbon fiber, glass fiber, metal fiber, silica sand, feldspar, carbon black, titanium dioxide, zinc oxide, antimony trioxide, magnesium hydroxide, asbestos, zeolite, molybdenum, diatomaceous earth, sericite, Inorganic fillers such as shirasu, calcium hydroxide, calcium sulfite, sodium sulfate, bentonite, kaolinite, and graphite may be contained.
ポリスチレン系樹脂組成物を構成するポリスチレン系樹脂としては、スチレン、α−メチルスチレン、ｐ−メチルスチレン、ｐ−ｔｅｒｔ−ブチルスチレンなどのモノビニル系芳香族単量体からなる単量体を重合して得られる重合体が挙げられ、代表的にはポリスチレン（ＧＰＰＳ）が挙げられる。また、ポリブタジエン（ＰＢＤ）、スチレン−ブタジエン共重合体（ＳＢＲ）などのゴム状物質をスチレン系モノマーに溶解し、塊状重合法または塊状懸濁重合法などにより製造したゴム変性スチレン系重合体が挙げられ、代表的には、ハイインパクトポリスチレン（ＨＩＰＳ）、ミドルインパクトポリスチレン（ＭＩＰＳ）などが挙げられる。また、シアノ基を有するアクリロニトリルのシアン化ビニル系単量体からなる単量体を重合して得られる重合体が挙げられ、代表的にはアクリロニトリル−スチレン共重合体（ＡＳ樹脂）、ポリブタジエンにアクリロニトリルとスチレンとが重合したＡＢＳ（アクリロニトリル−ブタジエン−スチレン共重合体）樹脂組成物が挙げられる。また、ポリブタジエンにメタクリル酸メチルとスチレンとが重合して得られる重合体であるＭＢＳ（メチルメタクリレート−ブタジエン−スチレン共重合体）樹脂組成物が挙げられる。 As the polystyrene resin constituting the polystyrene resin composition, a monomer composed of a monovinyl aromatic monomer such as styrene, α-methylstyrene, p-methylstyrene, p-tert-butylstyrene is polymerized. Examples of the resulting polymer include polystyrene (GPPS). In addition, rubber-modified styrene polymers prepared by dissolving a rubber-like substance such as polybutadiene (PBD) or styrene-butadiene copolymer (SBR) in a styrene monomer and using a bulk polymerization method or a bulk suspension polymerization method are listed. Typically, high impact polystyrene (HIPS), middle impact polystyrene (MIPS) and the like can be mentioned. In addition, a polymer obtained by polymerizing a monomer composed of cyanonitrile vinyl cyanide monomer having a cyano group is exemplified. Typically, acrylonitrile-styrene copolymer (AS resin), polybutadiene and acrylonitrile are included. ABS (acrylonitrile-butadiene-styrene copolymer) resin composition obtained by polymerizing styrene and styrene. Further, MBS (methyl methacrylate-butadiene-styrene copolymer) resin composition, which is a polymer obtained by polymerizing methyl methacrylate and styrene on polybutadiene, can be mentioned.
ポリスチレン系樹脂組成物は、これらのポリスチレン系樹脂にスチレン系エラストマー、アクリル系熱可塑性エラストマーなどの公知の樹脂、タルク、マイカ、ワラストナイト、炭酸カルシウム、硫酸バリウム、炭酸マグネシウム、クレー、アルミナ、シリカ、硫酸カルシウム、炭素繊維、ガラス繊維、金属繊維、けい砂、けし石、カーボンブラック、二酸化チタン、酸化亜鉛、三酸化アンチモン、水酸化マグネシウム、アスベスト、ゼオライト、モリブデン、珪藻土、セリサイト、シラス、水酸化カルシウム、亜硫酸カルシウム、硫酸ソーダ、ベントナイト、カオリナイト、黒鉛などの無機充填材を含有していてもよい。 Polystyrene-based resin compositions include these polystyrene-based resins, known resins such as styrene-based elastomers and acrylic thermoplastic elastomers, talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, and silica. , Calcium sulfate, Carbon fiber, Glass fiber, Metal fiber, Silica sand, Silicate stone, Carbon black, Titanium dioxide, Zinc oxide, Antimony trioxide, Magnesium hydroxide, Asbestos, Zeolite, Molybdenum, Diatomaceous earth, Sericite, Shirasu, Water It may contain inorganic fillers such as calcium oxide, calcium sulfite, sodium sulfate, bentonite, kaolinite and graphite.
ポリカーボネート樹脂組成物としては、特に制限はなく種々のものが挙げられる。通常、２価フェノールとカーボネート前駆体との反応により製造される芳香族ポリカーボネートを用いることができる。すなわち、２価フェノールとカーボネート前駆体とを、溶液法あるいは溶融法（すなわち、２価フェノールとホスゲンの反応、あるいは、２価フェノールとジフェニルカーボネートなどとのエステル交換法）により反応させて製造されたものを使用することができる。 There is no restriction | limiting in particular as a polycarbonate resin composition, A various thing is mentioned. Usually, an aromatic polycarbonate produced by a reaction between a dihydric phenol and a carbonate precursor can be used. That is, it was produced by reacting a dihydric phenol and a carbonate precursor by a solution method or a melting method (that is, a reaction of a dihydric phenol and phosgene or a transesterification method of a dihydric phenol and diphenyl carbonate). Things can be used.
２価フェノールとしては、様々なものが挙げられるが、特に２，２−ビス（４−ヒドロキシフェニル）プロパン〔ビスフェノールＡ〕、ビス（４−ヒドロキシフェニル）メタン、１，１−ビス（４−ヒドロキシフェニル）エタン、２，２−ビス（４−ヒドロキシ−３，５−ジメチルフェニル）プロパン、４，４’−ジヒドロキシジフェニル、ビス（４−ヒドロキシフェニル）シクロアルカン、ビス（４−ヒドロキシフェニル）オキシド、ビス（４−ヒドロキシフェニル）スルフィド、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）スルホキシド、ビス（４−ヒドロキシフェニル）エーテル、ビス（４−ヒドロキシフェニル）ケトンなど、あるいはこれらのハロゲン置換体などが挙げられる。２価フェノールは、好ましくはビス（ヒドロキシフェニル）アルカン系であり、より好ましくはビスフェノールＡを主原料としたものである。この他の２価フェノールとしては、ハイドロキノン、レゾルシン、カテコールなどが挙げられる。これらの２価フェノールは、それぞれ単独で用いてもよいし、２種以上を混合して用いてもよい。 Various divalent phenols can be mentioned, and in particular, 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxy). Phenyl) ethane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl) oxide, Bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) ketone, or their halogens Examples include substitution products. The dihydric phenol is preferably a bis (hydroxyphenyl) alkane, more preferably bisphenol A as a main raw material. Examples of other dihydric phenols include hydroquinone, resorcin, and catechol. These dihydric phenols may be used alone or in combination of two or more.
カーボネート前駆体としては、カルボニルハライド、カルボニルエステル、またはハロホルメートなどが挙げられる。具体的にはホスゲン、２価フェノールのジハロホーメート、ジフェニルカーボネート、ジメチルカーボネート、ジエチルカーボネートなどが挙げられる。 Examples of the carbonate precursor include carbonyl halide, carbonyl ester, and haloformate. Specific examples include phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate, diethyl carbonate and the like.
ポリカーボネート樹脂組成物は、これらのポリカーボネート系樹脂以外に、アクリロニトリル系エラストマー、スチレン系エラストマーなどの公知の樹脂やタルク、マイカ、ワラストナイト、炭酸カルシウム、硫酸バリウム、炭酸マグネシウム、クレー、アルミナ、シリカ、硫酸カルシウム、炭素繊維、ガラス繊維、金属繊維、けい砂、けし石、カーボンブラック、二酸化チタン、酸化亜鉛、三酸化アンチモン、水酸化マグネシウム、アスベスト、ゼオライト、モリブデン、珪藻土、セリサイト、シラス、水酸化カルシウム、亜硫酸カルシウム、硫酸ソーダ、ベントナイト、カオリナイト、黒鉛などの無機充填材を含有していてもよい。 In addition to these polycarbonate resins, the polycarbonate resin composition is a known resin such as acrylonitrile elastomer, styrene elastomer, talc, mica, wollastonite, calcium carbonate, barium sulfate, magnesium carbonate, clay, alumina, silica, Calcium sulfate, carbon fiber, glass fiber, metal fiber, silica sand, silica stone, carbon black, titanium dioxide, zinc oxide, antimony trioxide, magnesium hydroxide, asbestos, zeolite, molybdenum, diatomaceous earth, sericite, shirasu, hydroxylation Inorganic fillers such as calcium, calcium sulfite, sodium sulfate, bentonite, kaolinite, and graphite may be contained.
その他の熱可塑性樹脂組成物としては、たとえばアルキド樹脂、アミノ樹脂、ビスマレイミドトリアジン樹脂、塩素化ポリエーテル、アリル樹脂、エポキシ樹脂、エチレン−酢酸ビニル−塩化ビニル共重合体、エチレン−塩化ビニル共重合体、ニトリル樹脂、ポリエステル、オレフィンビニルアルコール共重合体、フェノール樹脂、ポリアセタール、ポリアクリレート、ポリアリルスルフォン、ポリベンゾイミダゾール、ポリブタジエン、ポリブチレン、ポリブチレンテレフタレート、ポリエーテルエーテルケトン、ポリエーテルケトン、ポリエーテルニトリル、ポリエーテルスルフォン、ポリエチレンテレフタレート、ポリケトン、メタクリル樹脂、ポリメチルペンテン、ポリフェニレンエーテル、ポリフェニレンスルフィド、ポリスルフォン、ポリウレタン、ポリビニルアセタール、ポリビニルアルコール、ポリ塩化ビニル、ポリ塩化ビニリデン、シリコーン樹脂、ポリ酢酸ビニル、キシレン樹脂、熱可塑性エラストマー、エチレンプロピレンゴム、クロロプレンゴム、ブチルゴム、ニトリルゴムが挙げられる。 Examples of other thermoplastic resin compositions include alkyd resins, amino resins, bismaleimide triazine resins, chlorinated polyethers, allyl resins, epoxy resins, ethylene-vinyl acetate-vinyl chloride copolymers, ethylene-vinyl chloride copolymers. Polymer, nitrile resin, polyester, olefin vinyl alcohol copolymer, phenol resin, polyacetal, polyacrylate, polyallyl sulfone, polybenzimidazole, polybutadiene, polybutylene, polybutylene terephthalate, polyether ether ketone, polyether ketone, polyether nitrile , Polyethersulfone, polyethylene terephthalate, polyketone, methacrylic resin, polymethylpentene, polyphenylene ether, polyphenylene sulfide, polysulfur Emissions, polyurethane, polyvinyl acetal, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, silicone resins, polyvinyl acetate, xylene resins, thermoplastic elastomers, ethylene propylene rubber, chloroprene rubber, butyl rubber, nitrile rubber.
使用済み熱可塑性樹脂組成物には、除去しきれなかった固形異物が含まれている。固形異物としては、炭化水素系ゴム、シリコーンゴム、ウレタン、金属屑、金属酸化物などの濃色系のものが多く、大きさは１００μｍ角以上であることが多い。 The used thermoplastic resin composition contains solid foreign substances that could not be removed. As solid foreign substances, there are many dark-colored ones such as hydrocarbon rubber, silicone rubber, urethane, metal scrap, and metal oxide, and the size is often 100 μm square or more.
［吸油性無機化合物］
本発明における吸油性無機化合物は、好ましくは、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の無機化合物であり、より好ましくは吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上のアルミナ、ベーマイトなどの酸化アルミニウム、ケイ酸カルシウム、カオリナイトおよび炭酸カルシウムから選ばれる少なくともいずれかを含む淡色系無機化合物である。
[Oil-absorbing inorganic compounds]
The oil-absorbing inorganic compound in the present invention is preferably an inorganic compound having an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more, more preferably an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2. It is a light-colored inorganic compound containing at least one selected from aluminum oxide such as alumina and boehmite, calcium silicate, kaolinite and calcium carbonate.
吸油性無機化合物の添加量は、使用済み熱可塑性樹脂組成物１００重量部に対して、好ましくは０．５〜５重量部である。無機化合物の吸油量測定値は、フタル酸ジオクチル吸油量およびあまに油吸油量があるが、ここでは、ＪＩＳ Ｋ５１０１−１３−１およびＫ５１０１−１３−２に規定されている精製あまに油および煮あまに油の吸油量測定値が好ましい。 The amount of the oil-absorbing inorganic compound added is preferably 0.5 to 5 parts by weight with respect to 100 parts by weight of the used thermoplastic resin composition. The measured values of the oil absorption of inorganic compounds include dioctyl phthalate oil absorption and oil absorption, but here, refined sesame oil and boiled oil as defined in JIS K5101-13-1 and K5101-13-2. The oil absorption measurement value of oil is preferred.
吸油性無機化合物の比表面積は、ＢＥＴ式（Brunauer, Emmett and Teller's equation）で求めた比表面積値であることが好ましい。 The specific surface area of the oil-absorbing inorganic compound is preferably a specific surface area value determined by the BET equation (Brunauer, Emmett and Teller's equation).
酸化アルミニウムは、化学式がＡｌ２Ｏ３で表されるアルミニウムの両性酸化物で、水酸化アルミニウムを焼成することによってできる白色粉末結晶であり、α−アルミナ、δ−アルミナ、θ−アルミナ、κ−アルミナおよびその他の形態的に異なるものがあり、また、製造法からコロイダルアルミナ、あるいはフュームドアルミナと呼ばれるものもある。本発明においては、これらのうちのいずれか、あるいは複数を混合して使用してもよいが、六方晶のα−アルミナを用いることが好ましい。吸油性能を上げるためには、比表面積を大きくする必要があり、そのため、粒子径も小さくなる。アルミナ（好ましくはα−アルミナ）の粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは、０．１〜１．０μｍである。たとえば、吸油量５０ｍｌ／１００ｇ、比表面積５．４ｍ２／ｇ、粒子径１．０μｍのアルミナ（Ｈ−４２Ｍ、東新化成（株）製）、吸油量６０ｍｌ／１００ｇ、比表面積５．９ｍ２／ｇ、粒子径０．７μｍのアルミナ（ＬＳ−２５０、日本軽金属（株）製）、吸油量５５ｍｌ／１００ｇ、比表面積３．２ｍ２／ｇ、粒子径０．８μｍのアルミナ（Ａ−１３−Ｍ、昭和電工（株）製）が使用できる。なお、アルミナの粒子径は、粒径測定装置を用いた動的光散乱法や透過型電子顕微鏡を用いた画像イメージング法で測定された値を指す。 Aluminum oxide is an amphoteric oxide of aluminum represented by the chemical formula Al 2 O 3 and is a white powder crystal formed by firing aluminum hydroxide, α-alumina, δ-alumina, θ-alumina, κ- There are alumina and other morphologically different ones, and there are also those called colloidal alumina or fumed alumina depending on the production method. In the present invention, any one of these or a mixture of these may be used, but hexagonal α-alumina is preferably used. In order to improve the oil absorption performance, it is necessary to increase the specific surface area, and therefore the particle diameter also decreases. The particle diameter of alumina (preferably α-alumina) is preferably 0.01 to 50 μm satisfying an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more, more preferably 0.1 to 1 μm. 0.0 μm. For example, oil absorption 50 ml / 100 g, specific surface area 5.4 m 2 / g, alumina with a particle size of 1.0 μm (H-42M, manufactured by Toshin Kasei Co., Ltd.), oil absorption 60 ml / 100 g, specific surface area 5.9 m 2 / G, alumina with a particle size of 0.7 μm (LS-250, manufactured by Nippon Light Metal Co., Ltd.), oil absorption 55 ml / 100 g, specific surface area 3.2 m 2 / g, alumina with a particle size of 0.8 μm (A-13- M, manufactured by Showa Denko KK). The particle diameter of alumina refers to a value measured by a dynamic light scattering method using a particle size measuring device or an image imaging method using a transmission electron microscope.
ベーマイトは、ＡｌＯＯＨまたはＡｌ２Ｏ３・Ｈ２Ｏの組成で示されるアルミナ一水和物で、斜方晶系の白色系粉末である。ベーマイトの平均粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは、０．１〜５．０μｍである。たとえば、吸油量２２０ｍｌ／１００ｇ、比表面積１１０ｍ２／ｇ、粒子径０．１μｍのベーマイト（Ｃ０１、大明化学工業（株）製）、吸油量８４ｍｌ／１００ｇ、比表面積１６ｍ２／ｇ、粒子径０．７μｍのベーマイト（Ｃ０６、大明化学工業（株）製）、吸油量６０ｍｌ／１００ｇ、比表面積３．０ｍ２／ｇ、粒子径２．３μｍのベーマイト（Ｃ２０、大明化学工業（株）製）が使用できる。なお、ベーマイトの粒子径は、アルミナの粒子径について上述したのと同様の方法で測定された値を指す。 Boehmite is an alumina monohydrate represented by a composition of AlOOH or Al 2 O 3 .H 2 O, and is an orthorhombic white powder. The average particle size of the boehmite is preferably 0.01 to 50 μm which satisfies the oil absorption of 50 ml / 100 g or more and the specific surface area of 1 m 2 / g or more, more preferably 0.1 to 5.0 μm. For example, oil absorption 220 ml / 100 g, specific surface area 110 m 2 / g, particle size 0.1 μm boehmite (C01, manufactured by Daimei Chemical Co., Ltd.), oil absorption 84 ml / 100 g, specific surface area 16 m 2 / g, particle size 0 .7 μm boehmite (C06, manufactured by Daimei Chemical Co., Ltd.), oil absorption 60 ml / 100 g, specific surface area 3.0 m 2 / g, particle size 2.3 μm boehmite (C20, manufactured by Daimei Chemical Co., Ltd.) Can be used. The particle diameter of boehmite indicates a value measured by the same method as described above for the particle diameter of alumina.
ケイ酸カルシウムは、酸化カルシウム（ＣａＯ）とケイ酸（ＳｉＯ２）が結合した化合物の総称であり、生石灰、珪石、水を主原料として、水熱反応により合成される。その中で、繊維状結晶を有するゾノトライト（６ＣａＯ・６ＳｉＯ２・Ｈ２Ｏ）および短冊状結晶を有するトバモライト（５ＣａＯ・６ＳｉＯ２・５Ｈ２Ｏ）を用いることが好ましい。ゾノトライトの粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは１〜５０μｍであり、トバモライトの粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは１〜５０μｍである。たとえば、吸油量６２０ｍｌ／１００ｇ、比表面積５６ｍ２／ｇ、粒子径２４μｍのケイ酸カルシウム（トバモライトＴＫ、日本インシュレーション（株）製）、吸油量４４０ｍｌ／１００ｇ、比表面積５５ｍ２／ｇ、粒子径１７μｍのケイ酸カルシウム（トバモライトＴＪ、日本インシュレーション（株）製）、吸油量４８０ｍｌ／１００ｇ、比表面積５０ｍ２／ｇ、粒子径４７μｍのケイ酸カルシウム（ゾノトライトＸＫ、日本インシュレーション（株）製）が使用できる。なお、ケイ酸カルシウムの粒子径は、アルミナの粒子径について上述したのと同様の方法で測定された値を指す。 Calcium silicate is a general term for compounds in which calcium oxide (CaO) and silicic acid (SiO 2 ) are bonded, and is synthesized by hydrothermal reaction using quick lime, silica, and water as main raw materials. Among them, it is preferable to use zonotolite (6CaO · 6SiO 2 · H 2 O) having a fibrous crystal and tobermorite (5CaO · 6SiO 2 · 5H 2 O) having a strip-like crystal. The particle diameter of zonotlite is preferably 0.01 to 50 μm satisfying an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more, more preferably 1 to 50 μm, and the particle diameter of tobermorite is an oil absorption. The amount is preferably 0.01 to 50 μm satisfying an amount of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more, more preferably 1 to 50 μm. For example, oil absorption amount 620 ml / 100 g, specific surface area 56 m 2 / g, calcium silicate (Tobermorite TK, manufactured by Nippon Insulation Co., Ltd.) having a particle diameter of 24 μm, oil absorption amount 440 ml / 100 g, specific surface area 55 m 2 / g, particle diameter 17 μm calcium silicate (Tobermorite TJ, manufactured by Nippon Insulation Co., Ltd.), oil absorption 480 ml / 100 g, specific surface area 50 m 2 / g, particle diameter 47 μm calcium silicate (Zonolite XK, manufactured by Nippon Insulation Co., Ltd.) Can be used. The particle diameter of calcium silicate refers to a value measured by the same method as described above for the particle diameter of alumina.
カオリナイトは、鉱物（ケイ酸塩鉱物）の一種で、結晶系は三斜晶系であり、その名は、粘土の産地である中国の高嶺（カオリン）に由来する。カオリナイトは、製造方法の違いにより、湿式と焼成がある。湿式カオリナイトは、水を利用して精製および漂白することにより、不純物を除去したものであり、白色度が高い。焼成カオリナイトは、湿式カオリナイトを焼成処理して、結晶水を除去したものであり、焼成処理により有機物が分解されるために、さらに白色度が高いことから、隠蔽力、耐候性に優れており、塗料、顔料、ゴム、プラスチック、化粧品などに使用されている。カオリナイトの粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは０．１〜１０μｍである。たとえば、吸油量１２０ｍｌ／１００ｇ、比表面積１５ｍ２／ｇ、粒子径０．７μｍのカオリナイト（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）、吸油量６０ｍｌ／１００ｇ、比表面積９．０ｍ２／ｇ、粒子径１．５μｍのカオリナイト（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）、吸油量６２ｍｌ／１００ｇ、比表面積４．０ｍ２／ｇ、粒子径１．３μｍのカオリナイト（オプチホワイト、白石カルシウム（株）製）が使用できる。なお、カオリナイトの粒子径は、アルミナの粒子径について上述したのと同様の方法で測定された値を指す。 Kaolinite is a kind of mineral (silicate mineral), the crystal system of which is triclinic, and its name is derived from China's kaolin. Kaolinite can be wet or fired depending on the manufacturing method. Wet kaolinite is a product obtained by removing impurities by purification and bleaching using water, and has high whiteness. The calcined kaolinite is obtained by calcining wet kaolinite to remove water of crystallization, and because the organic matter is decomposed by the calcining treatment, it has higher whiteness, so it has excellent hiding power and weather resistance. It is used in paints, pigments, rubber, plastics, cosmetics, etc. The particle size of kaolinite is preferably 0.01 to 50 μm, more preferably 0.1 to 10 μm, satisfying an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more. For example, an oil absorption amount of 120 ml / 100 g, a specific surface area of 15 m 2 / g, a kaolinite (Neogen 2000, manufactured by IMEYS) having a particle diameter of 0.7 μm, an oil absorption amount of 60 ml / 100 g, a specific surface area of 9.0 m 2 / g, a particle diameter of Kaolinite with 5 μm (GlomaxLL, manufactured by IMERYS), oil absorption of 62 ml / 100 g, specific surface area of 4.0 m 2 / g, and particle size of 1.3 μm can be used (Optiwhite, manufactured by Shiraishi Calcium Co., Ltd.). In addition, the particle diameter of kaolinite points out the value measured by the method similar to having mentioned above about the particle diameter of alumina.
炭酸カルシウムは、カルシウムの炭酸塩であり、貝殻や珊瑚の骨格、鶏卵の殻、石灰岩、大理石、鍾乳石、白亜（チョーク）の主成分である。無色結晶または白色粉末であり、中性の水にほとんど溶けないが、塩酸などの強酸と反応して、二酸化炭素を放出する。製造方法は、水酸化カルシウムに二酸化炭素を反応させて、合成する方法が一般的である。固体結晶には菱面体、三方晶系の結晶（方解石として産出）および斜方晶系（霰石として産出）の多形が存在し、常温常圧では三方晶系の方がやや安定である。他に、六方晶系のヴァテライトが知られているが非常に不安定である。室温で水溶液から炭酸カルシウムを沈殿させると三方晶系の結晶が生じるが、溶液を煮沸させながら沈殿させると斜方晶系のものが析出するが、この沈殿は放置により三方晶系に変化しやすい。炭酸カルシウムの粒子径は、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上を満足する０．０１〜５０μｍが好ましいが、より好ましくは０．１〜１０μｍである。たとえば、吸油量６０ｍｌ／１００ｇ、比表面積３．０ｍ２／ｇ、粒子径１．２μｍの炭酸カルシウム（軽微性軽質炭酸カルシウム、神島化学工業（株）製）、吸油量７０ｍｌ／１００ｇ、比表面積３．５ｍ２／ｇ、粒子径１．５μｍの炭酸カルシウム（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）、吸油量５３ｍｌ／１００ｇ、比表面積１２ｍ２／ｇ、粒子径０．１５μｍの炭酸カルシウム（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）が使用される。なお、炭酸カルシウムの粒子径は、アルミナの粒子径について上述したのと同様の方法で測定された値を指す。 Calcium carbonate is a carbonate of calcium, and is the main component of shells and shells of skeletons, eggshells, limestone, marble, stalactites, and chalk. It is a colorless crystal or white powder and hardly dissolves in neutral water, but reacts with a strong acid such as hydrochloric acid to release carbon dioxide. The production method is generally a method of synthesis by reacting carbon hydroxide with calcium hydroxide. Solid crystals include rhombohedral, trigonal crystals (produced as calcite), and orthorhombic (produced as meteorite) polymorphs, and the trigonal system is somewhat more stable at normal temperature and pressure. In addition, hexagonal vaterite is known but very unstable. When calcium carbonate is precipitated from an aqueous solution at room temperature, a trigonal crystal is formed. However, when the solution is precipitated while boiling, an orthorhombic crystal is precipitated, but this precipitate is likely to change to a trigonal crystal by standing. . The particle size of calcium carbonate is preferably 0.01 to 50 μm, more preferably 0.1 to 10 μm, which satisfies an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more. For example, an oil absorption of 60 ml / 100 g, a specific surface area of 3.0 m 2 / g, a calcium carbonate with a particle size of 1.2 μm (light and light calcium carbonate, manufactured by Kamishima Chemical Co., Ltd.), an oil absorption of 70 ml / 100 g, a specific surface area of 3 .5m 2 / g, calcium carbonate having a particle diameter of 1.5 [mu] m (calcium light carbonate EC, Konoshima Chemical Co., Ltd.), oil absorption 53 ml / 100 g, a specific surface area of 12m 2 / g, calcium carbonate having a particle diameter of 0.15μm (Brilliant 1500, manufactured by Shiroishi Kogyo Co., Ltd.) is used. The particle diameter of calcium carbonate refers to a value measured by the same method as described above for the particle diameter of alumina.
本発明における吸油性無機化合物は、好ましくは、吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の無機化合物であれば、種類を問わず、黒色系顔料のカーボンブラックや無機フィラーであるタルク、シリカなどを併用してもよい。たとえば、カーボンブラックの粒子径では、０．００１〜１μｍが好ましいが、より好ましくは１０〜２００ｎｍであり、タルクの粒子径では１μｍ以下が好ましく、シリカの粒子径では２０μｍ以下が好ましい。 The oil-absorbing inorganic compound in the present invention is preferably a black pigment carbon black or an inorganic filler as long as it is an inorganic compound having an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more. Some talc, silica and the like may be used in combination. For example, the particle size of carbon black is preferably 0.001 to 1 μm, more preferably 10 to 200 nm, the particle size of talc is preferably 1 μm or less, and the particle size of silica is preferably 20 μm or less.
［流動性調整剤］
本発明における流動性調整剤は、使用済み熱可塑性樹脂組成物に吸油性無機化合物を添加することによる流動性の悪化を防止するために添加される。流動性調整剤は、本来、滑剤、可塑剤としても用いられており、流動パラフィン、パラフィンワックス、合成ポリエチレンワックスなどの炭化水素系、ステアリン酸、パルミチン酸、オレイン酸などの脂肪酸系、ステアリルアルコール、セチルアルコール、オレイルアルコールなどの高級アルコール系、ステアリン酸アミド、オレイン酸アミド、エルカ酸アミド、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミドなどの脂肪酸アミド系、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸亜鉛などの金属石鹸系、ステアリン酸モノグリセリド、ステアリルステアレート、硬化油などのエステル系が挙げられる。その中で、脂肪酸系、高級アルコール系、脂肪酸アミド系、エステル系は、新材の流動性の調整に多く使用されており、前述のように、使用済み熱可塑性樹脂に多く残留していることから、成形温度付近である１８０〜２７０℃に揮発可能性のある化合物の追加添加はできる限り避ける必要がある。
[Flowability modifier]
The fluidity modifier in the present invention is added to prevent deterioration of fluidity due to the addition of the oil-absorbing inorganic compound to the used thermoplastic resin composition. Fluidity modifiers are originally used as lubricants and plasticizers, hydrocarbons such as liquid paraffin, paraffin wax and synthetic polyethylene wax, fatty acids such as stearic acid, palmitic acid and oleic acid, stearyl alcohol, Higher alcohols such as cetyl alcohol and oleyl alcohol, stearic acid amides, oleic acid amides, erucic acid amides, fatty acid amides such as methylene bis stearic acid amide, ethylene bis stearic acid amide, magnesium stearate, calcium stearate, zinc stearate And metal soaps such as stearic acid monoglyceride, stearyl stearate, and hardened oils. Among them, fatty acids, higher alcohols, fatty acid amides, and esters are often used to adjust the fluidity of new materials and, as mentioned above, remain in used thermoplastic resins. Therefore, it is necessary to avoid additional addition of a compound that may volatilize at 180 to 270 ° C., which is near the molding temperature.
本発明における流動性調整剤は、高分子量（数平均分子量が好ましくは３００〜２０，０００、より好ましくは５００〜１０，０００）の炭化水素系の流動パラフィン、パラフィンワックス、合成ポリエチレンワックス、ならびに、使用済み熱可塑性樹脂組成物の成形温度付近で揮発しない脂肪酸系、高級アルコール系、脂肪酸アミド系、金属石鹸系、エステル系の流動性調整剤から選ばれる少なくともいずれかであることが好ましく、より好ましくはパラフィンワックス、メチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステアリン酸モノグリセリド、ステアリルステアレート、硬化油などである。 The fluidity modifier in the present invention is a hydrocarbon liquid paraffin, paraffin wax, synthetic polyethylene wax having a high molecular weight (number average molecular weight is preferably 300 to 20,000, more preferably 500 to 10,000), and Preferably, it is at least one selected from fatty acid-based, higher alcohol-based, fatty acid amide-based, metal soap-based, ester-based fluidity modifiers that do not volatilize around the molding temperature of the used thermoplastic resin composition, and more preferably Are paraffin wax, methylene bis stearamide, ethylene bis stearamide, magnesium stearate, calcium stearate, stearic acid monoglyceride, stearyl stearate, hydrogenated oil and the like.
［耐熱安定剤］
銅、鉄、アルミニウムのような無機系金属は、熱可塑性樹脂組成物に対して、強い酸化力を有し、樹脂組成物を分解する可能性がある。また、固形異物として、金属屑、金属酸化物、異種樹脂などの樹脂組成物に対して、酸化劣化を加速する化合物が多く含まれていることから、ポリオレフィン系樹脂組成物における銅害による成形品表面の外観不良が発生する可能性がある。したがって、本発明の再生熱可塑性樹脂組成物は、吸油性無機化合物の添加に伴う熱可塑性樹脂や固形異物の劣化による物性低下を防ぎ、成形品表面の外観意匠性に優れたものとすることのできる再生熱可塑性樹脂組成物を得るため、耐熱安定剤を必須の成分として含有する。
[Heat resistance stabilizer]
Inorganic metals such as copper, iron, and aluminum have a strong oxidizing power against the thermoplastic resin composition, and may decompose the resin composition. In addition, since solid foreign substances contain many compounds that accelerate oxidative degradation with respect to resin compositions such as metal scraps, metal oxides, and dissimilar resins, molded products due to copper damage in polyolefin resin compositions There is a possibility of appearance defects on the surface. Therefore, the recycled thermoplastic resin composition of the present invention prevents deterioration of physical properties due to deterioration of the thermoplastic resin and solid foreign matters accompanying the addition of the oil-absorbing inorganic compound, and has excellent appearance design on the surface of the molded product. In order to obtain a regenerated thermoplastic resin composition, a heat-resistant stabilizer is contained as an essential component.
耐熱安定剤は、金属不活性剤およびヒンダードフェノール系の酸化防止剤を含み、さらに前記ヒンダードフェノール系の酸化防止剤と同量のリン系の酸化防止剤またはイオウ系の酸化防止剤のいずれかを含むことが好ましい。このような耐熱安定剤を添加することにより、吸油性無機化合物の添加に伴う熱可塑性樹脂や固形異物の劣化による物性低下を防ぎ、成形品表面の外観意匠性を優れたものとすることができる。 The heat resistance stabilizer includes a metal deactivator and a hindered phenol-based antioxidant, and further includes either the phosphorus-based antioxidant or the sulfur-based antioxidant in the same amount as the hindered phenol-based antioxidant. It is preferable that these are included. By adding such a heat stabilizer, it is possible to prevent deterioration in physical properties due to deterioration of the thermoplastic resin and solid foreign matters accompanying the addition of the oil-absorbing inorganic compound, and to improve the appearance design of the surface of the molded product. .
耐熱安定剤の構成比率は、特に制限されるものではないが、必要となる物性によりその都度調整することが望ましい。耐熱安定剤の添加量は、使用済み熱可塑性樹脂組成物１００重量部に対して、好ましくは０．０５〜１０重量部である。 The composition ratio of the heat stabilizer is not particularly limited, but it is desirable to adjust each time depending on the required physical properties. The addition amount of the heat stabilizer is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the used thermoplastic resin composition.
金属不活性剤としては、２’，３−ビス［［３−［３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル］プロピオニル］］プロピオノヒドラジド、３−（Ｎ−サリチロイル）アミノ−１，２，４−トリアゾール、デカメチレンジカルボン酸ジサリチロイルヒドラジド、Ｎ−フォーミイルサリチロイルヒドラジン、ベンゾトリアゾール、メチルベンゾトリアゾール、メチルベンゾトリアゾールカリウム塩、Ｎ，Ｎ−ジベンザール（オキザリルヒドラジド）、Ｎ，Ｎ−ビス（３，５−ジ−ｔ−ブチル−４−ハイドロキシハイドロシンナメート）などの公知の金属不活性剤が用いられる。これらの中でも、耐熱安定性の点で、デカメチレンジカルボン酸ジサリチロイルヒドラジドが好ましい。 Examples of metal deactivators include 2 ′, 3-bis [[3- [3,5-di-t-butyl-4-hydroxyphenyl] propionyl]] propionohydrazide, 3- (N-salicyloyl) amino-1 , 2,4-triazole, decamethylenedicarboxylic acid disalicyloyl hydrazide, N-formyl salicyloyl hydrazine, benzotriazole, methylbenzotriazole, methylbenzotriazole potassium salt, N, N-dibenzal (oxalyl hydrazide), Known metal deactivators such as N, N-bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) are used. Among these, decamethylene dicarboxylic acid disalicyloyl hydrazide is preferable in terms of heat resistance stability.
ヒンダードフェノール系の酸化防止剤としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、１，３，５−トリメチル−２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）ベンゼン、トリエチレングリコールビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］などの公知のヒンダードフェノール系酸化防止剤が用いられる。これらの中でも、耐熱安定性の点で、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネートが望ましい。 Examples of hindered phenol antioxidants include 2,6-di-t-butyl-p-cresol and tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). Propionate] methane, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl Known hindered phenolic antioxidants such as -4-hydroxybenzyl) benzene and triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] are used. Among these, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, stearyl β- (3,5-di-) in terms of heat stability. t-Butyl-4-hydroxyphenyl) propionate is preferred.
リン系の酸化防止剤としては、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト、テトラキス（２，４−ジ−ｔ−ブチルフェニル）［１，１−ビフェニル］−４，４’−ジイルビスホスフォナイト、ビス［２，４−ビス（１，１−ジメチルエチル）−６−メチルフェニル］エチルエステル亜リン酸、ビス（２，４−ジ−ｔ−ブチルフェニル）ペンタエリスリトールジホスファイト、トリアリルホスファイト、トリ（モノノニルフェニル）ホスファイトなどの公知のリン系酸化防止剤が用いられる。これらの中で、耐熱安定性の点で、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイトが望ましい。 Examples of phosphorus antioxidants include tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t-butylphenyl) [1,1-biphenyl] -4,4 ′. -Diylbisphosphonite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid, bis (2,4-di-t-butylphenyl) pentaerythritol di Known phosphorous antioxidants such as phosphite, triallyl phosphite, tri (monononylphenyl) phosphite are used. Among these, tris (2,4-di-t-butylphenyl) phosphite is desirable in terms of heat stability.
イオウ系の酸化防止剤としては、ジラウリル−３，３’−チオジプロピオネート、ジオクタデシル−３，３’−チオジプロピオネートなどの公知のイオウ系酸化防止剤が用いられる。これらの中でも、耐熱安定性の点で、ジオクタデシル−３，３’−チオジプロピオネートが好ましい。 As the sulfur-based antioxidant, known sulfur-based antioxidants such as dilauryl-3,3'-thiodipropionate and dioctadecyl-3,3'-thiodipropionate are used. Among these, dioctadecyl-3,3'-thiodipropionate is preferable from the viewpoint of heat stability.
［その他添加剤］
本発明の再生熱可塑性樹脂組成物は、本発明の目的を阻害しない限り、可塑剤、離型剤、難燃剤、難燃助剤、染料、顔料、帯電防止剤などの添加剤を配合することができる。なお、これらのそれぞれについてはその一種のみを単独で、又は二種以上を組み合わせて用いることができる。
[Other additives]
The regenerated thermoplastic resin composition of the present invention contains additives such as a plasticizer, a release agent, a flame retardant, a flame retardant aid, a dye, a pigment, and an antistatic agent, as long as the object of the present invention is not impaired. Can do. In addition, about each of these, only the 1 type can be used individually or in combination of 2 or more types.
可塑剤としては、ポリエチレングリコール、ポリアミドオリゴマー、エチレンビスステアロアマイド、フタル酸エステル、アジピン酸エステル、ポリスチレンオリゴマー、ポリエチレンワックス、シリコーンオイル、ミネラルオイルなどの公知の可塑剤から任意に選択して用いることができる。 As a plasticizer, it is arbitrarily selected from known plasticizers such as polyethylene glycol, polyamide oligomer, ethylene bisstearoamide, phthalic acid ester, adipic acid ester, polystyrene oligomer, polyethylene wax, silicone oil, and mineral oil. Can do.
離型剤としては、ポリエチレンワックス、シリコーンオイル、長鎖カルボン酸、長鎖カルボン酸金属塩などの公知の離型剤から任意に選択して用いることができる。 The release agent can be arbitrarily selected from known release agents such as polyethylene wax, silicone oil, long chain carboxylic acid, and long chain carboxylic acid metal salt.
難燃剤としては、トリクレジルホスフェート、トリフェニルホスフェート、トリス−３−クロロプロピルホスフェートなどのリン系難燃剤、２，２−ビス［４−（２，３−ジブロモプロポキシル）−３，５−ジブロモフェニル］プロパン、ビス(３，５−ジブロモ−４−ジブロモプロピルオキシフェニル）スルホン、エチレンビスペンタブロモベンゼン、ヘキサブロモシクロドデカンなどの臭素系難燃剤、シリコーン系難燃剤、水酸化マグネシウム、水酸化アルミニウムなどの水酸化物系難燃剤などの公知の難燃剤から任意に選択して用いることができる。 Examples of the flame retardant include phosphorus flame retardants such as tricresyl phosphate, triphenyl phosphate, and tris-3-chloropropyl phosphate, 2,2-bis [4- (2,3-dibromopropoxyl) -3,5- Brominated flame retardants such as dibromophenyl] propane, bis (3,5-dibromo-4-dibromopropyloxyphenyl) sulfone, ethylenebispentabromobenzene, hexabromocyclododecane, silicone flame retardant, magnesium hydroxide, hydroxylated It can be arbitrarily selected from known flame retardants such as hydroxide flame retardants such as aluminum.
難燃助剤としては、三酸化アンチモンなどのアンチモン化合物、その他の難燃助剤から任意に選択して用いることができる。 The flame retardant aid can be arbitrarily selected from antimony compounds such as antimony trioxide and other flame retardant aids.
＜再生熱可塑性樹脂組成物の製造方法＞
[使用済み熱可塑性樹脂組成物の前処理]
本発明の使用済み熱可塑性樹脂組成物は、吸油性無機化合物、流動性調整剤および耐熱安定剤を添加する前に、前処理として、表面色の濃淡選別および表面研磨の少なくともいずれかを施すことが好ましい。これによって、より一層、成形品表面の外観意匠性に優れた再生熱可塑性樹脂組成物が得られる。
<Method for Producing Recycled Thermoplastic Resin Composition>
[Pretreatment of used thermoplastic resin composition]
The used thermoplastic resin composition of the present invention is subjected to at least one of surface color density selection and surface polishing as pretreatment before adding the oil-absorbing inorganic compound, the fluidity modifier and the heat stabilizer. Is preferred. As a result, a recycled thermoplastic resin composition excellent in appearance design on the surface of the molded product can be obtained.
（濃淡選別）
使用済み熱可塑性樹脂組成物の濃淡選別とは、樹脂組成物表面の濃淡度合を指標として使用済み熱可塑性樹脂組成物から所望の成分を選別する方法である。たとえば、高い明度、光沢を有する淡色系の再生熱可塑性樹脂組成物を得るためには、光吸収性顔料であるカーボンブラックを含む濃色系樹脂組成物、濃色系異物の除去が必要であり、使用済み熱可塑性樹脂組成物の表面色をＣＣＤ（Charge Couple Device）カメラなどで検知することにより、濃色系樹脂組成物、濃色系異物を除去できる。より具体的には、たとえば、表面の明度７５％を閾値にして選別を行い、光吸収性顔料であるカーボンブラックを含む濃色系樹脂組成物、濃色系異物を除去して、明度７５％以上の使用済み熱可塑性樹脂組成物を得ることができる。なお、濃色系樹脂組成物、濃色系異物の除去方法は、ベルトコンベアなどの搬送装置を用いて、使用済み熱可塑性樹脂組成物を測定エリアまで搬送し、ＣＣＤカメラなどにより、使用済み熱可塑性樹脂組成物の濃淡を検知し、検知した濃色系樹脂組成物や濃色系異物に対して、空気銃（エジェクター）ノズルで撃ち落すことにより実施することができる。
(Tint selection)
The gradation selection of the used thermoplastic resin composition is a method of selecting a desired component from the used thermoplastic resin composition using the degree of density on the surface of the resin composition as an index. For example, in order to obtain a light-colored recycled thermoplastic resin composition having high brightness and gloss, it is necessary to remove a dark-colored resin composition containing carbon black as a light-absorbing pigment and dark-colored foreign matter. By detecting the surface color of the used thermoplastic resin composition with a CCD (Charge Couple Device) camera or the like, the dark color resin composition and the dark color foreign matter can be removed. More specifically, for example, selection is performed with a surface brightness of 75% as a threshold value, and a dark color resin composition containing carbon black as a light-absorbing pigment and dark foreign matter are removed to obtain a brightness of 75%. The above used thermoplastic resin composition can be obtained. The method for removing the dark color resin composition and the dark color foreign matter is to transport the used thermoplastic resin composition to the measurement area using a conveyor such as a belt conveyor, and use a CCD camera or the like to remove the used heat. It can be carried out by detecting the density of the plastic resin composition and shooting off the detected dark color resin composition or dark foreign matter with an air gun (ejector) nozzle.
（表面研磨）
使用済み熱可塑性樹脂組成物の表面研磨とは、樹脂組成物表面を研磨することにより、樹脂組成物の表面に付着している濃色系異物等を除去することであり、樹脂組成物の表面を刃物で切削することや、樹脂組成物同士を相互に摩擦させることにより行われる。使用済み熱可塑性樹脂組成物の表面研磨を施すことにより、高い明度、光沢を有する成形品表面の外観意匠性に優れた再生熱可塑性樹脂組成物を得ることができる。
(Surface polishing)
The surface polishing of the used thermoplastic resin composition is to remove dark foreign matters adhering to the surface of the resin composition by polishing the surface of the resin composition. Is cut by a blade, or the resin compositions are rubbed against each other. By subjecting the used thermoplastic resin composition to surface polishing, a recycled thermoplastic resin composition excellent in appearance design on the surface of a molded article having high brightness and gloss can be obtained.
［吸油性無機化合物、流動性調整剤および耐熱安定剤の添加］
本発明における吸油性無機化合物、流動性調整剤および耐熱安定剤は、通常粉末あるいは粒状で使用される。本発明の再生熱可塑性樹脂組成物は、使用済み熱可塑性樹脂組成物に吸油性無機化合物、流動性調整剤および耐熱安定剤を添加し、必要に応じて他の上記添加剤を添加して、混練することで得られる。
[Addition of oil-absorbing inorganic compound, fluidity modifier and heat stabilizer]
The oil-absorbing inorganic compound, fluidity modifier and heat stabilizer in the present invention are usually used in powder or granular form. The regenerated thermoplastic resin composition of the present invention is the addition of an oil-absorbing inorganic compound, a fluidity modifier and a heat stabilizer to the used thermoplastic resin composition, and, if necessary, other additives as described above, It is obtained by kneading.
混練の方法としては、溶融混練、溶媒キャストブレンド、ラテックスブレンド、ポリマーコンプレックスなどの物理的ブレンドを用いる方法が挙げられるが、特に溶融混練法が好ましい。上記材料を混練するための装置としては、タンブラ、ヘンシェルミキサ、ロータリーミキサ、スーパーミキサ、リボンタンブラ、Ｖブレンダなどが挙げられる。このような混練装置によって上記各材料を均一に分散させ、次いで、溶融混練した上で、ペレット化することが好ましい。溶融混練ペレット化には単軸、多軸、または、タンデム式押出機を用いるのが一般的であるが、これらの押出機以外に、バンバリーミキサ、ローラ、コ・ニーダ、ブラストミル、プラベンダーブラウトグラフなどを用いることもでき、これらを回分的、または連続的に運転される。また、溶融混練はせずに、樹脂ペレット、吸油性無機化合物、流動性調整剤、耐熱安定剤、その他添加剤それぞれを混ぜ合わせ、前記混合材を成形用樹脂として使用し成形機加熱筒内で溶融混練する、いわゆるモールドブレンドでの実施も可能である。 Examples of the kneading method include a method using physical blending such as melt kneading, solvent cast blending, latex blending, and polymer complex, and the melt kneading method is particularly preferable. Examples of the apparatus for kneading the material include a tumbler, a Henschel mixer, a rotary mixer, a super mixer, a ribbon tumbler, and a V blender. It is preferable to uniformly disperse each of the above materials by such a kneading apparatus, and then pelletize after melt-kneading. In general, single-screw, multi-screw, or tandem extruders are used for melt-kneading pelletization. Besides these extruders, Banbury mixers, rollers, co-kneaders, blast mills, and plastic benders are used. A graph or the like can also be used, and these are operated batchwise or continuously. In addition, resin pellets, oil-absorbing inorganic compounds, fluidity modifiers, heat stabilizers, and other additives are mixed without melting and kneading, and the mixture is used as a molding resin in a heating machine cylinder. It is also possible to carry out melt blending, so-called mold blending.
本発明にかかる成形品の製造方法は、特に制限はなく、公知の成形方法により成形することができるが、たとえば、射出成形で行う方法が挙げられる。 There is no restriction | limiting in particular in the manufacturing method of the molded article concerning this invention, Although it can shape | mold by a well-known shaping | molding method, For example, the method performed by injection molding is mentioned.
次に、本発明の実施例および比較例により詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Next, examples and comparative examples of the present invention will be described in detail, but the present invention is not limited to these examples.
実施例および比較例について、得られた再生熱可塑性樹脂組成物が、成形時に発生するガス量の減少度合を確認するために、ガス発生率で評価し、ガス発生率が５０％以下であるかと成形後の外観観察により、判断した。なお、ガス量の測定は、得られたペレット１０ｍｇについて、ガスクロマトグラフィー質量分析（ＧＣ／ＭＳ）にて、加熱温度２００〜２５０℃、３０分間の測定条件で行った時に発生したガス成分とし、ガス発生率は、吸油性無機化合物の添加前後で比較した。また、発生したガス種類が多いため、ガス発生量が最も多いステアリン酸およびパルミチン酸のガス発生量で比較した。 For the Examples and Comparative Examples, the obtained recycled thermoplastic resin compositions were evaluated by gas generation rate in order to confirm the degree of reduction in the amount of gas generated during molding, and whether the gas generation rate was 50% or less. Judgment was made by appearance observation after molding. In addition, the measurement of the gas amount is the gas component generated when the obtained pellets 10 mg are subjected to measurement conditions at a heating temperature of 200 to 250 ° C. for 30 minutes by gas chromatography mass spectrometry (GC / MS), The gas generation rate was compared before and after the addition of the oil-absorbing inorganic compound. Moreover, since there are many kinds of generated gas, the gas generation amount of stearic acid and palmitic acid with the largest gas generation amount was compared.
（外観評価）
外観評価には、射出成形機により作製した平板試験片（１００ｍｍ×１００ｍｍ×厚さ２ｍｍ）を用いた。該平板試験片について、光沢度を測定した。光沢度は、ＪＩＳ Ｚ８７４１「鏡面光沢度−測定方法」に準拠し、測定範囲を直径８ｍｍとし、変角光沢計により、入射角６０°−受光角６０°で測定を行った。外観判断基準は、ポリプロピレンおよびポリエチレン樹脂が光沢度が６０％以上、ポリスチレン、ＡＢＳ、ポリカーボネート樹脂が８０％以上であるものを合格（表では○）とした。
(Appearance evaluation)
A flat plate test piece (100 mm × 100 mm × thickness 2 mm) produced by an injection molding machine was used for appearance evaluation. The flatness test piece was measured for glossiness. The glossiness was measured according to JIS Z8741 “Specular Glossiness—Measurement Method”, with a measurement range of 8 mm in diameter, and with a gonioglossometer at an incident angle of 60 ° and a receiving angle of 60 °. Appearance criteria were determined to be acceptable (◯ in the table) for polypropylene and polyethylene resins having a glossiness of 60% or more and polystyrene, ABS, and polycarbonate resin of 80% or more.
＜実施例１＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）０．５重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．１重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 1>
Boehmite (oil absorption amount: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (C01 0.5 parts by weight, manufactured by Daimei Chemical Co., Ltd., 0.1 parts by weight of paraffin wax (Struktol RP11, manufactured by STRUKTOL) as a fluidity modifier, and decamethylenedicarboxylic acid disalicyloyl hydrazide (as heat resistance stabilizer) ADEKA STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADEKA STAB AO-60 , Manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) pho Phito (Adeka Stub 2112, manufactured by ADEKA) 0.05 parts by weight was added and mixed at 200 ° C. in an extruder while heating and melting to produce 3 to 5 mm pellets. . Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率４０％、光沢度６０％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例３に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 40% and a glossiness of 60%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 3 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５０ｍｌ／１００ｇ、比表面積：５．４ｍ２／ｇ、粒子径：１．０μｍ）（Ｈ−４２Ｍ、東新化成（株）製）１．０重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 2>
Α-alumina (oil absorption: 50 ml / 100 g, specific surface area: 5.4 m 2 / g, particle size: 1.100 parts by weight of polypropylene resin composition selected and collected from used home appliances as an oil-absorbing inorganic compound. 0 μm) (H-42M, manufactured by Toshin Kasei Co., Ltd.) 1.0 part by weight, 1.0 part by weight of stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) as a fluidity regulator, stable against heat 0.10 parts by weight of decamethylenedicarboxylic acid disalicyloyl hydrazide (ADEKA STAB CDA-6, manufactured by ADEKA Corporation) as an agent, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4 ′) -Hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) A mixture of 0.05 parts by weight of phosphite (Adeka Stub 2112, manufactured by ADEKA Corporation) added and mixed at 200 ° C. in an extruder while being heated and melted to produce 3 to 5 mm pellets did. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率４１％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例４に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 41% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 4 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例３＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）２．０重量部、流動性調整剤としてステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 3>
Calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (tobermorite) TK, manufactured by Nippon Insulation Co., Ltd.) 2.0 parts by weight, magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation) as a fluidity adjusting agent, 1.0 part by weight, decamethylene dicarboxylic as a heat stabilizer 0.10 parts by weight of acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] 0.05 parts by weight of methane (Adeka Stub AO-60, manufactured by ADEKA Corporation), Tris (2,4-di-) A mixture of 0.05 part by weight of t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Co., Ltd.) was mixed and kneaded in an extruder at 200 ° C. while heating and melting. A 5 mm pellet was prepared. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３０％、光沢度６４％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例５に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 30% and a glossiness of 64%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 5 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例４＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてカオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）３．０重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、ジオクタデシル−３，３’−チオジプロピオネート（ＤＳＴＰ「ヨシトミ」、（株）エーピーアイコーポレーション製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 4>
Kaolinite (oil absorption: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle diameter: 0.7 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances ( Neogen 2000 (manufactured by IMERYS) 3.0 parts by weight, stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight, ethylene bis-stearic acid amide (Alflow H-50L, manufactured by NOF CORPORATION) 1.0 parts by weight, heat decamethylene dicarboxylic acid disalicyloylhydrazide as stabilizers (STAB CDA-6, Ltd. ADEKA) 0.10 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADEKA 0.05 parts by weight of stub AO-60 (manufactured by ADEKA Corporation) and 0.05 parts by weight of dioctadecyl-3,3′-thiodipropionate (DSTP “Yoshitomi”, manufactured by API Corporation) Then, the mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３５％、光沢度６５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例６に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 65%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 6 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例５＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物として炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）５．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．２重量部、ステアリンステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤として、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 5>
Calcium carbonate (oil absorption: 70 ml / 100 g, specific surface area: 3.5 m 2 / g, particle size: 1.5 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances ) (Light calcium carbonate EC, manufactured by Kamishima Chemical Co., Ltd.) 5.0 parts by weight, paraffin wax (Struktol RP11, manufactured by STRUKTOL) as a fluidity adjusting agent 0.2 parts by weight, stearic stearate (Riquemar SL-800) , Manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight, and as a heat stabilizer, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adekastab CDA-6, manufactured by ADEKA Co., Ltd.) 0.10 part by weight, tetrakis [methylene- 3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane Add 0.05 parts by weight of ADK STAB AO-60, manufactured by ADEKA), 0.05 part by weight of Tris (2,4-di-t-butylphenyl) phosphite (ADEKA STAB 2112, manufactured by ADEKA) The mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率２５％、光沢度６８％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例７に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 25% and a glossiness of 68%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 7 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例６＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：８４ｍｌ／１００ｇ、比表面積：１６ｍ２／ｇ、粒子径：０．７μｍ）（Ｃ０６、大明化学工業（株）製）０．１重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．１重量部、カオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）０．１重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）０．２重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．２重量部、ステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 6>
Boehmite (oil absorption amount: 84 ml / 100 g, specific surface area: 16 m 2 / g, particle size: 0.7 μm) with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (C06 , Manufactured by Daimei Chemical Co., Ltd.), 0.1 part by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, manufactured by Nippon Insulation Co., Ltd.) ) 0.1 parts by weight, kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) (GlomaxLL, made by IMERYS) 0.1 parts by weight, calcium carbonate ( Oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 1.2 μm) (light and light calcium carbonate, manufactured by Kamishima Chemical Co., Ltd.) ) 0.2 parts by weight, 0.2 parts by weight of paraffin wax (Struktol RP11, manufactured by STRUKTOL) as a fluidity adjusting agent, 1.0 part by weight of magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation), Decamethylenedicarboxylic acid disalicyloyl hydrazide (ADEKA STAB CDA-6, manufactured by ADEKA) as a heat stabilizer, 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-) 4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, ADEKA Corporation) Made by adding 0.05 parts by weight and mixing in an extruder while heating and melting at 200 ° C. It knead | mixed and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３５％、光沢度６１％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例３に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 61%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 3 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例７＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：６０ｍｌ／１００ｇ、比表面積：５．９ｍ２／ｇ、粒子径：０．７μｍ）（ＬＳ−２５０、日本軽金属（株）製）０．２重量部、ケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）０．２重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）０．４重量部、炭酸カルシウム（吸油量：５３ｍｌ／１００ｇ、比表面積：１２ｍ２／ｇ、粒子径：０．１５μｍ）（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）０．２重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）０．５重量部、ステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）０．５重量部、耐熱安定剤として、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、ジオクタデシル−３，３’−チオジプロピオネート（ＤＳＴＰ「ヨシトミ」、（株）エーピーアイコーポレーション製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 7>
Α-alumina (oil absorption: 60 ml / 100 g, specific surface area: 5.9 m 2 / g, particle size: 0.00%) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. 7 μm) (LS-250, manufactured by Nippon Light Metal Co., Ltd.) 0.2 parts by weight, calcium silicate (oil absorption: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) (Zonolite XK, Nippon Insulation 0.2 parts by weight, Kaolinite (oil absorption: 62 ml / 100 g, specific surface area: 4.0 m 2 / g, particle size: 1.3 μm) (Optiwhite, manufactured by Shiraishi Calcium Co., Ltd.) 0.4 parts by weight of calcium carbonate (oil absorption: 53 ml / 100 g, a specific surface area: 12m 2 / g, particle diameter: 0.15μm) (Brilliant1500, Takumi Shiraishi 0.2 parts by weight manufactured by Co., Ltd., 0.5 parts by weight of stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.), magnesium stearate (magnesium stearate GR, NOF ( Co., Ltd.) 0.5 parts by weight, as a heat stabilizer, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA) 0.10 parts by weight, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (Adekastab AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, dioctadecyl-3,3'-thiodipropionate (DSTP “Yoshitomi”, manufactured by API Corporation) Add 0.05 parts by weight and mix at 200 ° C. It was kneaded in the extruder while molten, to prepare a pellet of 3 to 5 mm. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３８％、光沢度６１％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例４に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 38% and a glossiness of 61%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 4 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例８＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：２．３μｍ）（Ｃ２０、大明化学工業（株）製）１．０重量部、カオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）１．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．２重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）０．５重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 8>
Boehmite (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle diameter: 2.3 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (C20, manufactured by Daimei Chemical Industry Co., Ltd.) 1.0 part by weight, kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) (GlomaxLL, manufactured by IMERYS) ) 1.0 part by weight, 0.2 part by weight of paraffin wax (Struktol RP11, manufactured by STRUKTOL) as a fluidity adjusting agent, 0.5 part by weight of stearyl stearate (Riquemar SL-800, manufactured by Riken Vitamin Co., Ltd.), Decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation) as a heat stabilizer 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 weight Part and tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight were mixed and extruded at 200 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３５％、光沢度６０％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例５に比べて、成形時のガス発生量が格段に少ない再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 60%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 5 described later. It was found that this was a recycled polypropylene resin composition with much less gas generation.
＜実施例９＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５５ｍｌ／１００ｇ、比表面積：３．２ｍ２／ｇ、粒子径：０．８μｍ）（Ａ−１３−Ｍ、昭和電工（株）製）１．０重量部、ケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）２．０重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）１．０重量部、炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）１．０重量部、流動性調整剤としてエチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 9>
Α-alumina (oil absorption: 55 ml / 100 g, specific surface area: 3.2 m 2 / g, particle size: 0.00%) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. 8 μm) (A-13-M, Showa Denko Co., Ltd.) 1.0 part by weight, calcium silicate (oil absorption: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) (Zonolite XK, 2.0 parts by weight of Nippon Insulation Co., Ltd., kaolinite (oil absorption: 62 ml / 100 g, specific surface area: 4.0 m 2 / g, particle size: 1.3 μm) (Optiwhite, Shiraishi Calcium Co., Ltd.) Ltd.) 1.0 part by weight of calcium carbonate (oil absorption: 70 ml / 100 g, a specific surface area: 3.5 m 2 / g, particle diameter: 1.5 [mu] m) (light calcium carbonate EC, Konoshima Chemical Co., Ltd.) 1.0 parts by weight, ethylenebisstearic acid amide (Alflow H-50L, NOF Corporation) 1.0 parts by weight, stearyl stearate (Riquemar SL-800, Riken Vitamin) 1.0 part by weight manufactured by Co., Ltd., decamethylene dicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Co., Ltd.) 0.10 parts by weight, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) ) Extruder while adding 0.05 parts by weight of phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) and mixing at 200 ° C. while heating and melting By kneading a medium to prepare a pellet of 3 to 5 mm. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率２６％、光沢度６７％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例７に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 26% and a glossiness of 67%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 7 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１０＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：８４ｍｌ／１００ｇ、比表面積：１６ｍ２／ｇ、粒子径：０．７μｍ）（Ｃ０６、大明化学工業（株）製）０．２重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．５重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）０．２重量部、炭酸カルシウム（吸油量：５３ｍｌ／１００ｇ、比表面積：１２ｍ２／ｇ、粒子径：０．１５μｍ）（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）０．１重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．１重量部、ステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 10>
Boehmite (oil absorption amount: 84 ml / 100 g, specific surface area: 16 m 2 / g, particle size: 0.7 μm) with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (C06 0.2 parts by weight, manufactured by Daimei Chemical Co., Ltd., calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, manufactured by Nippon Insulation Co., Ltd.) ) 0.5 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle size: 0.7 μm) (Neogen 2000, manufactured by IMERYS) 0.2 parts by weight, calcium carbonate (oil absorption) : 53 ml / 100 g, specific surface area: 12 m 2 / g, particle size: 0.15 μm) (Brillant 1500, Shiroishi Kogyo Co., Ltd.) 0.1 part by weight, 0.1 part by weight of paraffin wax (Struktol RP11, manufactured by STRUKTOL), 1.0 part by weight of stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) , Decamethylenedicarboxylic acid disalicyloylhydrazide (ADEKA STAB CDA-6, manufactured by ADEKA Corporation) as a heat stabilizer, 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl) -4'-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, Co., Ltd.) (Made by ADEKA) Add 0.05 parts by weight and mix at 200 ° C while heating and melting. It knead | mixed in and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３７％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例４に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 37% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 4 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１１＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５５ｍｌ／１００ｇ、比表面積：３．２ｍ２／ｇ、粒子径：０．８μｍ）（Ａ−１３−Ｍ、昭和電工（株）製）１．０重量部、ベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）１．０重量部、ケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）１．０重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）１．０重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）１．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．２重量部、ステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）０．１重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）０．１重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 11>
Α-alumina (oil absorption: 55 ml / 100 g, specific surface area: 3.2 m 2 / g, particle size: 0.00%) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. 8 μm) (A-13-M, Showa Denko Co., Ltd.) 1.0 part by weight, boehmite (oil absorption: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) (C01, Daimei Chemical Industry Co., Ltd.) 1.0 part by weight, calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) (Tobermorite TK, manufactured by Nippon Insulation Co., Ltd.) 1 .0 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, a specific surface area: 15 m 2 / g, particle size: 0.7μm) (Neogen2000, IMERYS Co.) 1.0 fold Parts, calcium carbonate (oil absorption: 60 ml / 100 g, a specific surface area: 3.0 m 2 / g, particle diameter: 1.2 [mu] m) (minor resistance precipitated calcium carbonate, Konoshima Chemical Ltd. Co.) 1.0 part by weight, Paraffin wax (Struktol RP11, manufactured by STRUKTOL) 0.2 parts by weight, stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 0.1 parts by weight, ethylenebisstearic acid amide (Alflow) H-50L, manufactured by NOF Corporation) 0.1 parts by weight, stearyl stearate (Riquemar SL-800, manufactured by Riken Vitamin Co., Ltd.) 1.0 parts by weight, decamethylene dicarboxylate disalicylo as a heat stabilizer Ilhydrazide (ADEKA STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t- (Butylphenyl) phosphite (Adeka Stub 2112, manufactured by ADEKA) 0.05 parts by weight was mixed and kneaded in an extruder at 200 ° C. while being heated and melted. A pellet was prepared. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３０％、光沢度６８％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例７に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 30% and a glossiness of 68%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 7 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１２＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）１．０重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（ＮＥＯＧＥＮ２０００、ＩＭＥＲＹＳ社製）１．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 12>
Calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (tobermorite) TK, manufactured by Nippon Insulation Co., Ltd., 1.0 part by weight, kaolinite (oil absorption: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle size: 0.7 μm) (NEOGEN2000, manufactured by IMERYS) 0 parts by weight, paraffin wax (Struktol RP11, manufactured by STRUKTOL) 0.4 parts by weight as a fluidity modifier, decamethylene dicarboxylic acid disalicyloyl hydrazide (Adekastab CDA-6, manufactured by ADEKA Corporation) as a heat stabilizer 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′- -T-butyl-4'-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112 , Manufactured by ADEKA Co., Ltd.) 0.05 parts by weight was added and mixed at 200 ° C. in an extruder while being heated and melted to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３５％、光沢度６１％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例５に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 61%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 5 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１３＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：６０ｍｌ／１００ｇ、比表面積：５．９ｍ２／ｇ、粒子径：０．７μｍ）（ＬＳ−２５０、日本軽金属（株）製）０．２重量部、ケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）０．２重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）０．１重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．１重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 13>
Α-alumina (oil absorption: 60 ml / 100 g, specific surface area: 5.9 m 2 / g, particle size: 0.00%) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances. 7 μm) (LS-250, manufactured by Nippon Light Metal Co., Ltd.) 0.2 parts by weight, calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) (Tobermorite TK, Nippon Insulation) Ration Co., Ltd.) 0.2 parts by weight, calcium carbonate (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 1.2 μm) (light and light calcium carbonate, Kamishima Chemical Industries ( Co., Ltd.) 0.1 part by weight, paraffin wax (Struktol RP11, manufactured by STRUKTOL) 0.1 part by weight as a fluidity modifier, ethylene bisste 1.0 parts by weight of phosphoric acid amide (Alflow H-50L, NOF Corporation), decamethylene dicarboxylic acid disalicyloyl hydrazide (ADK STAB CDA-6, manufactured by ADEKA Corporation) 0.10 as a heat stabilizer Parts by weight, 0.05 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation), Tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight was added and mixed in an extruder while being heated and melted at 200 ° C. And kneaded to prepare 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表１に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率４３％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例３に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 1 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 43% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 3 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１４＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：２．３μｍ）（Ｃ２０、大明化学工業（株）製）０．２重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．２重量部、カオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）０．１重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＲＰ１１、ＳＴＲＵＫＴＯＬ社製）０．１重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 14>
Boehmite (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle diameter: 2.3 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition selected and collected from used home appliances (C20, manufactured by Daimei Chemical Co., Ltd.) 0.2 parts by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, Nippon Insulation Co., Ltd. )) 0.2 parts by weight, kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) (GlomaxLL, made by IMERYS) 0.1 parts by weight, flow 0.1 parts by weight of paraffin wax (Struktol RP11, manufactured by STRUKTOL) as a property modifier, and decamethylene dicarbo as a heat stabilizer 0.10 parts by weight of disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) Propionate] methane (Adeka Stub AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t-butylphenyl) phosphite (Adeka Stub 2112, manufactured by ADEKA Corporation) 0.05 weight The part added and mixed was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３８％、光沢度６３％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例３に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 38% and a glossiness of 63%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 3 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１５＞
使用済み家電製品より選別回収したポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５０ｍｌ／１００ｇ、比表面積：５．４ｍ２／ｇ、粒子径：１．０μｍ）（Ｈ−４２Ｍ、東新化成（株）製）２．０重量部、ケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）１．０重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）２．０重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 15>
Α-alumina (oil absorption: 50 ml / 100 g, specific surface area: 5.4 m 2 / g, particle size: 1.100 parts by weight of polypropylene resin composition selected and collected from used home appliances as an oil-absorbing inorganic compound. 0 μm) (H-42M, manufactured by Toshin Kasei Co., Ltd.) 2.0 parts by weight, calcium silicate (oil absorption: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) (Zonolite XK, Japan 1.0 part by weight of Insulation Co., Ltd., calcium carbonate (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 1.2 μm) (light and light calcium carbonate, Kamishima Chemical Industries) 2.0 parts by weight manufactured by Co., Ltd., 1.0 part by weight of stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.), ethylene bis Arymic acid amide (Alflow H-50L, manufactured by NOF Corporation) 1.0 part by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (ADK STAB CDA-6, manufactured by ADEKA Corporation) 0.10 as a heat stabilizer Parts by weight, 0.05 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation), Tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight was added and mixed in an extruder while being heated and melted at 200 ° C. And kneaded to produce 3-5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られたペレットを用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリプロピレン樹脂組成物は、ガス発生率３０％、光沢度６５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例７に比べて、成形品表面の外観意匠性に優れた再生ポリプロピレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and glossiness using the obtained pellets. As a result, the recycled polypropylene resin composition of the present invention has a gas generation rate of 30% and a glossiness of 65%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 7 described later. It turned out that it is the reproduction | regeneration polypropylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１６＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）０．５重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０１６、ＳＴＲＵＫＴＯＬ社製）０．１重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 16>
Calcium silicate (oil absorption amount: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of polyethylene resin composition selected and collected from used household electrical appliances (Zonolite XK, manufactured by Nippon Insulation Co., Ltd.) 0.5 parts by weight, paraffin wax (Struktol TR016, manufactured by STRUKTOL) 0.1 part by weight as a fluidity regulator, decamethylenedicarboxylic acid disalicyloyl hydrazide as a heat stabilizer (ADK STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO— 60, 0.05 part by weight (manufactured by ADEKA Corporation), Tris (2,4-di-) -Butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was mixed and kneaded in an extruder at 200 ° C. while being heated and melted. A pellet was prepared. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリエチレン樹脂組成物は、ガス発生率３９％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例９に比べて、成形品表面の外観意匠性に優れた再生ポリエチレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition of the present invention has a gas generation rate of 39% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 9 described later. It turned out that it is the reproduction | regeneration polyethylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１７＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：８４ｍｌ／１００ｇ、比表面積：１６ｍ２／ｇ、粒子径：０．７μｍ）（Ｃ０６、大明化学工業（株）製）０．３重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）０．２重量部、流動性調整剤としてステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、ジオクタデシル−３，３’−チオジプロピオネート（ＤＳＴＰ「ヨシトミ」、（株）エーピーアイコーポレーション製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 17>
Boehmite (oil absorption amount: 84 ml / 100 g, specific surface area: 16 m 2 / g, particle size: 0.7 μm) with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances (C06 , Manufactured by Daimei Chemical Co., Ltd.), 0.3 parts by weight, kaolinite (oil absorption: 62 ml / 100 g, specific surface area: 4.0 m 2 / g, particle size: 1.3 μm) (Optiwhite, Shiroishi Calcium Co., Ltd. )) 0.2 parts by weight, magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation) as a fluidity adjusting agent, 1.0 parts by weight as a heat stabilizer, decamethylenedicarboxylic acid disalicyloyl hydrazide ( ADEKA STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydro Cyphenyl) propionate] methane (Adeka Stub AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, dioctadecyl-3,3′-thiodipropionate (DSTP “Yoshitomi”, manufactured by API Corporation) 0 The mixture obtained by adding 0.05 parts by weight was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリエチレン樹脂組成物は、ガス発生率４０％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例９に比べて、成形品表面の外観意匠性に優れた再生ポリエチレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition of the present invention has a gas generation rate of 40% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 9 described later. It turned out that it is the reproduction | regeneration polyethylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１８＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：６０ｍｌ／１００ｇ、比表面積：５．９ｍ２／ｇ、粒子径：０．７μｍ）（ＬＳ−２５０、日本軽金属（株）製）０．５重量部、炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）０．５重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）０．５重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）０．５重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 18>
Α-alumina (oil absorption: 60 ml / 100 g, specific surface area: 5.9 m 2 / g, particle size: 0.1%) with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances. 7 μm) (LS-250, manufactured by Nippon Light Metal Co., Ltd.) 0.5 parts by weight, calcium carbonate (oil absorption: 70 ml / 100 g, specific surface area: 3.5 m 2 / g, particle size: 1.5 μm) (light carbonic acid 0.5 parts by weight of calcium EC, manufactured by Kamishima Chemical Co., Ltd., 0.5 parts by weight of stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.), ethylenebisstearic acid amide ( Alfro H-50L, manufactured by NOF Corporation) 0.5 parts by weight, decamethylene dicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, as heat stabilizer) ADEKA Co., Ltd.) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, ADEKA Corporation) 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) and mixed at 200 ° C. The mixture was kneaded in an extruder while being heated and melted to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリエチレン樹脂組成物は、ガス発生率４１％、光沢度６２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１０に比べて、成形品表面の外観意匠性に優れた再生ポリエチレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition of the present invention has a gas generation rate of 41% and a glossiness of 62%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 10 described later. It turned out that it is the reproduction | regeneration polyethylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例１９＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５５ｍｌ／１００ｇ、比表面積：３．２ｍ２／ｇ、粒子径：０．８μｍ）（Ａ−１３−Ｍ、昭和電工（株）製）０．４重量部、ベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）０．４重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．４重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）０．４重量部、炭酸カルシウム（吸油量：５３ｍｌ／１００ｇ、比表面積：１２ｍ２／ｇ、粒子径：０．１５μｍ）（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）０．４重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０１６、ＳＴＲＵＫＴＯＬ社製）０．１重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 19>
Α-alumina (oil absorption: 55 ml / 100 g, specific surface area: 3.2 m 2 / g, particle size: 0.1%) with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances. 8 μm) (A-13-M, manufactured by Showa Denko KK) 0.4 parts by weight, boehmite (oil absorption: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) (C01, Daimei Chemical Industry Co., Ltd.) 0.4 parts by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, manufactured by Nippon Insulation Co., Ltd.) 0 .4 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, a specific surface area: 15 m 2 / g, particle size: 0.7μm) (Neogen2000, IMERYS Co.) 0.4 wt , Calcium carbonate (oil absorption: 53 ml / 100 g, a specific surface area: 12m 2 / g, particle diameter: 0.15μm) (Brilliant1500, Shiraishi Kogyo Co.) 0.4 parts by weight of paraffin wax as a fluidity modifier ( Struktol TR016, made by STRUKTOL) 0.1 parts by weight, stearyl stearate (Riquemar SL-800, made by Riken Vitamin Co., Ltd.) 1.0 parts by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adekastab) CDA-6 (manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Adeka Stab AO-60, (Manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t-butylpheny) Lu) Phosphite (Adeka Stub 2112, manufactured by ADEKA) 0.05 parts by weight was added and mixed at 200 ° C. in an extruder while being heated and melted, and 3 to 5 mm pellets Was made. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリエチレン樹脂組成物は、ガス発生率３５％、光沢度６４％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１１に比べて、成形品表面の外観意匠性に優れた再生ポリエチレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 64%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 11 described later. It turned out that it is the reproduction | regeneration polyethylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２０＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：２．３μｍ）（Ｃ２０、大明化学工業（株）製）２．０重量部、ケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）１．０重量部、炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）２．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０１６、ＳＴＲＵＫＴＯＬ社製）１．０重量部、ステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）０．５重量部、ステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）０．５重量部、耐熱安定剤としてデカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−t−ブチル−4’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、ジオクタデシル−３，３’−チオジプロピオネート（ＤＳＴＰ「ヨシトミ」、（株）エーピーアイコーポレーション製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Example 20>
Boehmite (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 2.3 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances (C20, manufactured by Daimei Chemical Co., Ltd.) 2.0 parts by weight, calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) (Tobermorite TK, Nippon Insulation Co., Ltd. )) 1.0 parts by weight, calcium carbonate (oil absorption: 70 ml / 100 g, specific surface area: 3.5 m 2 / g, particle size: 1.5 μm) (light calcium carbonate EC, manufactured by Kamishima Chemical Co., Ltd.) 2.0 parts by weight, 1.0 part by weight of paraffin wax (Struktol TR016, manufactured by STRUKTOL) as a fluidity adjusting agent, monoglyceryl stearate 0.5 parts by weight (Rikemar S-100A, manufactured by Riken Vitamin Co., Ltd.), 0.5 parts by weight of magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation), decamethylene dicarboxylic acid as a heat stabilizer 0.10 parts by weight of disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] Methane (Adeka Stub AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, dioctadecyl-3,3′-thiodipropionate (DSTP “Yoshitomi”, manufactured by API Corporation) 0.05 part by weight Was added and mixed at 200 ° C. in an extruder while being heated and melted to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表２に示す。この結果、本発明の再生ポリエチレン樹脂組成物は、ガス発生率２８％、光沢度６５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１２に比べて、成形品表面の外観意匠性に優れた再生ポリエチレン樹脂組成物であることが分かった。 Table 2 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition of the present invention has a gas generation rate of 28% and a glossiness of 65%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 12 described later. It turned out that it is the reproduction | regeneration polyethylene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２１＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）０．５重量部、流動性調整剤としてステアリルアテアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Example 21>
Calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances (tobermorite) TK, manufactured by Nippon Insulation Co., Ltd.) 0.5 parts by weight, stearyl attearate (Riquemar SL-800, manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight as a fluidity regulator, stearyl β- as a heat stabilizer (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) Add 0.05 parts by weight and mix at 220 ° C. with heating. It was kneaded in the extruder while, to prepare a pellet of 3 to 5 mm. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリスチレン樹脂組成物は、ガス発生率３５％、光沢度８０％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１４に比べて、成形品表面の外観意匠性に優れた再生ポリスチレン樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition of the present invention has a gas generation rate of 35% and a glossiness of 80%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 14 described later. It turned out that it is the reproduction | regeneration polystyrene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２２＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５０ｍｌ／１００ｇ、比表面積：５．４ｍ２／ｇ、粒子径：１．０μｍ）（Ｈ−４２Ｍ、東新化成（株）製）０．１重量部、ベーマイト（吸油量：８４ｍｌ／１００ｇ、比表面積：１６ｍ２／ｇ、粒子径：０．７μｍ）（Ｃ０６、大明化学工業（株）製）０．１重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．１重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）０．１重量部、炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）０．１重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０７１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Example 22>
Α-alumina (oil absorption: 50 ml / 100 g, specific surface area: 5.4 m 2 / g, particle size: 1.100 parts by weight of polystyrene resin composition selected and collected from used home appliances as an oil-absorbing inorganic compound. 0 μm) (H-42M, manufactured by Toshin Kasei Co., Ltd.) 0.1 parts by weight, boehmite (oil absorption: 84 ml / 100 g, specific surface area: 16 m 2 / g, particle size: 0.7 μm) (C06, Daimei Chemical) Kogyo Co., Ltd.) 0.1 parts by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, Nippon Insulation Co., Ltd.) 1 part by weight, kaolinite (oil absorption: 62 ml / 100 g, a specific surface area: 4.0 m 2 / g, particle size: 1.3 .mu.m) (Opti White, manufactured by Shiraishi calcium Co.) 0.1 parts by weight, coal Calcium (oil absorption: 70 ml / 100 g, a specific surface area: 3.5 m 2 / g, particle diameter: 1.5 [mu] m) (manufactured by precipitated calcium carbonate EC, Konoshima Chemical Co.) 0.1 parts by weight, fluidity modifier Paraffin wax (Struktol TR071, manufactured by STRUKTOL) 0.4 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, Co., Ltd.) as heat stabilizer ADEKA) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, ADEKA Co., Ltd.) 0.05 parts by weight were added and mixed, Then, the mixture was kneaded in an extruder while being heated and melted to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリスチレン樹脂組成物は、ガス発生率４０％、光沢度８１％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１４に比べて、成形品表面の外観意匠性に優れた再生ポリスチレン樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition of the present invention has a gas generation rate of 40% and a glossiness of 81%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 14 described later. It turned out that it is the reproduction | regeneration polystyrene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２３＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５０ｍｌ／１００ｇ、比表面積：５．４ｍ２／ｇ、粒子径：１．０μｍ）（Ｈ−４２Ｍ、東新化成（株）製）０．３重量部、ケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）０．１重量部、カオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）０．３重量部、炭酸カルシウム（吸油量：５３ｍｌ／１００ｇ、比表面積：１２ｍ２／ｇ、粒子径：０．１５μｍ）（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）０．３重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０７１、ＳＴＲＵＫＴＯＬ社製）０．１重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Example 23>
Α-alumina (oil absorption: 50 ml / 100 g, specific surface area: 5.4 m 2 / g, particle size: 1.100 parts by weight of polystyrene resin composition selected and collected from used home appliances as an oil-absorbing inorganic compound. 0 μm) (H-42M, manufactured by Toshin Kasei Co., Ltd.) 0.3 parts by weight, calcium silicate (oil absorption: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) (Zonolite XK, Japan 0.1 parts by weight of Insulation Co., Ltd., kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) (GlomaxLL, manufactured by IMERYS) 0.3 parts of calcium carbonate (oil absorption: 53 ml / 100 g, a specific surface area: 12m 2 / g, particle diameter: 0.15μm) (Brilliant1500, Shiraishi Kogyo Co., 0.3 parts by weight, 0.1 part by weight of paraffin wax (Struktol TR071, made by STRUKTOL) as a fluidity adjusting agent, 1.0 part by weight of ethylenebisstearic acid amide (Alflow H-50L, made by NOF Corporation) , Stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA) as a heat stabilizer, 0.05 parts by weight, Tris (2,4-di -T-Butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was added and mixed at 220 ° C. in an extruder while being heated and melted. ˜5 mm pellets were made. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリスチレン樹脂組成物は、ガス発生率３６％、光沢度８４％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１５に比べて、成形品表面の外観意匠性に優れた再生ポリスチレン樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition of the present invention has a gas generation rate of 36% and a glossiness of 84%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 15 described later. It turned out that it is the reproduction | regeneration polystyrene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２４＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：２．３μｍ）（Ｃ２０、大明化学工業（株）製）１．０重量部、ケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）２．０重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）１．０重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）１．０重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Example 24>
Boehmite (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle diameter: 2.3 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances (C20, manufactured by Daimei Chemical Co., Ltd.) 1.0 part by weight, calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) (Tobermorite TK, Nippon Insulation Co., Ltd. )) 2.0 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle size: 0.7 μm) (Neogen 2000, manufactured by IMERYS) 1.0 part by weight, calcium carbonate ( Oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 1.2 μm) (light, light calcium carbonate, Kamishima Chemical Co., Ltd. )) 1.0 part by weight, stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight, stearyl stearate (Riquemar SL-800, Riken Vitamin Co., Ltd.) 1.0 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA) 0.05 parts by weight as a heat stabilizer A mixture of 0.05 part by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Co., Ltd.) mixed and heated at 220 ° C. while being melted by heating. It knead | mixed in and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリスチレン樹脂組成物は、ガス発生率２５％、光沢度８９％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１６に比べて、成形品表面の外観意匠性に優れた再生ポリスチレン樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition of the present invention has a gas generation rate of 25% and a glossiness of 89%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 16 described later. It turned out that it is the reproduction | regeneration polystyrene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２５＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）３．０重量部、カオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）２．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ０７１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、エチレンビスステアリン酸アミド（アルフローＨ−５０Ｌ、日油（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Example 25>
Boehmite (oil absorption amount: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances (C01 , Manufactured by Daimei Chemical Co., Ltd.), 3.0 parts by weight, kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) (GlomaxLL, manufactured by IMERYS) 2 0.0 part by weight, paraffin wax (Struktol TR071, manufactured by STRUKTOL) 0.4 part by weight, ethylenebisstearic acid amide (Alflow H-50L, manufactured by NOF Corporation) as a fluidity modifier, Stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB) as a heat stabilizer 0.05 parts by weight of O-50, manufactured by ADEKA), 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) The mixture was kneaded in an extruder while being heated and melted at 220 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリスチレン樹脂組成物は、ガス発生率２４％、光沢度９０％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１６に比べて、成形品表面の外観意匠性に優れた再生ポリスチレン樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition of the present invention has a gas generation rate of 24% and a glossiness of 90%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 16 described later. It turned out that it is the reproduction | regeneration polystyrene resin composition excellent in the external appearance design property of the goods surface.
＜実施例２６＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、吸油性無機化合物としてカオリナイト（吸油量：６０ｍｌ／１００ｇ、比表面積：９．０ｍ２／ｇ、粒子径：１．５μｍ）（ＧｌｏｍａｘＬＬ、ＩＭＥＲＹＳ社製）０．５重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ２５１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Example 26>
Kaolinite (oil absorption: 60 ml / 100 g, specific surface area: 9.0 m 2 / g, particle size: 1.5 μm) with respect to 100 parts by weight of ABS resin composition selected and collected from used home appliances ) (GlomaxLL, made by IMERYS) 0.5 parts by weight, paraffin wax (Struktol TR251, made by STRUKTOL) as a fluidity adjusting agent 0.4 parts by weight, stearyl β- (3,5-di-t as a heat stabilizer -Butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, ADEKA Corporation) Made by adding 0.05 parts by weight in an extruder while heating and melting at 240 ° C. It knead | mixed and produced the 3-5 mm pellet. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ＡＢＳ樹脂組成物は、ガス発生率３６％、光沢度８５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１８に比べて、成形品表面の外観意匠性に優れた再生ＡＢＳ機脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition of the present invention has a gas generation rate of 36% and a glossiness of 85%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 18 described later. It was found to be a recycled ABS machine oil composition having an excellent appearance design on the product surface.
＜実施例２７＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：６０ｍｌ／１００ｇ、比表面積：５．９ｍ２／ｇ、粒子径：０．７μｍ）（ＬＳ−２５０、日本軽金属（株）製）０．１重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）０．２重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）０．２重量部、流動性調整剤としてステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Example 27>
Α-alumina (oil absorption: 60 ml / 100 g, specific surface area: 5.9 m 2 / g, particle size: 0.8%) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the ABS resin composition selected and collected from used home appliances. 7 μm) (LS-250, manufactured by Nippon Light Metal Co., Ltd.) 0.1 parts by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, Nippon Insulation) 0.2 parts by weight, Kaolinite (oil absorption: 62 ml / 100 g, specific surface area: 4.0 m 2 / g, particle size: 1.3 μm) (Optiwhite, manufactured by Shiraishi Calcium Co., Ltd.) 0.2 part by weight, stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight as a fluidity regulator, stearyl β- as a heat stabilizer (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (Adeka Stub 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was added and mixed at 240 ° C. while being heated and melted, and kneaded in an extruder to produce 3 to 5 mm pellets. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ＡＢＳ樹脂組成物は、ガス発生率４１％、光沢度８５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１８に比べて、成形品表面の外観意匠性に優れた再生ＡＢＳ樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition of the present invention has a gas generation rate of 41% and a glossiness of 85%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 18 described later. It was found to be a recycled ABS resin composition excellent in appearance design on the surface of the product.
＜実施例２８＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）０．５重量部、ケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）０．２重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）０．３重量部、流動性調整剤としてステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）０．５重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）０．５重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Example 28>
Boehmite (oil absorption amount: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the ABS resin composition selected and collected from used home appliances (C01 0.5 parts by weight, manufactured by Daimei Chemical Co., Ltd., calcium silicate (oil absorption: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) (Zonolite XK, manufactured by Nippon Insulation Co., Ltd.) ) 0.2 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle size: 0.7 μm) (Neogen 2000, manufactured by IMERYS) 0.3 parts by weight, as a fluidity regulator Magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation) 0.5 parts by weight, stearyl stearate (Riquemar S -800, manufactured by Riken Vitamin Co., Ltd.) 0.5 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, ADEKA Corporation) as a heat stabilizer 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) and mixed at 240 ° C. The mixture was kneaded in an extruder while being heated and melted to produce 3 to 5 mm pellets. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ＡＢＳ樹脂組成物は、ガス発生率３４％、光沢度９０％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例１９に比べて、成形品表面の外観意匠性に優れた再生ＡＢＳ樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition of the present invention has a gas generation rate of 34% and a glossiness of 90%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 19 described later. It was found to be a recycled ABS resin composition excellent in appearance design on the surface of the product.
＜実施例２９＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、吸油性無機化合物としてα−アルミナ（吸油量：５５ｍｌ／１００ｇ、比表面積：３．２ｍ２／ｇ、粒子径：０．８μｍ）（Ａ−１３−Ｍ、昭和電工（株）製）１．０重量部、ベーマイト（吸油量：８４ｍｌ／１００ｇ、比表面積：１６ｍ２／ｇ、粒子径：０．７μｍ）（Ｃ０６、大明化学工業（株）製）１．０重量部、ケイ酸カルシウム（吸油量：６２０ｍｌ／１００ｇ、比表面積：５６ｍ２／ｇ、粒子径：２４μｍ）（トバモライトＴＫ、日本インシュレーション（株）製）１．０重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）１．０重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）１．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ２５１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、ステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）１．０重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Example 29>
With respect to 100 parts by weight of the ABS resin composition selected and collected from the used home appliance, α-alumina (oil absorption amount: 55 ml / 100 g, specific surface area: 3.2 m 2 / g, particle size: 0.8%) as an oil-absorbing inorganic compound. 8 μm) (A-13-M, manufactured by Showa Denko KK) 1.0 part by weight, boehmite (oil absorption: 84 ml / 100 g, specific surface area: 16 m 2 / g, particle size: 0.7 μm) (C06, Daimei Chemical Industry Co., Ltd.) 1.0 part by weight, calcium silicate (oil absorption: 620 ml / 100 g, specific surface area: 56 m 2 / g, particle size: 24 μm) (Tobermorite TK, manufactured by Nippon Insulation Co., Ltd.) 1 .0 parts by weight, kaolinite (oil absorption: 120 ml / 100 g, a specific surface area: 15 m 2 / g, particle size: 0.7μm) (Neogen2000, IMERYS Co.) 1.0 part by weight, carbonate Ca Siumu (oil absorption: 60 ml / 100 g, a specific surface area: 3.0 m 2 / g, particle diameter: 1.2 [mu] m) (minor resistance precipitated calcium carbonate, manufactured by Konoshima Chemical Co.) 1.0 parts by weight, fluidity modifier Paraffin wax (Struktol TR251, STRUKTOL) 0.4 parts by weight, magnesium stearate (magnesium stearate GR, NOF Corporation) 1.0 parts by weight, stearyl stearate (Riquemar SL-800, RIKEN) Vitamin Co., Ltd.) 1.0 part by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Adekastab AO-50, manufactured by ADEKA Co.) as a heat stabilizer. 05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, ADEKA Corporation) ) A mixture by adding 0.05 part by weight, at 240 ° C., and kneaded in an extruder while heating and melting, to prepare a pellet of 3 to 5 mm. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ＡＢＳ樹脂組成物は、ガス発生率２６％、光沢度９２％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例２０に比べて、成形品表面の外観意匠性に優れた再生ＡＢＳ樹脂組成物であることがわかった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition of the present invention has a gas generation rate of 26% and a glossiness of 92%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 20 described later. It was found to be a recycled ABS resin composition excellent in the appearance design of the product surface.
＜実施例３０＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：２．３μｍ）（Ｃ２０、大明化学工業（株）製）２．０重量部、カオリナイト（吸油量：１２０ｍｌ／１００ｇ、比表面積：１５ｍ２／ｇ、粒子径：０．７μｍ）（Ｎｅｏｇｅｎ２０００、ＩＭＥＲＹＳ社製）１．０重量部、炭酸カルシウム（吸油量：７０ｍｌ／１００ｇ、比表面積：３．５ｍ２／ｇ、粒子径：１．５μｍ）（軽質炭酸カルシウムＥＣ、神島化学工業（株）製）２．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ２５１、ＳＴＲＵＫＴＯＬ社製）１．０重量部、ステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Example 30>
Boehmite (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 2.3 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the ABS resin composition selected and collected from used home appliances (C20, manufactured by Daimei Chemical Co., Ltd.) 2.0 parts by weight, kaolinite (oil absorption amount: 120 ml / 100 g, specific surface area: 15 m 2 / g, particle size: 0.7 μm) (Neogen 2000, manufactured by IMERYS) 1 0.0 part by weight, calcium carbonate (oil absorption: 70 ml / 100 g, specific surface area: 3.5 m 2 / g, particle size: 1.5 μm) (light calcium carbonate EC, manufactured by Kamishima Chemical Co., Ltd.) 2.0 weight Parts, 1.0 part by weight of paraffin wax (Struktol TR251, STRUKTOL) as a fluidity modifier, stearyl stearate (Riquemar SL-8) 00, manufactured by Riken Vitamin Co., Ltd.) 1.0 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) as a heat stabilizer ) 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed at 240 ° C. While heating and melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ＡＢＳ樹脂組成物は、ガス発生率３７％、光沢度８９％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例２０に比べて、成形品表面の外観意匠性に優れた再生ＡＢＳ樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition of the present invention has a gas generation rate of 37% and a glossiness of 89%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 20 described later. It was found to be a recycled ABS resin composition excellent in appearance design on the surface of the product.
＜実施例３１＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、吸油性無機化合物として炭酸カルシウム（吸油量：５３ｍｌ／100ｇ、比表面積：１２ｍ２／ｇ、粒子径：０．１５μｍ）（Ｂｒｉｌｌｉａｎｔ１５００、白石工業（株）製）０．５重量部、流動性調整剤としてステアリン酸マグネシウム（マグネシウムステアレートＧＲ、日油（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Example 31>
Calcium carbonate (oil absorption: 53 ml / 100 g, specific surface area: 12 m 2 / g, particle size: 0.15 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances ( Brilliant 1500, manufactured by Shiroishi Kogyo Co., Ltd.) 0.5 parts by weight, magnesium stearate (magnesium stearate GR, manufactured by NOF Corporation) as a fluidity regulator, stearyl β- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite ( ADK STAB 2112 (manufactured by ADEKA Co., Ltd.) was added and mixed with 0.05 parts by weight, and heated and melted at 260 ° C. It was kneaded in a reluctant extruder to prepare a pellet of 3 to 5 mm. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリカーボネート樹脂組成物は、ガス発生率４５％、光沢度８５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例２２に比べて、成形品表面の外観意匠性に優れた再生ポリカーボネート樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition of the present invention has a gas generation rate of 45% and a glossiness of 85%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 22 described later. It turned out that it is the reproduction | regeneration polycarbonate resin composition excellent in the external appearance design property of the product surface.
＜実施例３２＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、吸油性無機化合物としてケイ酸カルシウム（吸油量：４８０ｍｌ／１００ｇ、比表面積：５０ｍ２／ｇ、粒子径：４７μｍ）（ゾノトライトＸＫ、日本インシュレーション（株）製）０．３重量部、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）０．２重量部、流動性調整剤としてステアリルステアレート（リケマールＳＬ−８００、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Example 32>
Calcium silicate (oil absorption amount: 480 ml / 100 g, specific surface area: 50 m 2 / g, particle size: 47 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances (zonotlite) XK, manufactured by Nippon Insulation Co., Ltd. 0.3 parts by weight, calcium carbonate (oil absorption: 60 ml / 100 g, specific surface area: 3.0 m 2 / g, particle size: 1.2 μm) (light and light calcium carbonate, 0.2 parts by weight (manufactured by Kamishima Chemical Co., Ltd.), 1.0 parts by weight of stearyl stearate (Riquemar SL-800, manufactured by Riken Vitamin Co., Ltd.) as a fluidity regulator, and stearyl β- (3 , 5-Di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 weight Part, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight was mixed and extruded at 260 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリカーボネート樹脂組成物は、ガス発生率３９％、光沢度８７％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例２２に比べて、成形品表面の外観意匠性に優れた再生ポリカーボネート樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition of the present invention has a gas generation rate of 39% and a glossiness of 87%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 22 described later. It turned out that it is the reproduction | regeneration polycarbonate resin composition excellent in the external appearance design property of the product surface.
＜実施例３３＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、吸油性無機化合物としてベーマイト（吸油量：２２０ｍｌ／１００ｇ、比表面積：１１０ｍ２／ｇ、粒子径：０．１μｍ）（Ｃ０１、大明化学工業（株）製）１．０重量部、ケイ酸カルシウム（吸油量：４４０ｍｌ／１００ｇ、比表面積：５５ｍ２／ｇ、粒子径：１７μｍ）（トバモライトＴＪ、日本インシュレーション（株）製）３．０重量部、カオリナイト（吸油量：６２ｍｌ／１００ｇ、比表面積：４．０ｍ２／ｇ、粒子径：１．３μｍ）（オプチホワイト、白石カルシウム（株）製）１．０重量部、流動性調整剤としてパラフィンワックス（Ｓｔｒｕｋｔｏｌ ＴＲ２５１、ＳＴＲＵＫＴＯＬ社製）０．４重量部、ステアリン酸モノグリセリド（リケマールＳ−１００Ａ、理研ビタミン（株）製）１．０重量部、耐熱安定剤としてステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Example 33>
Boehmite (oil absorption amount: 220 ml / 100 g, specific surface area: 110 m 2 / g, particle size: 0.1 μm) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances (C01 , Manufactured by Daimei Chemical Co., Ltd.) 1.0 part by weight, calcium silicate (oil absorption: 440 ml / 100 g, specific surface area: 55 m 2 / g, particle size: 17 μm) (Tobermorite TJ, manufactured by Nippon Insulation Co., Ltd.) ) 3.0 parts by weight, kaolinite (oil absorption: 62 ml / 100 g, specific surface area: 4.0 m 2 / g, particle size: 1.3 μm) (Optiwhite, manufactured by Shiroishi Calcium Co., Ltd.) 1.0 part by weight , 0.4 parts by weight of paraffin wax (Struktol TR251, STRUKTOL) as a fluidity regulator, stearic acid monoglyceride (Riquemar S-100A, manufactured by Riken Vitamin Co., Ltd.) 1.0 part by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, ( What was added and mixed with 0.05 parts by weight of ADEKA Co., Ltd.), 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (Adeka Stub 2112, ADEKA Co., Ltd.) The mixture was kneaded in an extruder while being heated and melted at 260 ° C. to produce 3 to 5 mm pellets. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表３に示す。この結果、本発明の再生ポリカーボネート樹脂組成物は、ガス発生率２２％、光沢度９５％であり、成形時のガス発生量が少なく、外観が良好で、後述する比較例２３に比べて、成形品表面の外観意匠性に優れた再生ポリカーボネート樹脂組成物であることが分かった。 Table 3 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition of the present invention has a gas generation rate of 22% and a glossiness of 95%, has a small amount of gas generation during molding, has a good appearance, and is molded as compared with Comparative Example 23 described later. It turned out that it is the reproduction | regeneration polycarbonate resin composition excellent in the external appearance design property of the product surface.
＜比較例１＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 1>
Decamethylenedicarboxylic acid disalicyloyl hydrazide (Adekastab CDA-6, manufactured by ADEKA Corp.) with respect to 100 parts by weight of the polypropylene resin composition which is collected and collected from used home appliances and is not subjected to density sorting or surface polishing. 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 weight Part and tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight were mixed and extruded at 200 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率１００％、光沢度５８％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition had a gas generation rate of 100% and a glossiness of 58%, had a large amount of gas generation during molding, and had a poor appearance.
＜比較例２＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、吸油性無機化合物として、炭酸カルシウム（吸油量：６０ｍｌ／１００ｇ、比表面積：３．０ｍ２／ｇ、粒子径：１．２μｍ）（軽微性軽質炭酸カルシウム、神島化学工業（株）製）０．１重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative example 2>
Calcium carbonate (oil absorption: 60 ml / 100 g, specific surface area: 3.3) as an oil-absorbing inorganic compound with respect to 100 parts by weight of the polypropylene resin composition that has been collected and collected from used home appliances and has not been subjected to density sorting or surface polishing. 0 m 2 / g, particle size: 1.2 μm) (light and light calcium carbonate, manufactured by Kamishima Chemical Industry Co., Ltd.) 0.1 part by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (ADK STAB CDA-6, ADEKA) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (Adeka Stub AO-60, manufactured by ADEKA) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 weight What was added and mixed in an amount was kneaded in an extruder while heating and melting at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率８０％、光沢度５９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition had a gas generation rate of 80%, a glossiness of 59%, a large amount of gas generation during molding, and a poor appearance.
＜比較例３＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）０．５重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 3>
As an inorganic compound, talc (oil absorption amount: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) (general-purpose talc MS, manufactured by Nippon Talc Co., Ltd.) 0.5 parts by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA) 0.10 weight Parts, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris ( 2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) added with 0.05 part by weight was mixed The mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率９０％、光沢度５８％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition had a gas generation rate of 90%, a glossiness of 58%, a large amount of gas generation during molding, and a poor appearance.
＜比較例４＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）１．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative example 4>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 ) as an inorganic compound with respect to 100 parts by weight of the polypropylene resin composition that is sorted and collected from used home appliances and is not subjected to density sorting or surface polishing. / G, particle diameter: 2.8 μm) (KS-800, manufactured by Calfine Co., Ltd.) 1.0 part by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Co., Ltd.) 0 10 parts by weight, 0.05 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) , 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed. The resulting product was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率７５％、光沢度５９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition had a gas generation rate of 75%, a glossiness of 59%, a large amount of gas generation during molding, and a poor appearance.
＜比較例５＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）１．０重量部、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）１．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、ジオクタデシル−３，３’−チオジプロピオネート（ＤＳＴＰ「ヨシトミ」、（株）エーピーアイコーポレーション製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 5>
As an inorganic compound, talc (oil absorption amount: 26 ml / 100 g, specific surface area: 4.5 m 2 //) is collected from 100 parts by weight of the polypropylene resin composition that is sorted and collected from used home appliances and is not subjected to density sorting or surface polishing. g, particle diameter: 14 μm) (general-purpose talc MS, manufactured by Nippon Talc Co., Ltd.) 1.0 part by weight, titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle diameter: 0.20 μm) (R-24, Sakai Chemical Industry Co., Ltd.) 1.0 part by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation) 0.10 part by weight, tetrakis [methylene- 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, A mixture of 0.05 part by weight of octadecyl-3,3′-thiodipropionate (DSTP “Yoshitomi”, manufactured by API Corporation) was mixed at 200 ° C. while heating and melting. It knead | mixed in and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率７０％、光沢度６１％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition has a gas generation rate of 70% and a glossiness of 61%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例６＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）３．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 6>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 ) as an inorganic compound with respect to 100 parts by weight of the polypropylene resin composition that is sorted and collected from used home appliances and is not subjected to density sorting or surface polishing. / G, particle size: 2.8 μm) (KS-800, manufactured by Calfine Co., Ltd.) 3.0 parts by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Co., Ltd.) 0 10 parts by weight, 0.05 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) , 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed. The resulting product was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率６０％、光沢度５９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition had a gas generation rate of 60%, a glossiness of 59%, a large amount of gas generation during molding, and a poor appearance.
＜比較例７＞
使用済み家電製品より選別回収し、濃淡選別や表面研磨を施していないポリプロピレン樹脂組成物１００重量部に対して、無機化合物として、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）５．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 7>
Titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g) as an inorganic compound with respect to 100 parts by weight of the polypropylene resin composition that has been collected and collected from used home appliances and has not been subjected to density sorting or surface polishing. , Particle diameter: 0.20 μm) (R-24, Sakai Chemical Industry Co., Ltd.) 5.0 parts by weight, decamethylene dicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Corporation) 10 parts by weight, 0.05 parts by weight of tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) What added and mixed 0.05 weight part of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) The mixture was kneaded in an extruder while being heated and melted at 200 ° C. to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリプロピレン樹脂組成物は、ガス発生率５２％、光沢度６３％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polypropylene resin composition has a gas generation rate of 52% and a glossiness of 63%, and the appearance is improved, but the amount of gas generation during molding is large.
＜比較例８＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 8>
Decamethylenedicarboxylic acid disalicyloyl hydrazide (ADEKA STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene- 3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-) A mixture of 0.05 part by weight of t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Co., Ltd.) was mixed and kneaded in an extruder at 200 ° C. while heating and melting. A 5 mm pellet was prepared. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリエチレン樹脂組成物は、ガス発生率１００％、光沢度５７％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition had a gas generation rate of 100% and a glossiness of 57%, had a large amount of gas generation during molding, and had a poor appearance.
＜比較例９＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）０．５重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 9>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) as an inorganic compound with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances (KS-800, manufactured by Calfine Co., Ltd.) 0.5 parts by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA Co., Ltd.) 0.10 parts by weight, tetrakis [methylene-3 -(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t -Butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight was added and mixed, and the mixture was heated and melted at 200 ° C. Then, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリエチレン樹脂組成物は、ガス発生率８５％、光沢度５８％であり、成形時のガス発生量が多く、外観が不良であった。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition had a gas generation rate of 85%, a glossiness of 58%, a large amount of gas generation during molding, and a poor appearance.
＜比較例１０＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、無機化合物として、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）１．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 10>
Titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle size: 0.20 μm) as an inorganic compound with respect to 100 parts by weight of the polyethylene resin composition selected and collected from used home appliances (R -24, Sakai Chemical Industry Co., Ltd.) 1.0 part by weight, decamethylene dicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, ADEKA Co., Ltd.) 0.10 part by weight, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t- Butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was mixed and extruded at 200 ° C. while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリエチレン樹脂組成物は、ガス発生率８０％、光沢度６０％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition has a gas generation rate of 80% and a glossiness of 60%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例１１＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）１．０重量部、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）１．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 11>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) as an inorganic compound with respect to 100 parts by weight of polyethylene resin composition selected and collected from used home appliances (KS-800, manufactured by Calfine Co., Ltd.) 1.0 part by weight, titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle size: 0.20 μm) (R-24, Sakai Chemical Industrial Co., Ltd.) 1.0 parts by weight, decamethylenedicarboxylic acid disalicyloyl hydrazide (Adeka Stub CDA-6, manufactured by ADEKA) 0.10 parts by weight, tetrakis [methylene-3- (3 ′, 5 '-Di-t-butyl-4'-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris (2,4-di-t- Tilphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) 0.05 parts by weight was mixed and kneaded in an extruder at 200 ° C. while being heated and melted to obtain 3 to 5 mm pellets Was made. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリエチレン樹脂組成物は、ガス発生率７７％、光沢度６０％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition has a gas generation rate of 77% and a glossiness of 60%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例１２＞
使用済み家電製品より選別回収したポリエチレン樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）５．０重量部、デカメチレンジカルボン酸ジサリチロイルヒドラジド（アデカスタブＣＤＡ−６、（株）ＡＤＥＫＡ製）０．１０重量部、テトラキス［メチレン−３−（３’，５’−ジ−ｔ−ブチル−４’−ヒドロキシフェニル）プロピオネート］メタン（アデカスタブＡＯ−６０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２００℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２００℃、金型温度５０℃の条件で、平板試験片を成形した。
<Comparative Example 12>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound for 100 parts by weight of polyethylene resin composition selected and collected from used home appliances (general talc) MS, manufactured by Nippon Talc Co., Ltd.) 5.0 parts by weight, decamethylene dicarboxylic acid disalicyloyl hydrazide (ADK STAB CDA-6, manufactured by ADEKA Corporation) 0.10 parts by weight, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (ADK STAB AO-60, manufactured by ADEKA Corporation) 0.05 parts by weight, tris (2,4-di-t-butylphenyl) ) Phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was added and mixed, and extruded at 200 ° C while heating and melting. It knead | mixed in the machine and produced the 3-5 mm pellet. Next, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 200 ° C. and a mold temperature of 50 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表４に示す。この結果、再生ポリエチレン樹脂組成物は、ガス発生率６０％、光沢度６０％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 4 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polyethylene resin composition has a gas generation rate of 60% and a glossiness of 60%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例１３＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Comparative Example 13>
Stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances ) 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) and mixed at 220 ° C. While heating and melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリスチレン樹脂組成物は、ガス発生率１００％、光沢度７８％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition had a gas generation rate of 100% and a glossiness of 78%, had a large amount of gas generation during molding, and had a poor appearance.
＜比較例１４＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、無機化合物として、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）０．５重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Comparative example 14>
Titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle size: 0.20 μm) as an inorganic compound with respect to 100 parts by weight of the polystyrene resin composition selected and collected from used home appliances (R -24, Sakai Chemical Industry Co., Ltd.) 0.5 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Adekastab AO-50, manufactured by ADEKA) 0 .05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed, and the mixture was heated and melted at 220 ° C. The mixture was kneaded in an extruder while producing 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリスチレン樹脂組成物は、ガス発生率９２％、光沢度７９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition had a gas generation rate of 92%, a glossiness of 79%, a large amount of gas generation during molding, and a poor appearance.
＜比較例１５＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）０．５重量部、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）０．５重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Comparative Example 15>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances (general talc) MS, manufactured by Nippon Talc Co., Ltd.) 0.5 parts by weight, calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) (KS-800, Co., Ltd.) Calfine) 0.5 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris ( 2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was added and mixed at 220 ° C. with heating and melting. Then, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリスチレン樹脂組成物は、ガス発生率７８％、光沢度８０％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition has a gas generation rate of 78% and a glossiness of 80%, and the appearance is improved, but the amount of gas generation during molding is large.
＜比較例１６＞
使用済み家電製品より選別回収したポリスチレン樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）５．０重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２２０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２２０℃、金型温度５５℃の条件で、平板試験片を成形した。
<Comparative Example 16>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) as an inorganic compound with respect to 100 parts by weight of polystyrene resin composition selected and collected from used home appliances (KS-800, manufactured by Calfine Co., Ltd.) 5.0 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed, and heated at 220 ° C. While melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Next, a flat plate test piece was molded by an injection molding machine under the conditions of a resin temperature (molding temperature) of 220 ° C. and a mold temperature of 55 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリスチレン樹脂組成物は、ガス発生率５２％、光沢度８２％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polystyrene resin composition has a gas generation rate of 52% and a glossiness of 82%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例１７＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Comparative Example 17>
Stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) with respect to 100 parts by weight of ABS resin composition selected and collected from used home appliances ) 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) was added and mixed at 240 ° C. While heating and melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ＡＢＳ樹脂組成物は、ガス発生率１００％、光沢度７８％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition had a gas generation rate of 100% and a glossiness of 78%, had a large amount of gas generation during molding, and had a poor appearance.
＜比較例１８＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）０．１重量部、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）０．２重量部、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）０．２重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Comparative Example 18>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound for 100 parts by weight of ABS resin composition selected and collected from used home appliances (general talc MS, manufactured by Nippon Talc Co., Ltd. 0.1 parts by weight, calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) (KS-800, Co., Ltd.) Calfine) 0.2 parts by weight, titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle size: 0.20 μm) (R-24, Sakai Chemical Industry Co., Ltd.) 2 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA) 0.05 part by weight, Tris (2,4-di-) t-butyl Nyl) phosphite (Adeka Stub 2112, manufactured by ADEKA) 0.05 parts by weight was mixed and kneaded in an extruder while being heated and melted at 240 ° C. to obtain 3 to 5 mm pellets Was made. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ＡＢＳ樹脂組成物は、ガス発生率９１％、光沢度７９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition had a gas generation rate of 91%, a glossiness of 79%, a large amount of gas generation during molding, and a poor appearance.
＜比較例１９＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）０．５重量部、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）０．５重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Comparative Example 19>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound for 100 parts by weight of ABS resin composition selected and collected from used home appliances (general talc MS, manufactured by Nippon Talc Co., Ltd.) 0.5 parts by weight, calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) (KS-800, Co., Ltd.) Calfine) 0.5 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 parts by weight, Tris ( 2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) 0.05 parts by weight was added and mixed at 240 ° C. while heating and melting. It knead | mixed in the extruder and produced the 3-5 mm pellet. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ＡＢＳ樹脂組成物は、ガス発生率７７％、光沢度８０％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition has a gas generation rate of 77% and a glossiness of 80%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例２０＞
使用済み家電製品より選別回収したＡＢＳ樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）５．０重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２４０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２４０℃、金型温度６０℃の条件で、平板試験片を成形した。
<Comparative Example 20>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound for 100 parts by weight of ABS resin composition selected and collected from used home appliances (general talc MS, manufactured by Nippon Talc Co., Ltd.) 5.0 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 While adding and mixing 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) and heating and melting at 240 ° C. It knead | mixed in the extruder and produced the 3-5 mm pellet. Subsequently, the flat plate test piece was shape | molded on the conditions of resin temperature (molding temperature) 240 degreeC and metal mold | die temperature 60 degreeC with the injection molding machine.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ＡＢＳ樹脂組成物は、ガス発生率５５％、光沢度８２％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled ABS resin composition has a gas generation rate of 55% and a glossiness of 82%, and the appearance is improved, but a large amount of gas is generated during molding.
＜比較例２１＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Comparative Example 21>
Stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances ) 0.05 parts by weight, 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA) was added and mixed at 260 ° C. While heating and melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリカーボネート樹脂組成物は、ガス発生率１００％、光沢度７９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition had a gas generation rate of 100%, a glossiness of 79%, a large amount of gas generation during molding, and a poor appearance.
＜比較例２２＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、無機化合物として、タルク（吸油量：２６ｍｌ／１００ｇ、比表面積：４．５ｍ２／ｇ、粒子径：１４μｍ）（汎用タルクＭＳ、日本タルク（株）製）０．５重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Comparative Example 22>
Talc (oil absorption: 26 ml / 100 g, specific surface area: 4.5 m 2 / g, particle size: 14 μm) as an inorganic compound with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances (general talc MS, manufactured by Nippon Talc Co., Ltd.) 0.5 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA Corporation) 0.05 While adding and mixing 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) and heating and melting at 260 ° C. It knead | mixed in the extruder and produced the 3-5 mm pellet. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリカーボネート樹脂組成物は、ガス発生率９１％、光沢度７９％であり、成形時のガス発生量が多く、外観が不良であった。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition had a gas generation rate of 91%, a glossiness of 79%, a large amount of gas generation during molding, and a poor appearance.
＜比較例２３＞
使用済み家電製品より選別回収したポリカーボネート樹脂組成物１００重量部に対して、無機化合物として、炭酸カルシウム（吸油量：１７ｍｌ／１００ｇ、比表面積：０．７ｍ２／ｇ、粒子径：２．８μｍ）（ＫＳ−８００、（株）カルファイン製）２．０重量部、二酸化チタン（吸油量：２４ｍｌ／１００ｇ、比表面積：５ｍ２／ｇ、粒子径：０．２０μｍ）（Ｒ−２４、堺化学工業（株）製）３．０重量部、ステアリルβ−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート（アデカスタブＡＯ−５０、（株）ＡＤＥＫＡ製）０．０５重量部、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファイト（アデカスタブ２１１２、（株）ＡＤＥＫＡ製）０．０５重量部を添加して混合したものを、２６０℃で、加熱溶融しながら押出機の中で混練して、３〜５ｍｍのペレットを作製した。次いで、射出成形機により、樹脂温度（成形温度）２６０℃、金型温度９０℃の条件で、平板試験片を成形した。
<Comparative Example 23>
Calcium carbonate (oil absorption: 17 ml / 100 g, specific surface area: 0.7 m 2 / g, particle size: 2.8 μm) as an inorganic compound with respect to 100 parts by weight of the polycarbonate resin composition selected and collected from used home appliances (KS-800, manufactured by Calfine Co., Ltd.) 2.0 parts by weight, titanium dioxide (oil absorption: 24 ml / 100 g, specific surface area: 5 m 2 / g, particle size: 0.20 μm) (R-24, Sakai Chemical Kogyo Co., Ltd.) 3.0 parts by weight, stearyl β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (ADK STAB AO-50, manufactured by ADEKA) 0.05 part by weight, A mixture obtained by adding 0.05 parts by weight of tris (2,4-di-t-butylphenyl) phosphite (ADK STAB 2112, manufactured by ADEKA Corporation) and mixing at 260 ° C. with heating While melting, the mixture was kneaded in an extruder to produce 3 to 5 mm pellets. Subsequently, a flat plate test piece was molded by an injection molding machine under conditions of a resin temperature (molding temperature) of 260 ° C. and a mold temperature of 90 ° C.
得られた試験片を用いて、ガス発生率、光沢度を測定した結果を表５に示す。この結果、再生ポリカーボネート樹脂組成物は、ガス発生率５１％、光沢度８５％であり、外観は改善されるが、成形時のガス発生量が多い。 Table 5 shows the results of measuring the gas generation rate and the glossiness using the obtained test pieces. As a result, the recycled polycarbonate resin composition has a gas generation rate of 51% and a glossiness of 85%, and the appearance is improved, but a large amount of gas is generated during molding.
Claims (6)
吸油量５０ｍｌ／１００ｇ以上、比表面積１ｍ２／ｇ以上の吸油性無機化合物０．５〜５重量部と、
流動性調整剤０．１〜５重量部と、
耐熱安定剤０．０５〜１０重量部とを含有する再生熱可塑性樹脂組成物であって、
前記吸油性無機化合物が、粒子径０．１〜１．０μｍのアルミナ、粒子径０．１〜５．０μｍのベーマイト、粒子径１〜５０μｍのケイ酸カルシウム、粒子径０．１〜１０μｍの炭酸カルシウムから選ばれる少なくともいずれかである、再生熱可塑性樹脂組成物。 100 parts by weight of the used thermoplastic resin composition;
0.5 to 5 parts by weight of an oil-absorbing inorganic compound having an oil absorption of 50 ml / 100 g or more and a specific surface area of 1 m 2 / g or more;
0.1 to 5 parts by weight of a fluidity modifier,
A recycled thermoplastic resin composition containing 0.05 to 10 parts by weight of a heat stabilizer,
The oil-absorbing inorganic compound is alumina having a particle size 0.1 to 1.0 [mu] m, boehmite particle diameter 0.1 to 5.0 [mu] m, calcium silicate particle size 1~50μm beam, particle element size 0.1~10μm A recycled thermoplastic resin composition, which is at least one selected from calcium carbonate.
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