JP6608124B2 - Thermoplastic resin composition having deodorant performance and molded article - Google Patents
Thermoplastic resin composition having deodorant performance and molded article Download PDFInfo
- Publication number
- JP6608124B2 JP6608124B2 JP2013244494A JP2013244494A JP6608124B2 JP 6608124 B2 JP6608124 B2 JP 6608124B2 JP 2013244494 A JP2013244494 A JP 2013244494A JP 2013244494 A JP2013244494 A JP 2013244494A JP 6608124 B2 JP6608124 B2 JP 6608124B2
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- JP
- Japan
- Prior art keywords
- thermoplastic resin
- polyamide
- resin composition
- salt
- phthalocyanine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 59
- 239000011342 resin composition Substances 0.000 title claims description 28
- 239000002781 deodorant agent Substances 0.000 title description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 62
- -1 phthalocyanine compound Chemical class 0.000 claims description 59
- 229920005989 resin Polymers 0.000 claims description 45
- 239000011347 resin Substances 0.000 claims description 45
- 239000004952 Polyamide Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 44
- 239000002184 metal Substances 0.000 claims description 44
- 229920002647 polyamide Polymers 0.000 claims description 44
- 150000003839 salts Chemical class 0.000 claims description 42
- 239000000178 monomer Substances 0.000 claims description 28
- 239000008188 pellet Substances 0.000 claims description 18
- 125000000524 functional group Chemical group 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000004043 dyeing Methods 0.000 claims description 7
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000004898 kneading Methods 0.000 claims description 4
- 229920006122 polyamide resin Polymers 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 239000000835 fiber Substances 0.000 description 43
- 238000000034 method Methods 0.000 description 22
- 229920001577 copolymer Polymers 0.000 description 21
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 14
- 229920000578 graft copolymer Polymers 0.000 description 11
- 230000001877 deodorizing effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 229920002292 Nylon 6 Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 7
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 7
- 235000019645 odor Nutrition 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000005060 rubber Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000004677 Nylon Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 229920002857 polybutadiene Polymers 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- KMHSUNDEGHRBNV-UHFFFAOYSA-N 2,4-dichloropyrimidine-5-carbonitrile Chemical compound ClC1=NC=C(C#N)C(Cl)=N1 KMHSUNDEGHRBNV-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920005990 polystyrene resin Polymers 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229920000800 acrylic rubber Polymers 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229920005669 high impact polystyrene Polymers 0.000 description 3
- 239000004797 high-impact polystyrene Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000009967 direct dyeing Methods 0.000 description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000003063 flame retardant Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000005185 salting out Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- KYPOHTVBFVELTG-OWOJBTEDSA-N (e)-but-2-enedinitrile Chemical compound N#C\C=C\C#N KYPOHTVBFVELTG-OWOJBTEDSA-N 0.000 description 1
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- RPPHVWXGHJVLOL-UHFFFAOYSA-N 1-(4,5-dihydro-1,3-oxazol-2-yl)prop-2-en-1-one Chemical compound C=CC(=O)C1=NCCO1 RPPHVWXGHJVLOL-UHFFFAOYSA-N 0.000 description 1
- BQTPKSBXMONSJI-UHFFFAOYSA-N 1-cyclohexylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1CCCCC1 BQTPKSBXMONSJI-UHFFFAOYSA-N 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BWKTWZBHXAMSQP-UHFFFAOYSA-N 2-(propylamino)ethyl prop-2-enoate Chemical compound CCCNCCOC(=O)C=C BWKTWZBHXAMSQP-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- CRQSAKXMWFFXJG-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methyl]oxirane Chemical compound C1=CC(C=C)=CC=C1CC1OC1 CRQSAKXMWFFXJG-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- BQBSIHIZDSHADD-UHFFFAOYSA-N 2-ethenyl-4,5-dihydro-1,3-oxazole Chemical compound C=CC1=NCCO1 BQBSIHIZDSHADD-UHFFFAOYSA-N 0.000 description 1
- HMEVYZZCEGUONQ-UHFFFAOYSA-N 2-ethenyl-5-methyl-4,5-dihydro-1,3-oxazole Chemical compound CC1CN=C(C=C)O1 HMEVYZZCEGUONQ-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- TVONJMOVBKMLOM-UHFFFAOYSA-N 2-methylidenebutanenitrile Chemical compound CCC(=C)C#N TVONJMOVBKMLOM-UHFFFAOYSA-N 0.000 description 1
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- LPIQIQPLUVLISR-UHFFFAOYSA-N 2-prop-1-en-2-yl-4,5-dihydro-1,3-oxazole Chemical compound CC(=C)C1=NCCO1 LPIQIQPLUVLISR-UHFFFAOYSA-N 0.000 description 1
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- NMSZFQAFWHFSPE-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxycarbonyl)but-3-enoic acid Chemical compound OC(=O)CC(=C)C(=O)OCC1CO1 NMSZFQAFWHFSPE-UHFFFAOYSA-N 0.000 description 1
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
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- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 1
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- 230000000996 additive effect Effects 0.000 description 1
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- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
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- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
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- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- ACLSSWSISQYUTB-UHFFFAOYSA-N ethylamino 2-methylprop-2-enoate Chemical compound CCNOC(=O)C(C)=C ACLSSWSISQYUTB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
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- 239000003999 initiator Substances 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
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- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
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- 238000009987 spinning Methods 0.000 description 1
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- 125000000547 substituted alkyl group Chemical group 0.000 description 1
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- 229910052717 sulfur Inorganic materials 0.000 description 1
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- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical group ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
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- ZMZDMBWJUHKJPS-UHFFFAOYSA-M thiocyanate group Chemical group [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、耐衝撃性、寸法安定性に優れるだけでなく、消臭性能を有する熱可塑性樹脂組成物及び該熱可塑性樹脂組成物から得られた成形体に関する。 The present invention relates to a thermoplastic resin composition having not only excellent impact resistance and dimensional stability but also deodorizing performance, and a molded body obtained from the thermoplastic resin composition.
生活環境水準向上の意識が高まる中、さまざまな課題の解決が要望されている。とりわけ住環境における臭気に関する改善要望が増加しており、例えば、建材の接着剤等に使用されている化学物質に起因する臭気や、煙草臭、人体からの分泌物に起因する臭気など、原因となる要素が複数存在することが多く、それぞれに有効な対策が必要となっている。 As awareness of improving living environment standards increases, solutions to various issues are demanded. In particular, there is an increasing demand for improvement in odors in the living environment, such as odors caused by chemical substances used in building material adhesives, cigarette odors, odors caused by secretions from the human body, etc. In many cases, there are multiple elements, and effective countermeasures are required for each.
特許文献１には、煙草臭に多く含まれるアルデヒド類を除去する手段として、ヒドラジド化合物を合成樹脂に配合した樹脂組成物が提案されている。
また、特許文献２には、イソ吉草酸、酪酸などの低級脂肪酸に起因する発酵臭を除去する手段として、ハイドロタルサイト化合物と２価または３価金属の酸化物を含有する樹脂組成物が開示されている。
Patent Document 1 proposes a resin composition in which a hydrazide compound is blended with a synthetic resin as a means for removing aldehydes that are abundantly contained in tobacco odor.
Patent Document 2 discloses a resin composition containing a hydrotalcite compound and a divalent or trivalent metal oxide as a means for removing fermentation odor caused by lower fatty acids such as isovaleric acid and butyric acid. Has been.
しかし、これら従来の技術では、多量の無機化合物を樹脂中に配合する必要があり、様々な形状の部品への適用する際に、耐衝撃性等の物性や成形性に劣るという欠点があった。 However, in these conventional techniques, it is necessary to mix a large amount of an inorganic compound in the resin, and there is a drawback that physical properties such as impact resistance and moldability are inferior when applied to parts of various shapes. .
本発明の目的は、耐衝撃性、寸法安定性に優れるだけでなく、消臭性能を有する熱可塑性樹脂組成物及び該熱可塑性樹脂組成物から得られた成形体を提供することにある。 An object of the present invention is to provide a thermoplastic resin composition having not only excellent impact resistance and dimensional stability but also deodorizing performance and a molded body obtained from the thermoplastic resin composition.
本発明者らは、従来技術の問題点を解決するために鋭意検討した結果、特定の金属フタロシアニン化合物またはその塩を担持したポリアミドと熱可塑性樹脂とを溶融混合した熱可塑性樹脂組成物を用いることにより、上記目的を達成できることを見出し、本発明に到達した。 As a result of intensive investigations to solve the problems of the prior art, the present inventors use a thermoplastic resin composition obtained by melt-mixing a polyamide carrying a specific metal phthalocyanine compound or a salt thereof and a thermoplastic resin. Thus, the inventors have found that the above object can be achieved, and have reached the present invention.
すなわち、本発明は、下記化学式（ＩＩ）で示される金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）と熱可塑性樹脂（Ｂ）とを含むことを特徴とする熱可塑性樹脂組成物に関する。なお、熱可塑性樹脂（Ｂ）はゴム強化スチレン系樹脂を含み、かつ、ポリアミド樹脂を含まないものである。
式（ＩＩ）中、ＭはＦｅ、Ｃｏ、Ｍｎ、Ｔｉ、Ｖ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｏ、Ｗ、Ｏｓから選択される金属、Ｒ １ 、Ｒ ２ 、Ｒ ３ 及びＲ ４ はスルホン酸基であり、ｎ１、ｎ２、ｎ３及びｎ４は０〜４で１≦ｎ１＋ｎ２＋ｎ３＋ｎ４≦８を満たす数である。
That is, the present invention relates to a thermoplastic resin composition comprising a polyamide (A) carrying a metal phthalocyanine compound represented by the following chemical formula (II) or a salt thereof and a thermoplastic resin (B). The thermoplastic resin (B) contains a rubber-reinforced styrene resin and does not contain a polyamide resin .
In formula (II), M is a metal selected from Fe, Co, Mn, Ti, V, Ni, Cu, Zn, Mo, W, and Os, and R 1 , R 2 , R 3, and R 4 are sulfonic acid groups N1, n2, n3, and n4 are numbers 0 to 4 that satisfy 1 ≦ n1 + n2 + n3 + n4 ≦ 8.
本発明により、耐衝撃性、寸法安定性に優れるだけでなく、消臭性能を有する熱可塑性樹脂組成物及び該熱可塑性樹脂組成物から得られた成形体を提供することが出来る。 According to the present invention, it is possible to provide a thermoplastic resin composition having not only excellent impact resistance and dimensional stability but also deodorizing performance and a molded body obtained from the thermoplastic resin composition.
以下、本発明を詳しく説明する。
本発明で用いられる金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）は、下記化学式（Ｉ）（式（Ｉ）中、ＭはＦｅ、Ｃｏ、Ｍｎ、Ｔｉ、Ｖ、Ｎｉ、Ｃｕ、Ｚｎ、Ｍｏ、Ｗ、Ｏｓから選択される金属）で示される金属フタロシアニン化合物またはその塩を担持したポリアミドである。
The polyamide (A) supporting the metal phthalocyanine compound or a salt thereof used in the present invention has the following chemical formula (I) (wherein M is Fe, Co, Mn, Ti, V, Ni, Cu, Zn, A metal carrying a metal phthalocyanine compound or a salt thereof selected from Mo, W and Os.
下記化学式（ＩＩ）で表される金属フタロシアニン化合物またはその塩であることが好ましい。
上記化学式（ＩＩ）において、式（ＩＩ）中、ＭはＦｅ、Ｃｏ、Ｃｕ及びＮｉから選択される金属、Ｒ１、Ｒ２、Ｒ３及びＲ４は同一または異なるカルボキシル基（ＣＯＯＨ基）またはスルホン酸基（ＳＯ３Ｈ基）であり、ｎ１、ｎ２、ｎ３及びｎ４は０〜４で１≦ｎ１＋ｎ２＋ｎ３＋ｎ４≦８を満たす数である金属フタロシアニン化合物またはその塩であることがより好ましい。 In the chemical formula (II), in the formula (II), M is a metal selected from Fe, Co, Cu and Ni, and R 1 , R 2 , R 3 and R 4 are the same or different carboxyl groups (COOH groups) or It is more preferably a metal phthalocyanine compound or a salt thereof that is a sulfonic acid group (SO 3 H group), and n1, n2, n3, and n4 are 0 to 4 and satisfy 1 ≦ n1 + n2 + n3 + n4 ≦ 8.
金属フタロシアニン化合物の塩としては、例えば無機塩基との塩、有機塩基との塩等が挙げられる。無機塩基との塩の好適な例としては、例えばナトリウム塩、カリウム塩などのアルカリ金属塩；カルシウム塩、マグネシウム塩などのアルカリ土類金属塩；ならびに銅（ＩＩ）塩、アンモニウム塩などが挙げられる。有機塩基との塩の好適な例としては、例えばトリメチルアミン、トリエチルアミン、ピリジン、ピコリン、エタノールアミン、ジエタノールアミン、トリエタノールアミン、ジシクロヘキシルアミン等との塩が挙げられる。 Examples of the salt of the metal phthalocyanine compound include a salt with an inorganic base and a salt with an organic base. Preferable examples of the salt with an inorganic base include alkali metal salts such as sodium salt and potassium salt; alkaline earth metal salts such as calcium salt and magnesium salt; and copper (II) salt and ammonium salt. . Preferable examples of the salt with an organic base include salts with trimethylamine, triethylamine, pyridine, picoline, ethanolamine, diethanolamine, triethanolamine, dicyclohexylamine and the like.
式（ＩＩ）中、ＭがＦｅ、Ｒ１、Ｒ２、Ｒ３及びＲ４がすべて−ＣＯＯＨ基、ｎ１、ｎ２、ｎ３及びｎ４が各々１であると、下記式（ＩＩＩ）
式（ＩＩ）中、ＭがＣｏ、Ｒ１及びＲ３が−ＣＯＯＨ基である場合、下記式（ＩＶ）
式（ＩＩ）中、ＭがＣｏ、Ｒ１及びＲ３が−ＳＯ３Ｈ基である場合、下記式（Ｖ）
式（ＩＩ）中、ＭがＦｅ、Ｒ１及びＲ３が−ＳＯ３Ｈ基であると、下記式（ＶＩ）
式（ＩＩ）中、ＭがＦｅ、Ｒ１、Ｒ２、Ｒ３及びＲ４がすべて−ＣＯＯＨ基、ｎ１、ｎ２、ｎ３及びｎ４が各々２であると、下記式（ＶＩＩ）
本発明で用いられる金属フタロシアニン化合物またはその塩は、特に消臭性能を考慮すると、鉄フタロシアニンテトラカルボン酸、鉄フタロシアニンオクタカルボン酸、鉄フタロシアニンモノスルホン酸、鉄フタロシアニンジスルホン酸、コバルトフタロシアニンモノスルホン酸、コバルトフタロシアニンジスルホン酸またはその塩であることが好ましい。後述するポリアミドに対するフタロシアニン化合物またはその塩の担持性を考慮すると、官能基はスルホン酸基であることが好ましい。 The metal phthalocyanine compound or a salt thereof used in the present invention is iron phthalocyanine tetracarboxylic acid, iron phthalocyanine octacarboxylic acid, iron phthalocyanine monosulfonic acid, iron phthalocyanine disulfonic acid, cobalt phthalocyanine monosulfonic acid, especially considering deodorizing performance. Cobalt phthalocyanine disulfonic acid or a salt thereof is preferable. In consideration of the supportability of the phthalocyanine compound or its salt to the polyamide described later, the functional group is preferably a sulfonic acid group.
前記金属フタロシアニン化合物またはその塩はポリアミドに担持した後に、熱可塑性樹脂（Ｂ）と混合され、溶融して成形することから、耐熱性を有していることが好ましい。従来の消臭剤は、耐熱性と消臭性能を両立するものが少ないが、金属フタロシアニン化合物またはその塩は、耐熱性及び消臭性能のいずれの機能も有しており好ましい。金属フタロシアニン化合物またはその塩の熱分解温度は２８０℃以上であることが好ましい。より好ましくは、３００〜３２０℃である。 Since the metal phthalocyanine compound or a salt thereof is supported on polyamide and then mixed with the thermoplastic resin (B) and melted and molded, it preferably has heat resistance. Although few conventional deodorizers have both heat resistance and deodorizing performance, metal phthalocyanine compounds or salts thereof are preferred because they have both functions of heat resistance and deodorizing performance. The thermal decomposition temperature of the metal phthalocyanine compound or a salt thereof is preferably 280 ° C. or higher. More preferably, it is 300-320 degreeC.
本発明で用いられる金属フタロシアニン化合物またはその塩は、公知の方法により製造されるものであり、例えば、「フタロシアニン −化学と機能−」（白井汪芳、小林長夫著、株式会社アイピーシー出版、平成９年２月２８日発行）に記載の方法により、製造することができる。例えば、鉄フタロシアニンテトラカルボン酸は、ニトロベンゼンにトリメリット酸無水物と、尿素と、モリブデン酸アンモニウムと、塩化第二鉄無水物とを加えて撹拌し、加熱還流させて沈殿物を得、得られた沈殿物にアルカリを加えて加水分解し、次いで酸を加えて酸性にすることで得ることができる。コバルトフタロシアニンオクタカルボン酸は、上記鉄フタロシアニンテトラカルボン酸の原料であるトリメリット酸無水物に代えてピロメリット酸無水物、塩化第二鉄無水物に代えて塩化第二コバルトを用いて同様の方法で製造可能である。コバルトフタロシアニンモノスルホン酸は、無官能のコバルトフタロシアニンにクロルスルホン酸を反応させてスルホン化を行うことで得ることができる。 The metal phthalocyanine compound or a salt thereof used in the present invention is produced by a known method. For example, “phthalocyanine-chemistry and function” (written by Yoshiyoshi Shirai, Nagao Kobayashi, IP Publishing Co., Ltd., Heisei) (Issued February 28, 1997). For example, iron phthalocyanine tetracarboxylic acid is obtained by adding trimellitic anhydride, urea, ammonium molybdate, and ferric chloride anhydride to nitrobenzene, stirring and heating to reflux to obtain a precipitate. The precipitate is hydrolyzed by adding an alkali, and then acidified by adding an acid. Cobalt phthalocyanine octacarboxylic acid is a similar method using pyromellitic anhydride instead of trimellitic anhydride, which is a raw material of iron phthalocyanine tetracarboxylic acid, and ferric chloride instead of ferric chloride anhydride. Can be manufactured. Cobalt phthalocyanine monosulfonic acid can be obtained by sulfonation by reacting nonfunctional cobalt phthalocyanine with chlorosulfonic acid.
ポリアミドに担持させる金属フタロシアニン化合物またはその塩の量は、ポリアミドに対して０．１〜１０質量％であるとよい。好ましくは、０．２〜５質量％であり、より好ましくは０．３〜１質量％である。この範囲内であると、金属フタロシアニン化合物の酸化還元触媒機能に優れ、また低コストで容易にポリアミドに担持させることができる。 The amount of the metal phthalocyanine compound or a salt thereof supported on the polyamide is preferably 0.1 to 10% by mass with respect to the polyamide. Preferably, it is 0.2-5 mass%, More preferably, it is 0.3-1 mass%. Within this range, the metal phthalocyanine compound has an excellent redox catalyst function and can be easily supported on polyamide at low cost.
本発明で用いられる金属フタロシアニン化合物またはその塩は、その中心金属に臭気原因物質を配位し、配位結合により結合し、硫化水素やメルカプタン類などの一部の臭気原因物質に対しては、空気中の酸素によって酸化分解するので、その作用は永続的である。また、本発明で使用される金属フタロシアニン化合物またはその塩は、窒素酸化物（ＮＯｘ）や硫黄酸化物（ＳＯｘ）などの有害物質を吸着する機能を有するので、様々な分野で利用できる。 The metal phthalocyanine compound or salt thereof used in the present invention coordinates an odor-causing substance to the central metal and binds by a coordinate bond, and for some odor-causing substances such as hydrogen sulfide and mercaptans, Its action is permanent because it is oxidatively decomposed by oxygen in the air. Further, the metal phthalocyanine compound or a salt thereof used in the present invention has a function of adsorbing harmful substances such as nitrogen oxide (NOx) and sulfur oxide (SOx), and thus can be used in various fields.
本発明で用いられる金属フタロシアニン化合物またはその塩を担持させるポリアミドとしては、例えば、ナイロン６、ナイロン１１、ナイロン１２、ナイロン６６、ナイロン６１０，ナイロン６Ｔ、ナイロン６Ｉ、ナイロン９Ｔ、ナイロンＭ５Ｔ、ＭＸＤナイロンなどが挙げられる。ポリアミドは、親水性を有するのでフタロシアニン化合物が結合し易いという特性がある。 Examples of the polyamide supporting the metal phthalocyanine compound or a salt thereof used in the present invention include nylon 6, nylon 11, nylon 12, nylon 66, nylon 610, nylon 6T, nylon 6I, nylon 9T, nylon M5T, and MXD nylon. Is mentioned. Since polyamide has hydrophilicity, it has a characteristic that phthalocyanine compounds are easily bonded.
ポリアミドの形態は、例えば、ペレット状、繊維状、フレーク状、パウダー状など特に制限は無いが、金属フタロシアニン化合物またはその塩の担持しやすさという観点や、熱可塑性樹脂（Ｂ）と混合する際の取り扱い性という観点から、繊維状またはペレット状であることが好ましい。 The form of the polyamide is not particularly limited, for example, in the form of pellets, fibers, flakes, powders, etc., but from the viewpoint of easy loading of the metal phthalocyanine compound or a salt thereof, when mixed with the thermoplastic resin (B) From the viewpoint of handleability, it is preferably in the form of fibers or pellets.
ポリアミド繊維は通常の紡糸法を用いて繊維化されたものが用いられる。ポリアミド繊維の断面形状は特に限定されず、円形、異形、中空などいずれであってもよい。 As the polyamide fiber, a fiber obtained by using a normal spinning method is used. The cross-sectional shape of the polyamide fiber is not particularly limited, and may be any shape such as a circular shape, an irregular shape, and a hollow shape.
ポリアミド繊維に金属フタロシアニン化合物またはその塩を担持させる方法は、ポリアミド繊維を金属フタロシアニン化合物またはその塩を含む溶液へ浸漬させる方法、あるいは直接染色、イオン染色による染色法等、公知の方法が用いられる。 As a method for supporting a metal phthalocyanine compound or a salt thereof on a polyamide fiber, a known method such as a method of immersing a polyamide fiber in a solution containing a metal phthalocyanine compound or a salt thereof, a direct dyeing method, or a dyeing method using ion dyeing is used.
前記ポリアミド繊維は、熱可塑性樹脂（Ｂ）に混合して分散し易くするために、繊維長を短繊維に調整することが好ましい。このとき、金属フタロシアニン化合物またはその塩は、所定の繊維長に調整した後に担持処理してもよいし、先に繊維表面に担持処理した後に所定の繊維長に調整してもよい。繊維長を調整する方法としては、繊維（例えば、トウ（連続繊維）などの繊維束）をカッター（刃）で切断する方法、繊維（例えば、ステープル繊維など）をグラインドミル等ですり潰すようにして裁断（粉砕）する方法などが挙げられる。カッターで切断した短繊維は繊維長が一定であり、すり潰して裁断した短繊維は、繊維長がランダムである。なお、すり潰すようにして裁断された微細繊維は、任意のメッシュを有する篩にかけて分級したものを用いるとよい。 The polyamide fiber is preferably adjusted to a short fiber length in order to be easily mixed and dispersed in the thermoplastic resin (B). At this time, the metal phthalocyanine compound or a salt thereof may be supported after being adjusted to a predetermined fiber length, or may be adjusted to a predetermined fiber length after first being supported on the fiber surface. As a method for adjusting the fiber length, a method of cutting a fiber (for example, a fiber bundle such as tow (continuous fiber)) with a cutter (blade), or a method of grinding the fiber (for example, staple fiber) with a grind mill or the like. And cutting (grinding). The short fiber cut by the cutter has a constant fiber length, and the short fiber ground and cut has a random fiber length. In addition, it is good to use what was classified with the sieve which has arbitrary meshes as the fine fiber cut | disconnected by grinding.
前記ポリアミド短繊維は、繊維長が０．０５〜２ｍｍであることが好ましい。より好ましくは、０．１〜１ｍｍであり、さらにより好ましくは、０．３〜０．７ｍｍである。繊維長が上記範囲内にあると、熱可塑性樹脂（Ｂ）に混合したときに、分散性が良好である。 The polyamide short fiber preferably has a fiber length of 0.05 to 2 mm. More preferably, it is 0.1-1 mm, More preferably, it is 0.3-0.7 mm. When the fiber length is within the above range, the dispersibility is good when mixed with the thermoplastic resin (B).
前記ポリアミド短繊維は、繊度が１〜１０ｄｔｅｘであることが好ましい。より好ましくは、２〜５ｄｔｅｘである。繊度が上記範囲内にあると、熱可塑性樹脂（Ｂ）に混合したときに、分散性が良好である。 The polyamide short fiber preferably has a fineness of 1 to 10 dtex. More preferably, it is 2 to 5 dtex. When the fineness is within the above range, the dispersibility is good when mixed with the thermoplastic resin (B).
ポリアミドペレットとしては、例えば、ユニチカ株式会社製 「ユニチカナイロン６ Ａ１０３０ＢＲＬ」や、宇部興産株式会社製「ＵＢＥナイロン６ １０１５Ｂ」など市販のものが使用できる。ペレット形状は特に限定されず、円柱形、球形、中空などいずれであってもよい。 As the polyamide pellets, for example, commercially available products such as “Unitika nylon 6 A1030BRL” manufactured by Unitika Ltd. and “UBE nylon 6 1015B” manufactured by Ube Industries, Ltd. can be used. The pellet shape is not particularly limited, and may be any of a cylindrical shape, a spherical shape, a hollow shape, and the like.
ポリアミドペレットに金属フタロシアニン化合物またはその塩を担持させる方法は、ポリアミドペレットを金属フタロシアニン化合物またはその塩を含む溶液へ浸漬させる方法、あるいは直接染色、イオン染色による染色法等、公知の方法が用いられる。 As a method of supporting the metal phthalocyanine compound or a salt thereof on the polyamide pellet, a known method such as a method of immersing the polyamide pellet in a solution containing the metal phthalocyanine compound or a salt thereof, a direct dyeing method, a dyeing method using ion dyeing, or the like is used.
前記ポリアミドペレットの大きさは、長径０．５〜４ｍｍ、短径０．３〜３ｍｍであることが好ましい。ペレットの大きさが上記範囲内にあると、金属フタロシアニン化合物またはその塩の担持し易くなる。 The polyamide pellets preferably have a major axis of 0.5 to 4 mm and a minor axis of 0.3 to 3 mm. When the size of the pellet is within the above range, the metal phthalocyanine compound or a salt thereof is easily supported.
本発明で用いられる熱可塑性樹脂（Ｂ）は、例えば、ポリエチレン樹脂、ポリプロピレン樹脂等のポリオレフィン樹脂、ポリスチレン樹脂、ＡＳ樹脂、ＭＳ樹脂、ＨＩＰＳ樹脂、ＡＢＳ樹脂、ＡＥＳ樹脂、ＡＳＡ樹脂等のスチレン系樹脂、ポリブチレンテレフタレート樹脂、ポリエチレンテレフタレート樹脂、ポリ乳酸樹脂等のポリエステル樹脂、ポリメチルメタクリレート樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリアセタール樹脂などが挙げられるが、目的とする物性に応じてこれらの熱可塑性樹脂を適宜選択する事ができる。また、これらの熱可塑性樹脂は単独でも使用可能であるが、２種以上組み合わせて使用しても良い。 Examples of the thermoplastic resin (B) used in the present invention include polyolefin resins such as polyethylene resins and polypropylene resins, polystyrene resins such as polystyrene resins, AS resins, MS resins, HIPS resins, ABS resins, AES resins, and ASA resins. , Polyester resins such as polybutylene terephthalate resin, polyethylene terephthalate resin, polylactic acid resin, polymethyl methacrylate resin, polycarbonate resin, polyphenylene ether resin, polyacetal resin, etc., and these thermoplastic resins depending on the desired physical properties Can be selected as appropriate. Moreover, although these thermoplastic resins can be used alone, they may be used in combination of two or more.
金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）との相溶性の観点から、熱可塑性樹脂（Ｂ）として、スチレン重合体（ＰＳ樹脂）、スチレン・アクリロニトリル共重合体（ＡＳ樹脂）、α−メチルスチレン・アクリロニトリル共重合体（αＭＳ−ＡＣＮ樹脂）、メタクリル酸メチル・スチレン共重合体（ＭＳ樹脂）、メタクリル酸メチル・アクリロニトリル・スチレン共重合体（ＭＡＳ樹脂）、スチレン・Ｎ−フェニルマレイミド共重合体（Ｓ−ＮＰＭＩ樹脂）、スチレン・Ｎ−フェニルマレイミド・アクリロニトリル共重合体（Ｓ−Ａ−ＮＰＭＩ樹脂）、ゴム強化ポリスチレン樹脂（ＨＩＰＳ樹脂）、アクリロニトリル・ブタジエン系ゴム・スチレン重合体（ＡＢＳ樹脂）、アクリロニトリル・アクリル系ゴム・スチレン重合体（ＡＡＳ樹脂）、メタクリル酸メチル・ブタジエン系ゴム・スチレン樹脂（ＭＢＳ樹脂）、アクリロニトリル・エチレン−プロピレン系ゴム・スチレン重合体（ＡＥＳ樹脂）等のスチレン系樹脂を用いる事が好ましい。 From the viewpoint of compatibility with the polyamide (A) carrying a metal phthalocyanine compound or a salt thereof, as the thermoplastic resin (B), a styrene polymer (PS resin), a styrene / acrylonitrile copolymer (AS resin), α- Methyl styrene / acrylonitrile copolymer (αMS-ACN resin), methyl methacrylate / styrene copolymer (MS resin), methyl methacrylate / acrylonitrile / styrene copolymer (MAS resin), styrene / N-phenylmaleimide copolymer Copolymer (S-NPMI resin), styrene / N-phenylmaleimide / acrylonitrile copolymer (SA-NPMI resin), rubber reinforced polystyrene resin (HIPS resin), acrylonitrile / butadiene rubber / styrene polymer (ABS resin) , Acrylonitrile / Acrylic rubber / Steel It is preferable to use a styrene resin such as an ethylene polymer (AAS resin), methyl methacrylate / butadiene rubber / styrene resin (MBS resin), acrylonitrile / ethylene-propylene rubber / styrene polymer (AES resin).
本発明で用いられる熱可塑性樹脂（Ｂ）は熱可塑性樹脂組成物の衝撃強度、成形加工性等の観点から、ゴム強化ポリスチレン樹脂（ＨＩＰＳ樹脂）、アクリロニトリル・ブタジエン系ゴム・スチレン重合体（ＡＢＳ樹脂）、アクリロニトリル・アクリル系ゴム・スチレン重合体（ＡＡＳ樹脂）、メタクリル酸メチル・ブタジエン系ゴム・スチレン樹脂（ＭＢＳ樹脂）、アクリロニトリル・エチレン−プロピレン系ゴム・スチレン重合体（ＡＥＳ樹脂）等のゴム強化スチレン系樹脂を用いる事がより好ましい。 The thermoplastic resin (B) used in the present invention is a rubber-reinforced polystyrene resin (HIPS resin), acrylonitrile / butadiene rubber / styrene polymer (ABS resin) from the viewpoint of impact strength, molding processability, etc. of the thermoplastic resin composition. ), Acrylonitrile / acrylic rubber / styrene polymer (AAS resin), methyl methacrylate / butadiene rubber / styrene resin (MBS resin), acrylonitrile / ethylene-propylene rubber / styrene polymer (AES resin), etc. It is more preferable to use a styrene resin.
ゴム強化スチレン系樹脂はゴム状重合体の存在下に芳香族ビニル系単量体、シアン化ビニル系単量体、これらと共重合可能な他のビニル系単量体を重合して得られるグラフト共重合体または、該グラフト共重合体と上記単量体を共重合して得られる共重合体から構成される樹脂である。 Rubber-reinforced styrene resins are grafts obtained by polymerizing aromatic vinyl monomers, vinyl cyanide monomers, and other vinyl monomers copolymerizable with these in the presence of rubbery polymers. A resin comprising a copolymer or a copolymer obtained by copolymerizing the graft copolymer and the above monomer.
グラフト共重合体に用いられるゴム状重合体としては、特に制限はないが、ポリブタジエンゴム、スチレン−ブタジエンゴム（ＳＢＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）等のジエン系ゴム、エチレン−プロピレンゴム、エチレン−プロピレン−非共役ジエン（エチリデンノルボルネン、ジシクロペンタジエン等）ゴム等のエチレン−プロピレン系ゴム、ポリブチルアクリレート等のアクリル系ゴム、シリコーン系ゴム、更にはこれらのゴムから選ばれた一種以上の複合ゴムなどが挙げられ、一種または二種以上用いることができる。 The rubbery polymer used for the graft copolymer is not particularly limited, but diene rubbers such as polybutadiene rubber, styrene-butadiene rubber (SBR) and acrylonitrile-butadiene rubber (NBR), ethylene-propylene rubber, ethylene -Propylene-non-conjugated diene (ethylidene norbornene, dicyclopentadiene, etc.) rubber such as ethylene-propylene rubber, acrylic rubber such as polybutyl acrylate, silicone rubber, and one or more composites selected from these rubbers Examples thereof include rubber, and one kind or two or more kinds can be used.
グラフト共重合体及び共重合体を構成する芳香族ビニル系単量体としては、スチレン、α−メチルスチレン、パラメチルスチレン、ブロムスチレン等が挙げられ、一種または二種以上用いることができる。特にスチレン、α−メチルスチレンが好ましい。シアン化ビニル系単量体としては、アクリロニトリル、メタクリロニトリル、エタクリロニトリル、フマロニトリル等が挙げられ、一種または二種以上用いることができる。特にアクリロニトリルが好ましい。 Examples of the graft copolymer and the aromatic vinyl monomer constituting the copolymer include styrene, α-methylstyrene, paramethylstyrene, bromostyrene, and the like, and one or more of them can be used. In particular, styrene and α-methylstyrene are preferable. Examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and one or more of them can be used. Particularly preferred is acrylonitrile.
共重合可能な他のビニル系単量体としては、（メタ）アクリル酸エステル系単量体、マレイミド系単量体、アミド系単量体等が挙げられ、一種または二種以上用いることができる。（メタ）アクリル酸エステル系単量体としては（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸ブチル、アクリル酸２−エチルヘキシル、（メタ）アクリル酸フェニル、（メタ）アクリル酸４−ｔ−ブチルフェニル、（メタ）アクリル酸（ジ）ブロモフェニル、（メタ）アクリル酸クロルフェニル等を例示でき、マレイミド系単量体としてはＮ−フェニルマレイミド、Ｎ−シクロヘキシルマレイミド等を例示でき、アミド系単量体としてはアクリルアミド、メタクリルアミド等を例示できる。 Examples of other copolymerizable vinyl monomers include (meth) acrylic acid ester monomers, maleimide monomers, amide monomers, and the like, and one or more can be used. . (Meth) acrylic acid ester monomers include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate, (meth) acrylic Acid phenyl, (meth) acrylic acid 4-t-butylphenyl, (meth) acrylic acid (di) bromophenyl, (meth) acrylic acid chlorophenyl, and the like. As the maleimide monomer, N-phenylmaleimide, N-cyclohexylmaleimide and the like can be exemplified, and examples of the amide monomer include acrylamide and methacrylamide.
ゴム強化スチレン系樹脂中に含まれるゴム状重合体の重量平均粒子径は物性バランスの観点から０．０５〜２．０μｍであることが好ましく、０．１〜１．０μｍであることがより好ましい。ゴム強化スチレン系樹脂の超薄切片を作製し、ゴム状重合体の染色処理を行った後、透過型電子顕微鏡で写真撮影を行い、画像解析装置を用いてゴム粒子の面積を計測し、その円相当径を求めることで重量平均粒子径を算出する事が出来る。 The weight average particle diameter of the rubber-like polymer contained in the rubber-reinforced styrene resin is preferably 0.05 to 2.0 μm, more preferably 0.1 to 1.0 μm from the viewpoint of physical property balance. . After making an ultra-thin section of rubber-reinforced styrene resin and dyeing the rubbery polymer, taking a picture with a transmission electron microscope, measuring the area of the rubber particles using an image analyzer, By calculating the equivalent circle diameter, the weight average particle diameter can be calculated.
グラフト共重合体のグラフト率（グラフト共重合体のアセトン可溶分量と不溶分量及びグラフト共重合体中の複合ゴムの重量から求める。）、及びグラフト共重合体と共重合体のアセトン可溶分の還元粘度（０．４ｇ/１００ｃｃ、Ｎ，Ｎジメチルホルムアミド溶液として３０℃で測定）に特に制限はなく、要求性能によって任意の構造のものを使用することができるが、物性バランスの観点から、グラフト率は５〜１５０％であることが好ましく、還元粘度は０．２〜２．０ｄｌ／ｇであることが好ましい。 Graft rate of the graft copolymer (determined from the acetone soluble and insoluble amounts of the graft copolymer and the weight of the composite rubber in the graft copolymer), and the acetone soluble content of the graft copolymer and copolymer. There is no particular limitation on the reduced viscosity (measured at 30 ° C. as an N, N dimethylformamide solution) of 0.4 g / 100 cc, and any structure can be used depending on the required performance, but from the viewpoint of balance of physical properties, The graft ratio is preferably 5 to 150%, and the reduced viscosity is preferably 0.2 to 2.0 dl / g.
熱可塑性樹脂（Ｂ）としてゴム強化スチレン系樹脂を用いる場合、物性バランスの観点からグラフト共重合体２０〜８０重量％、共重合体２０〜８０重量％（グラフト共重合体と共重合体の合計は１００重量％）であることが好ましく、グラフト共重合体３０〜７０重量％、共重合体３０〜７０重量％であることがより好ましい。 When a rubber-reinforced styrene-based resin is used as the thermoplastic resin (B), the graft copolymer is 20 to 80% by weight and the copolymer is 20 to 80% by weight (the total of the graft copolymer and the copolymer) from the viewpoint of physical property balance. Is preferably 100% by weight), more preferably 30 to 70% by weight of the graft copolymer and 30 to 70% by weight of the copolymer.
本発明で用いられる熱可塑性樹脂（Ｂ）には、金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）との相容性をさらに向上させる目的で、ポリアミドの末端基と反応性を有する官能基を有する単量体を含むことが好ましい。 The thermoplastic resin (B) used in the present invention has a functional group reactive with the end group of the polyamide for the purpose of further improving the compatibility with the polyamide (A) carrying a metal phthalocyanine compound or a salt thereof. It is preferable to include a monomer having
ポリアミドの末端基と反応性を有する官能基としては、例えばカルボキシル基、ヒドロキシル基、エポキシ基、アミノ基またはオキサゾリン基が挙げられる。 Examples of the functional group having reactivity with the end group of polyamide include a carboxyl group, a hydroxyl group, an epoxy group, an amino group, and an oxazoline group.
カルボキシル基を含有する単量体としては、アクリル酸、メタクリル酸、マレイン酸、フタル酸、イタコン酸、無水マレイン酸等が、ヒドロキシル基を含有する単量体としては、アクリル酸２−ヒドロキシエチル、メタクリル酸２−ヒドロキシエチル、アクリル酸３−ヒドロキシプロピル、メタクリル酸３−ヒドロキシプロピル等が、エポキシ基を含有する単量体としては、アクリル酸グリシジル、メタクリル酸グリシジル、イタコン酸グリシジル、アリルグリシジルエーテル、ｐ−グリシジルスチレン等が、アミノ基を含有する単量体としては、アクリルアミド、メタクリルアミド、Ｎ−メチルアクリルアミド、アクリル酸アミノエチル、アクリル酸プロピルアミノエチル、メタクリル酸ジメチルアミノエチル、メタクリル酸エチルアミノプロピル等が、オキサゾリン基を含有する単量体としては、２−ビニル−２−オキサゾリン、５−メチル−２−ビニル−２−オキサゾリン、２−イソプロペニル−オキサゾリン、２−アクロイル−オキサゾリン、２−スチリル−オキサゾリン等が挙げられ、それぞれ1種または２種以上用いることができる。 As a monomer containing a carboxyl group, acrylic acid, methacrylic acid, maleic acid, phthalic acid, itaconic acid, maleic anhydride, etc., and as a monomer containing a hydroxyl group, 2-hydroxyethyl acrylate, As monomers containing 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, etc., which contain epoxy groups, glycidyl acrylate, glycidyl methacrylate, glycidyl itaconate, allyl glycidyl ether, p-Glycidyl styrene and the like include amino group-containing monomers such as acrylamide, methacrylamide, N-methylacrylamide, aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, and ethylamino methacrylate. Examples of the monomer containing oxazoline group such as ropyl include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 2-isopropenyl-oxazoline, 2-acryloyl-oxazoline, 2- Examples include styryl-oxazoline, and one or more of each can be used.
本発明で用いられる熱可塑性樹脂（Ｂ）に、これら官能基を含有する単量体を導入する方法については特に制限は無く、官能基を含有する単量体を熱可塑性樹脂（Ｂ）の重合時に添加することにより共重合させることが可能であり、またこれら官能基を含有する熱可塑性樹脂と他の熱可塑性樹脂を混合すること、さらには熱可塑性樹脂と官能基を含有する単量体とを押出機内で溶融混練する際にラジカル開始剤（例えば、ｔ−ブチル−２−エチルーパーペキサノエート等）を添加して反応させる方法等を採用することが可能である。 There is no particular limitation on the method for introducing the monomer containing the functional group into the thermoplastic resin (B) used in the present invention, and the monomer containing the functional group is polymerized with the thermoplastic resin (B). It is possible to copolymerize by adding at times, and to mix the thermoplastic resin containing these functional groups with other thermoplastic resins, and further to the thermoplastic resin and the monomer containing the functional group It is possible to employ a method in which a radical initiator (for example, t-butyl-2-ethyl-perpexanoate or the like) is added and reacted when melt kneading in an extruder.
熱可塑性樹脂（Ｂ）としてゴム強化スチレン系樹脂を用いる場合は、上述のグラフト共重合体と共重合体の他に、官能基を含有する単量体と他のビニル系単量体を用いて重合を行うことで得られた官能基を含有する共重合体を用いることで、熱可塑性樹脂（Ｂ）に官能基を含有する単量体を導入する方法が挙げられる。 When using a rubber-reinforced styrene resin as the thermoplastic resin (B), in addition to the above graft copolymer and copolymer, a monomer containing a functional group and another vinyl monomer are used. The method of introduce | transducing the monomer containing a functional group into a thermoplastic resin (B) by using the copolymer containing the functional group obtained by superposing | polymerizing is mentioned.
本発明の熱可塑性樹脂組成物に関して金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）と熱可塑性樹脂（Ｂ）の構成比率に特に制限は無く、目的とする消臭性能と物性バランスに合わせて適宜使用量を設定すれば良いが、金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）を１０〜９０重量％、熱可塑性樹脂（Ｂ）を１０〜９０重量％用いる事が好ましく、金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）を２０〜８０重量％、熱可塑性樹脂（Ｂ）を２０〜８０重量％用いる事がより好ましい。（金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）と熱可塑性樹脂（Ｂ）の合計は１００重量％） In the thermoplastic resin composition of the present invention, there is no particular limitation on the constituent ratio of the polyamide (A) supporting the metal phthalocyanine compound or its salt and the thermoplastic resin (B), and according to the desired deodorant performance and physical property balance. What is necessary is just to set usage-amount suitably, It is preferable to use 10-90 weight% of polyamides (A) which carry | supported the metal phthalocyanine compound or its salt, and 10-90 weight% of thermoplastic resins (B), and a metal phthalocyanine compound Alternatively, it is more preferable to use 20 to 80% by weight of the polyamide (A) supporting the salt and 20 to 80% by weight of the thermoplastic resin (B). (The total of the polyamide (A) supporting the metal phthalocyanine compound or a salt thereof and the thermoplastic resin (B) is 100% by weight)
本発明においては、必要に応じて公知の他の添加剤、例えばヒンダードアミン系の光安定剤、ヒンダードフェノール系、含硫黄有機化合物系、含リン有機化合物系等の酸化防止剤、フェノール系、アクリレート系等の熱安定剤、ベンゾエート系、ベンゾトリアゾール系、ベンゾフェノン系、サリシレート系の紫外線吸収剤、有機ニッケル系、高級脂肪酸アミド類等の滑剤、リン酸エステル類等の可塑剤、ポリブロモフェニルエーテル、テトラブロモビスフェノール−Ａ、臭素化エポキシオリゴマー、臭素化等の含ハロゲン系化合物、リン系化合物、三酸化アンチモン等の難燃剤・難燃助剤、臭気マスキング剤、カーボンブラック、酸化チタン、顔料、及び染料等を添加することもできる。更に、タルク、炭酸カルシウム、水酸化アルミニウム、ガラス繊維、ガラスフレーク、ガラスビーズ、炭素繊維、金属繊維等の補強剤や充填剤を添加することができる。 In the present invention, other known additives as necessary, for example, hindered amine light stabilizers, hindered phenol-based, sulfur-containing organic compound-based antioxidants, phenol-based, acrylates, etc. Heat stabilizers such as benzoate, benzotriazole, benzophenone, salicylate UV absorbers, organic nickel, lubricants such as higher fatty acid amides, plasticizers such as phosphate esters, polybromophenyl ether, Tetrabromobisphenol-A, brominated epoxy oligomers, halogenated compounds such as brominated compounds, phosphorus compounds, flame retardants and flame retardants such as antimony trioxide, odor masking agents, carbon black, titanium oxide, pigments, and Dye etc. can also be added. Furthermore, reinforcing agents and fillers such as talc, calcium carbonate, aluminum hydroxide, glass fibers, glass flakes, glass beads, carbon fibers, and metal fibers can be added.
本発明の熱可塑性樹脂組成物は、上述の成分を混合することで得ることができる。混合するために、例えば、押出し機、ロール、バンバリーミキサー、ニーダー等の公知の混練装置を用いることができる。 The thermoplastic resin composition of the present invention can be obtained by mixing the above-described components. In order to mix, well-known kneading apparatuses, such as an extruder, a roll, a Banbury mixer, a kneader, can be used, for example.
また、上記にて得られた熱可塑性樹脂組成物は、射出成形や押出成形等、その他多様な成形方法により、各種成形品として成形することが可能である。 Moreover, the thermoplastic resin composition obtained above can be molded as various molded articles by various other molding methods such as injection molding and extrusion molding.
以下に実施例を示して本発明を具体的に説明するが、本発明はこれらによって何ら制限されるものではない。なお、実施例中にて示す「部」及び「％」は重量に基づくものである。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” are based on weight.
金属フタロシアニン化合物の分解温度の測定
熱分析ＴＧ／ＤＴＡにより測定した。
装置；ＳＩＩ社製 ＥＸＳＴＡＲ６２００ＴＧ／ＤＴＡ
測定条件
サンプル量：２ｍｇ リファレンス量：２ｍｇ リファレンス：Ａｌ２Ｏ３
昇温速度：１０℃／ｍｉｎ 雰囲気：Ａｉｒ２００ｍｌ／ｍｉｎ 測定容器：Ａｌ
測定温度範囲：３０〜５５０℃
Measurement of decomposition temperature of metal phthalocyanine compound Measured by thermal analysis TG / DTA.
Equipment: EXSTAR6200TG / DTA manufactured by SII
Measurement conditions Sample amount: 2 mg Reference amount: 2 mg Reference: Al 2 O 3
Temperature rising rate: 10 ° C./min Atmosphere: Air 200 ml / min Measuring container: Al
Measurement temperature range: 30-550 ° C
コバルトフタロシアニン化合物を担持したポリアミド繊維（Ａ−１）の製造
繊度３．３ｄｔｅｘ、繊維長０．５ｍｍのナイロン６繊維を準備した。次に、濃度０．５％ｏｗｆ（ｏｎ ｗｅｉｇｈｔ ｆｉｂｅｒ：繊維重量比）のコバルトフタロシアニンモノスルホン酸ナトリウムの水溶液に２ｍｌ／Ｌになるように酢酸を加えた水溶液（浴比＝１：８）４００Ｌに、ナイロン６繊維を５０ｋｇ入れ、９０℃で２０分間攪拌することで、コバルトフタロシアニン化合物（コバルトフタロシアニンモノスルホン酸ナトリウム塩）を担持したポリアミド繊維（Ａ−１）を得た。上記コバルトフタロシアニン化合物の分解温度は、３１５℃であった。
Production fineness 3.3dtex polyamide fibers carrying cobalt phthalocyanine compound (A-1), were prepared nylon 6 fibers having a fiber length of 0.5 mm. Next, 400 L of an aqueous solution (bath ratio = 1: 8) in which acetic acid was added to an aqueous solution of 0.5% owf (on weight fiber: fiber weight ratio) of cobalt phthalocyanine monosulfonate to an amount of 2 ml / L Then, 50 kg of nylon 6 fiber was added and stirred at 90 ° C. for 20 minutes to obtain a polyamide fiber (A-1) carrying a cobalt phthalocyanine compound (cobalt phthalocyanine monosulfonate sodium salt). The decomposition temperature of the cobalt phthalocyanine compound was 315 ° C.
鉄フタロシアニン化合物を担時したポリアミド繊維（Ａ−２）の製造
繊度３．３ｄｔｅｘ、繊維長０．５ｍｍのナイロン６繊維を準備した。次に、濃度０．３％ｏｗｆの鉄フタロシアニンモノスルホン酸ナトリウムの水溶液に２ｍｌ／Ｌになるように酢酸を加えた水溶液（浴比＝１：８）４００Ｌに、ナイロン６繊維を５０ｋｇ入れ、９０℃で２０分間攪拌することで、鉄フタロシアニン化合物（鉄フタロシアニンモノスルホン酸ナトリウム塩）を担持したポリアミド繊維（Ａ−２）を得た。上記鉄フタロシアニン化合物の分解温度は、３００℃であった。
A nylon 6 fiber having a manufacturing fineness of 3.3 dtex and a fiber length of 0.5 mm was prepared for a polyamide fiber (A-2) carrying an iron phthalocyanine compound . Next, 50 kg of nylon 6 fiber was added to 400 L of an aqueous solution (bath ratio = 1: 8) in which acetic acid was added to an aqueous solution of 0.3% owf of sodium iron phthalocyanine monosulfonate at a concentration of 2 ml / L. By stirring at 20 ° C. for 20 minutes, a polyamide fiber (A-2) carrying an iron phthalocyanine compound (iron phthalocyanine monosulfonate sodium salt) was obtained. The decomposition temperature of the iron phthalocyanine compound was 300 ° C.
コバルトフタロシアニン化合物を担持したポリアミドペレット（Ａ−３）の製造
ナイロン６繊維の代わりにナイロンペレット（宇部興産製 １０１５Ｂ、長径３ｍｍ、短径２ｍｍ）を使用した以外は、（Ａ−１）と同様の方法で作成した。
Manufacture of polyamide pellet (A-3) carrying cobalt phthalocyanine compound The same as (A-1) except that nylon pellet (1015B, major axis 3 mm, minor axis 2 mm) was used instead of nylon 6 fiber. Created by the method.
熱可塑性樹脂組成物（Ｂ）の製造
＜ゴム強化スチレン系樹脂（Ｃ）の製造＞
窒素置換した反応器にスチレン−ブタジエンゴムラテックス（スチレン５重量％、重量平均粒子径０．４μｍ）５０部（固形分）、水１５０部、エチレンジアミン四酢酸二ナトリウム塩０．１部、硫酸第１鉄０．００１部、ナトリウムホルムアルデヒドスルホキシレート０．３部を入れ、６０℃に加熱後、スチレン３５部、アクリロニトリル１５部及びキュメンハイドロパーオキサイド０．２部からなる混合物を３時間に亘り連続的に添加し、更に６０℃で２時間重合した。その後、塩析・脱水・乾燥を行うことで、ゴム強化スチレン系樹脂（Ｃ）を得た。
Production of thermoplastic resin composition (B) < Production of rubber-reinforced styrene-based resin (C)>
In a nitrogen-substituted reactor, 50 parts (solid content) of styrene-butadiene rubber latex (styrene 5% by weight, weight average particle size 0.4 μm), 150 parts of water, 0.1 part of ethylenediaminetetraacetic acid disodium salt, sulfuric acid first Add 0.001 part of iron and 0.3 part of sodium formaldehyde sulfoxylate, heat to 60 ° C., and continuously mix a mixture of 35 parts of styrene, 15 parts of acrylonitrile and 0.2 part of cumene hydroperoxide for 3 hours. And further polymerized at 60 ° C. for 2 hours. Then, rubber-reinforced styrene resin (C) was obtained by performing salting-out, dehydration, and drying.
＜共重合体（Ｄ−１）の製造＞
公知のバルク重合法により、スチレン７６部及びアクリロニトリル２４部からなる共重合体（Ｄ−１）を得た。
＜共重合体（Ｄ−２）の製造＞
窒素置換したガラスリアクターに、脱イオン水１００重量部を添加した後、昇温を行い、６０℃に達した時点で過硫酸カリウム０．３部、メタクリル酸５部、スチレン７０部、アクリロニトリル２５部、ターシャリードデシルメルカプタン１．６部からなるモノマー混合溶液の６％及びドデシルベンゼンスルホン酸Ｎａ１部を脱イオン水２０部に溶解させた乳化剤水溶液１０％を添加した。その後６５℃まで昇温し残りのモノマー混合液及び乳化剤水溶液を連続添加した。その後７０℃に昇温し重合を完了した。塩化カルシウムを用いて塩析したのち脱水、乾燥することで、不飽和カルボン酸を含有した共重合体（Ｄ−２）を得た。
<Production of copolymer (D-1)>
A copolymer (D-1) comprising 76 parts of styrene and 24 parts of acrylonitrile was obtained by a known bulk polymerization method.
<Production of copolymer (D-2)>
After adding 100 parts by weight of deionized water to a nitrogen-replaced glass reactor, the temperature was raised, and when 60 ° C. was reached, 0.3 part of potassium persulfate, 5 parts of methacrylic acid, 70 parts of styrene, 25 parts of acrylonitrile Then, 6% of a monomer mixed solution composed of 1.6 parts of terrieric decyl mercaptan and 10% of an aqueous emulsifier solution in which 1 part of sodium dodecylbenzenesulfonate was dissolved in 20 parts of deionized water were added. Thereafter, the temperature was raised to 65 ° C., and the remaining monomer mixture and aqueous emulsifier solution were continuously added. Thereafter, the temperature was raised to 70 ° C. to complete the polymerization. After salting out using calcium chloride, dehydration and drying were performed to obtain a copolymer (D-2) containing an unsaturated carboxylic acid.
添加剤
滑剤：日本油脂（株）製 アルフローＨ５０Ｓ
Additive lubricant: Nippon Oil & Fats Co., Ltd. Alflow H50S
＜実施例１〜９及び比較例１〜３＞
表１に示す割合でゴム強化スチレン系樹脂（Ｃ）、共重合体（Ｄ−１）、共重合体（Ｄ−２）及び滑剤を混合した後、５０ｍｍ単軸押出機を用いて２５０℃にて溶融混練することで熱可塑性樹脂（Ｂ−１）〜（Ｂ−３）を得た。
また、表２に示す割合で金属フタロシアニン化合物を担持したポリアミド繊維及びペレット（Ａ）と、熱可塑性樹脂（Ｂ）を混合した後、５０ｍｍ単軸押出機を用いて２５０℃にて溶融混練することで熱可塑性樹脂組成物のペレットを得た。金属フタロシアニン化合物を担持したポリアミド繊維（Ａ−１）及び（Ａ−２）単独については、５０ｍｍ単軸押出機を用いて２６０℃にて溶融混練し、同様にペレットを得た。得られたペレットより各種成形品を射出成形機にて成形し、評価を行った。評価結果を表２に示す。なお、それぞれの評価方法を以下に示す。
<Examples 1-9 and Comparative Examples 1-3>
After mixing the rubber-reinforced styrene resin (C), the copolymer (D-1), the copolymer (D-2), and the lubricant at the ratio shown in Table 1, the temperature was increased to 250 ° C. using a 50 mm single screw extruder. Then, thermoplastic resins (B-1) to (B-3) were obtained by melt kneading.
Moreover, after mixing the polyamide fiber and the pellet (A) carrying the metal phthalocyanine compound at the ratio shown in Table 2 and the thermoplastic resin (B), the mixture is melt-kneaded at 250 ° C. using a 50 mm single screw extruder. The pellet of the thermoplastic resin composition was obtained. The polyamide fibers (A-1) and (A-2) alone carrying the metal phthalocyanine compound were melt-kneaded at 260 ° C. using a 50 mm single screw extruder to obtain pellets in the same manner. Various molded products were molded from the obtained pellets with an injection molding machine and evaluated. The evaluation results are shown in Table 2. In addition, each evaluation method is shown below.
耐衝撃性
各実施例及び比較例で得られたペレットを用いＩＳＯ試験方法２９４に準拠して試験片を成形し、耐衝撃性を測定した。
耐衝撃性はＩＳＯ１７９に準拠し、４ｍｍ厚みで、ノッチ付きシャルピー衝撃値を測定した。単位：ｋＪ／ｍ２
Impact Resistance Using the pellets obtained in each Example and Comparative Example, a test piece was molded according to ISO test method 294, and the impact resistance was measured.
The impact resistance was in conformity with ISO 179, and a Charpy impact value with a notch was measured at a thickness of 4 mm. Unit: kJ / m 2
寸法安定性
各実施例及び比較例で得られたペレットを用い、２５０℃に設定した射出成形機にて９０ｍｍ×１５０ｍｍ×３ｍｍｔの寸法の平板作成用金型（設定温度６０℃）を用いて射出成形品を得た。得られた平板を２３℃、５０％ＲＨ恒温室内に２４時間放置した後の長辺（１５０ｍｍ方向）の長さをＬ０とし、同平板を４０℃、９０％ＲＨの条件下で２００時間放置後の長さをＬ１とした場合、次式で表される値により評価を行った。
（Ｌ１−L０）／Ｌ０×１００ （％）
◎：０．８％未満
○：０．８〜１．０％
×：１．０％以上
Dimensional stability Using pellets obtained in each of the examples and comparative examples, injection was performed using a flat plate making mold (set temperature: 60 ° C.) having dimensions of 90 mm × 150 mm × 3 mmt on an injection molding machine set at 250 ° C. A molded product was obtained. The obtained flat plate was left in a constant temperature room at 23 ° C. and 50% RH for 24 hours, the length of the long side (150 mm direction) was L0, and the flat plate was left to stand at 40 ° C. and 90% RH for 200 hours. When the length of was set to L1, it evaluated by the value represented by following Formula.
(L1-L0) / L0 × 100 (%)
A: Less than 0.8% B: 0.8-1.0%
X: 1.0% or more
消臭性
各実施例及び比較例で得られたペレット１ｇを容量５リットルのテドラーバッグに入れ、既定濃度のガスを注入した後、密閉し、２４時間後のテドラーバッグ内のガス濃度をガス検知管で測定した。単位：ｐｐｍ。
ガス種：アンモニア、規定濃度：１００ｐｐｍ
ガス種：硫化水素、規定濃度：４ｐｐｍ
Deodorizing property 1 g of the pellets obtained in each Example and Comparative Example were put into a 5 liter Tedlar bag, injected with a predetermined concentration of gas, sealed, and the gas concentration in the Tedlar bag after 24 hours was measured with a gas detector tube. It was measured. Unit: ppm.
Gas type: ammonia, specified concentration: 100 ppm
Gas type: hydrogen sulfide, specified concentration: 4ppm
表２に示すように、実施例１〜９は本発明に関わる熱可塑性樹脂組成物の例であり、耐衝撃性、寸法安定性だけでなく、消臭性能に優れていた。 As shown in Table 2, Examples 1 to 9 are examples of the thermoplastic resin composition according to the present invention, and were excellent not only in impact resistance and dimensional stability but also in deodorizing performance.
表２に示すように、比較例１、３は熱可塑性樹脂（Ｂ）を含まないため、耐衝撃性、寸法安定性に劣っていた。また、比較例２は金属フタロシアニン化合物またはその塩を担持したポリアミド（Ａ）を用いていないため、消臭性能に劣っていた。 As shown in Table 2, since Comparative Examples 1 and 3 did not contain the thermoplastic resin (B), they were inferior in impact resistance and dimensional stability. Moreover, since the comparative example 2 did not use the polyamide (A) which carry | supported the metal phthalocyanine compound or its salt, it was inferior in the deodorizing performance.
本発明の熱可塑性樹脂組成物及び成形体は、耐衝撃性、寸法安定性だけでなく、消臭性能に優れるため、医療用部品やサニタリー用部品等への利用価値が高い。 The thermoplastic resin composition and the molded product of the present invention are excellent in deodorizing performance as well as impact resistance and dimensional stability, and thus have high utility value for medical parts and sanitary parts.
Claims (7)
式（ＩＩ）中、ＭはＣｏ、Ｒ１、Ｒ２、Ｒ３及びＲ４はスルホン酸基であり、ｎ１、ｎ２、ｎ３及びｎ４は０〜４で１≦ｎ１＋ｎ２＋ｎ３＋ｎ４≦８を満たす数である。 A thermoplastic resin composition comprising a polyamide (A) having a metal phthalocyanine compound represented by the following chemical formula (II) or a salt thereof supported by ion dyeing and a thermoplastic resin (B), Resin (B) is a thermoplastic resin composition containing a rubber-reinforced styrene resin and no polyamide resin.
In formula (II), M is Co 2, R 1, R 2, R 3 and R 4 are sulfonic acid groups, and n 1, n 2, n 3 and n 4 are numbers 0 to 4 and satisfy 1 ≦ n 1 + n 2 + n 3 + n 4 ≦ 8.
式（ＩＩ）中、ＭはＣｏ、Ｒ１、Ｒ２、Ｒ３及びＲ４はスルホン酸基であり、ｎ１、ｎ２、ｎ３及びｎ４は０〜４で１≦ｎ１＋ｎ２＋ｎ３＋ｎ４≦８を満たす数である。 A polyamide (A) and a thermoplastic resin (B) obtained by loading a metal phthalocyanine compound or a salt thereof obtained by putting the polyamide into an aqueous solution of a metal phthalocyanine compound or a salt thereof represented by the following chemical formula (II) by ion dyeing ; A method for producing a thermoplastic resin composition obtained by melt-kneading a thermoplastic resin (B), wherein the thermoplastic resin (B) contains a rubber-reinforced styrene resin and does not contain a polyamide resin. A method for producing a resin composition.
In formula (II), M is Co 2, R 1, R 2, R 3 and R 4 are sulfonic acid groups, and n 1, n 2, n 3 and n 4 are numbers 0 to 4 and satisfy 1 ≦ n 1 + n 2 + n 3 + n 4 ≦ 8.
The method for producing a thermoplastic resin composition according to claim 5, wherein the polyamide (A) has a pellet form.
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