JP4714526B2 - Polypropylene resin composition - Google Patents
Polypropylene resin composition Download PDFInfo
- Publication number
- JP4714526B2 JP4714526B2 JP2005230485A JP2005230485A JP4714526B2 JP 4714526 B2 JP4714526 B2 JP 4714526B2 JP 2005230485 A JP2005230485 A JP 2005230485A JP 2005230485 A JP2005230485 A JP 2005230485A JP 4714526 B2 JP4714526 B2 JP 4714526B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polypropylene resin
- resin composition
- acid amide
- ethylene
- 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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- -1 Polypropylene Polymers 0.000 title claims description 64
- 229920001155 polypropylene Polymers 0.000 title claims description 56
- 239000004743 Polypropylene Substances 0.000 title claims description 55
- 239000011342 resin composition Substances 0.000 title claims description 38
- 229920001577 copolymer Polymers 0.000 claims description 21
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 20
- 239000005977 Ethylene Substances 0.000 claims description 20
- 239000004711 α-olefin Substances 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 239000011256 inorganic filler Substances 0.000 claims description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 14
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- 150000004665 fatty acids Chemical class 0.000 claims description 12
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 9
- 239000003086 colorant Substances 0.000 claims description 9
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920001384 propylene homopolymer Polymers 0.000 claims description 4
- 238000000465 moulding Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000000806 elastomer Substances 0.000 description 10
- 238000001746 injection moulding Methods 0.000 description 10
- 239000000454 talc Substances 0.000 description 9
- 229910052623 talc Inorganic materials 0.000 description 9
- 238000004898 kneading Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- MYONAGGJKCJOBT-UHFFFAOYSA-N benzimidazol-2-one Chemical compound C1=CC=CC2=NC(=O)N=C21 MYONAGGJKCJOBT-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 2
- XHSVWKJCURCWFU-UHFFFAOYSA-N 19-[3-(19-amino-19-oxononadecyl)phenyl]nonadecanamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCC1=CC=CC(CCCCCCCCCCCCCCCCCCC(N)=O)=C1 XHSVWKJCURCWFU-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000021189 garnishes Nutrition 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- OSNILPMOSNGHLC-UHFFFAOYSA-N 1-[4-methoxy-3-(piperidin-1-ylmethyl)phenyl]ethanone Chemical compound COC1=CC=C(C(C)=O)C=C1CN1CCCCC1 OSNILPMOSNGHLC-UHFFFAOYSA-N 0.000 description 1
- ALDZNWBBPCZXGH-UHFFFAOYSA-N 12-hydroxyoctadecanamide Chemical compound CCCCCCC(O)CCCCCCCCCCC(N)=O ALDZNWBBPCZXGH-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- DKNLMUCCEFHGNE-UHFFFAOYSA-N 2,2-dihydroxy-3-methylideneoctadecanamide Chemical compound CCCCCCCCCCCCCCCC(=C)C(O)(O)C(N)=O DKNLMUCCEFHGNE-UHFFFAOYSA-N 0.000 description 1
- VESQWGARFWAICR-UHFFFAOYSA-N 2,2-dihydroxyoctadecanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCC(O)(O)C(N)=O VESQWGARFWAICR-UHFFFAOYSA-N 0.000 description 1
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- WZSFTHVIIGGDOI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3-[2-methyl-3-[(4,5,6,7-tetrachloro-3-oxoisoindol-1-yl)amino]anilino]isoindol-1-one Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C2=C1C(NC1=CC=CC(NC=3C4=C(C(=C(Cl)C(Cl)=C4Cl)Cl)C(=O)N=3)=C1C)=NC2=O WZSFTHVIIGGDOI-UHFFFAOYSA-N 0.000 description 1
- DWDURZSYQTXVIN-UHFFFAOYSA-N 4-[(4-aminophenyl)-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]aniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 DWDURZSYQTXVIN-UHFFFAOYSA-N 0.000 description 1
- IYHIFXGFKVJNBB-UHFFFAOYSA-N 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonic acid Chemical compound C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S(O)(=O)=O IYHIFXGFKVJNBB-UHFFFAOYSA-N 0.000 description 1
- CGLVZFOCZLHKOH-UHFFFAOYSA-N 8,18-dichloro-5,15-diethyl-5,15-dihydrodiindolo(3,2-b:3',2'-m)triphenodioxazine Chemical compound CCN1C2=CC=CC=C2C2=C1C=C1OC3=C(Cl)C4=NC(C=C5C6=CC=CC=C6N(C5=C5)CC)=C5OC4=C(Cl)C3=NC1=C2 CGLVZFOCZLHKOH-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ORAWFNKFUWGRJG-UHFFFAOYSA-N Docosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCC(N)=O ORAWFNKFUWGRJG-UHFFFAOYSA-N 0.000 description 1
- 229920012753 Ethylene Ionomers Polymers 0.000 description 1
- XKTMIJODWOEBKO-UHFFFAOYSA-M Guinee green B Chemical compound [Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC=CC=2)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 XKTMIJODWOEBKO-UHFFFAOYSA-M 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 239000004233 Indanthrene blue RS Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- LMULDSDQRQVZMW-UHFFFAOYSA-N N-(5-chloro-2,4-dimethoxyphenyl)-4-[[5-(diethylsulfamoyl)-2-methoxyphenyl]diazenyl]-3-hydroxynaphthalene-2-carboxamide Chemical compound CCN(CC)S(=O)(=O)C1=CC=C(OC)C(N=NC=2C3=CC=CC=C3C=C(C=2O)C(=O)NC=2C(=CC(OC)=C(Cl)C=2)OC)=C1 LMULDSDQRQVZMW-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- 229910001308 Zinc ferrite Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 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 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- DGOBMKYRQHEFGQ-UHFFFAOYSA-L acid green 5 Chemical compound [Na+].[Na+].C=1C=C(C(=C2C=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C=2C=CC(=CC=2)S([O-])(=O)=O)C=CC=1N(CC)CC1=CC=CC(S([O-])(=O)=O)=C1 DGOBMKYRQHEFGQ-UHFFFAOYSA-L 0.000 description 1
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- HEQCHSSPWMWXBH-UHFFFAOYSA-L barium(2+) 1-[(2-carboxyphenyl)diazenyl]naphthalen-2-olate Chemical compound [Ba++].Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O.Oc1ccc2ccccc2c1N=Nc1ccccc1C([O-])=O HEQCHSSPWMWXBH-UHFFFAOYSA-L 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- 239000001055 blue pigment Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- PZTQVMXMKVTIRC-UHFFFAOYSA-L chembl2028348 Chemical compound [Ca+2].[O-]S(=O)(=O)C1=CC(C)=CC=C1N=NC1=C(O)C(C([O-])=O)=CC2=CC=CC=C12 PZTQVMXMKVTIRC-UHFFFAOYSA-L 0.000 description 1
- ZLFVRXUOSPRRKQ-UHFFFAOYSA-N chembl2138372 Chemical compound [O-][N+](=O)C1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 ZLFVRXUOSPRRKQ-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+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 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- VAPILSUCBNPFBS-UHFFFAOYSA-L disodium 2-oxido-5-[[4-[(4-sulfophenyl)diazenyl]phenyl]diazenyl]benzoate Chemical compound [Na+].[Na+].Oc1ccc(cc1C([O-])=O)N=Nc1ccc(cc1)N=Nc1ccc(cc1)S([O-])(=O)=O VAPILSUCBNPFBS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- VJJBJJBTUXPNEO-UHFFFAOYSA-N docosanamide;ethene Chemical compound C=C.CCCCCCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCCCCCC(N)=O VJJBJJBTUXPNEO-UHFFFAOYSA-N 0.000 description 1
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 1
- GFQOFGWPGYRLAO-UHFFFAOYSA-N dodecanamide;ethene Chemical compound C=C.CCCCCCCCCCCC(N)=O.CCCCCCCCCCCC(N)=O GFQOFGWPGYRLAO-UHFFFAOYSA-N 0.000 description 1
- LJZKUDYOSCNJPU-UHFFFAOYSA-N dotetracontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LJZKUDYOSCNJPU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 1
- ZJOLCKGSXLIVAA-UHFFFAOYSA-N ethene;octadecanamide Chemical compound C=C.CCCCCCCCCCCCCCCCCC(N)=O.CCCCCCCCCCCCCCCCCC(N)=O ZJOLCKGSXLIVAA-UHFFFAOYSA-N 0.000 description 1
- PLYDMIIYRWUYBP-UHFFFAOYSA-N ethyl 4-[[2-chloro-4-[3-chloro-4-[(3-ethoxycarbonyl-5-oxo-1-phenyl-4h-pyrazol-4-yl)diazenyl]phenyl]phenyl]diazenyl]-5-oxo-1-phenyl-4h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C1=NN(C=2C=CC=CC=2)C(=O)C1N=NC(C(=C1)Cl)=CC=C1C(C=C1Cl)=CC=C1N=NC(C(=N1)C(=O)OCC)C(=O)N1C1=CC=CC=C1 PLYDMIIYRWUYBP-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- FEEPBTVZSYQUDP-UHFFFAOYSA-N heptatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O FEEPBTVZSYQUDP-UHFFFAOYSA-N 0.000 description 1
- JAGIUTGWNQNUTM-UHFFFAOYSA-N hex-1-ene;oct-1-ene Chemical compound CCCCC=C.CCCCCCC=C JAGIUTGWNQNUTM-UHFFFAOYSA-N 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、耐汚れ性に優れたポリプロピレン樹脂組成物に関し、特に、耐汚れ性、物性バランスに優れ、かつ射出成形加工性が良好なポリプロピレン樹脂組成物に関する。 The present invention relates to a polypropylene resin composition excellent in stain resistance, and particularly relates to a polypropylene resin composition excellent in stain resistance and physical property balance and excellent in injection molding processability.
従来からポリプロピレンなどのポリオレフィンは、たとえば射出成形により部品などに成形され、各種用途に広く利用されている。このようなポリプロピレン成形品は、意匠性、耐傷つき性向上などのために通常部品表面に塗装が施されている。しかしながら、近年は、コスト合理化の観点から、また溶剤規制などの環境問題の観点から、樹脂に直接顔料を入れ着色することにより塗装を施さない、いわゆる原着材料としての使用が広がってきている。 Conventionally, polyolefins such as polypropylene have been molded into parts by injection molding, for example, and are widely used for various applications. Such polypropylene molded products are usually coated on the surface of the parts in order to improve design properties and scratch resistance. However, in recent years, from the viewpoint of cost rationalization and from the viewpoint of environmental problems such as solvent regulations, the use as a so-called original material that is not coated by coloring a resin directly into a resin is spreading.
例えば、プロピレン系樹脂;50〜95重量部と、アクリル系樹脂;5〜40重量部とからなる樹脂成分と着色剤、無機充填剤とから形成された原着材料からなる表面光沢に優れ、色の深みがある塗装不要な射出成形品(例えば、特許文献1参照。)が提案されている。また、エチレン系共重合体(エチレン−酢酸ビニル共重合体)10〜25重量%、プロピレン重合体4〜12重量%、ポリエチレン8〜23重量%、無機充填材20〜42重量%とから形成された材料からなる、表面傷付き性に優れた樹脂組成物が提案されている(例えば、特許文献2参照。)。さらに、プロピレン系ブロック共重合体50〜99.9重量%、ポリエチレン0.1〜10重量%、MFRが0.1〜60g/10分のエチレン−α−オレフィン共重合体エラストマー又はスチレン系エラストマー0〜30重量%、無機フィラー0〜50重量%、脂肪酸アミド又はその誘導体0.05〜3重量部、25℃における粘度が1万mm2/s以上のシリコーン化合物0〜3重量部、不飽和カルボン酸又はその誘導体で変性されたポリオレフィン0〜5重量部からなる耐傷つき性の良好な原着材料(例えば、特許文献3参照。)が提案されている。 For example, it has excellent surface gloss composed of a raw material formed from a resin component consisting of a propylene-based resin; 50 to 95 parts by weight and an acrylic resin; 5 to 40 parts by weight, a colorant, and an inorganic filler. There has been proposed an injection-molded product (see, for example, Patent Document 1) that does not require painting. Further, it is formed from 10 to 25% by weight of an ethylene copolymer (ethylene-vinyl acetate copolymer), 4 to 12% by weight of a propylene polymer, 8 to 23% by weight of polyethylene, and 20 to 42% by weight of an inorganic filler. There has been proposed a resin composition that is made of an excellent material and has excellent surface scratch resistance (see, for example, Patent Document 2). Further, an ethylene-α-olefin copolymer elastomer or a styrene elastomer 0 to 50 to 99.9% by weight of a propylene-based block copolymer, 0.1 to 10% by weight of polyethylene, and an MFR of 0.1 to 60 g / 10 min. -30% by weight, inorganic filler 0-50% by weight, fatty acid amide or derivative 0.05-3 parts by weight, silicone compound 0-25 parts by weight with a viscosity at 25 ° C. of 10,000 mm 2 / s or more, unsaturated carboxylic acid An original material having good scratch resistance (see, for example, Patent Document 3) comprising 0 to 5 parts by weight of a polyolefin modified with an acid or a derivative thereof has been proposed.
しかし、かかる提案では、雨水、油、埃、ダスト、虫などによる汚れ成分に対する考慮は一切なされていない。長期における屋内外での使用においては、成形品表面に前記汚れ成分に起因するしみ等の汚れが付着するといった問題が想定される。付着した汚れが落ちやすい耐汚れ性に優れた原着材料が出現すれば産業上利用価値はきわめて大きい。本発明者らの検討では、上記提案にかかる原着材料は、使用態様を想定した汚れ試験において付着した汚れが落ちにくく、耐汚れ性の性能が十分なものとはいえなかった。
本発明の目的は、上記欠点を解決しつつ、耐汚れ性に優れているポリプロピレン樹脂組成物を提供、特に成形性、物性バランスに優れ、その上耐汚れ性に優れているポリプロピレン樹脂組成物を提供することにある。 The object of the present invention is to provide a polypropylene resin composition excellent in stain resistance while solving the above-mentioned drawbacks, and in particular, a polypropylene resin composition excellent in moldability and physical property balance and excellent in stain resistance. It is to provide.
本発明者等は、上記課題を解決するために、種々の研究を重ねた結果、ポリプロピレン樹脂に特定のエチレン・酢酸ビニル共重合体(EVA)並びに脂肪酸アミド類を組み合わせることにより、成形性、物性バランスに優れ、特に従来の材料に比べて耐汚れ性を発現することを見出し、本発明を完成することに至ったものである。 In order to solve the above problems, the present inventors have made various studies, and as a result, by combining a specific ethylene / vinyl acetate copolymer (EVA) and a fatty acid amide with polypropylene resin, the moldability and physical properties are improved. It has been found that it is excellent in balance and particularly exhibits stain resistance as compared with conventional materials, and has completed the present invention.
すなわち、本発明の第1の発明によれば、下記成分(A)〜(E)を含有することを特徴とするポリプロピレン樹脂組成物が提供される。
(A)ポリプロピレン樹脂 40〜99.45重量%
(B)酢酸ビニル重合単位の比率が5〜25重量%であるエチレン・酢酸ビニル共重合体 0.5〜8重量%
(C)脂肪酸アミドまたはその誘導体 0.05〜2.5重量%
(D)熱可塑性エラストマー 0〜35重量%
(E)無機充填材 0〜35重量%
That is, according to 1st invention of this invention, the polypropylene resin composition characterized by containing the following component (A)-(E) is provided.
(A) Polypropylene resin 40 to 99.45% by weight
(B) Ethylene / vinyl acetate copolymer having a vinyl acetate polymer unit ratio of 5 to 25% by weight 0.5 to 8% by weight
(C) Fatty acid amide or derivative thereof 0.05 to 2.5% by weight
(D) Thermoplastic elastomer 0 to 35% by weight
(E) Inorganic filler 0 to 35% by weight
また、本発明の第2の発明によれば、第1の発明において、さらに、成分(A)〜(E)の合計100重量部に対して、(F)着色剤0.1〜50重量部を含有することを特徴とするポリプロピレン樹脂組成物が提供される。 According to the second invention of the present invention, in the first invention, 0.1 to 50 parts by weight of (F) colorant is further added to 100 parts by weight of components (A) to (E). The polypropylene resin composition characterized by containing is provided.
また、本発明の第3の発明によれば、第1又は2の発明において、ポリプロピレン樹脂が、MFRが30〜400g/10分のプロピレン単独重合部分を含み、MFRが10〜200g/10分のプロピレン・α−オレフィンブロック共重合体であることを特徴とするポリプロピレン樹脂組成物が提供される。 According to the third invention of the present invention, in the first or second invention, the polypropylene resin contains a propylene homopolymer portion having an MFR of 30 to 400 g / 10 min, and the MFR of 10 to 200 g / 10 min. A polypropylene resin composition is provided which is a propylene / α-olefin block copolymer.
本発明の樹脂組成物は、耐汚れ性に優れ、かつ機械物性および射出成形性にすぐれたポリプロピレン樹脂組成物であり、特に射出成形による特に各種工業部品、家電用部品、自動車部品として好適な樹脂組成物である。 The resin composition of the present invention is a polypropylene resin composition excellent in stain resistance and excellent in mechanical properties and injection moldability, and particularly suitable for various industrial parts, home appliance parts and automobile parts by injection molding. It is a composition.
本発明のポリプロピレン樹脂組成物は、(A)ポリプロピレン樹脂、(B)エチレン・酢酸ビニル共重合体、(C)脂肪酸アミドまたはその誘導体、(D)熱可塑性エラストマー、および、(E)無機充填材を含有し、さらに必要に応じて、(G)着色剤を含有するポリプロピレン樹脂組成物である。以下に、ポリプロピレン樹脂組成物の構成成分、ポリプロピレン樹脂組成物、ポリプロピレン樹脂組成物の製造方法、ポリプロピレン樹脂組成物の用途について詳細に説明する。 The polypropylene resin composition of the present invention comprises (A) a polypropylene resin, (B) an ethylene / vinyl acetate copolymer, (C) a fatty acid amide or a derivative thereof, (D) a thermoplastic elastomer, and (E) an inorganic filler. And (G) a polypropylene resin composition containing a colorant, if necessary. Below, the component of a polypropylene resin composition, a polypropylene resin composition, the manufacturing method of a polypropylene resin composition, and the use of a polypropylene resin composition are demonstrated in detail.
1.ポリプロピレン樹脂組成物の構成成分
(1)ポリプロピレン樹脂(A)
本発明のポリプロピレン樹脂組成物に用いるポリプロピレン樹脂(A)は、プロピレン単独重合体、プロピレンと炭素数2〜10のプロピレン以外のα−オレフィンとの共重合体、例えば、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−オレフィンブロック共重合体などから選ばれる樹脂である。共重合体に用いるα−オレフィンとしては、例えば、エチレン、1−ブテン、1−ヘキセン、4−メチル−1−ペンテン、1−オクテンなどから選ばれ、なかでも、エチレン、1−ブテン、1−ヘキセンが好ましく、特にエチレンが好ましい。
1. Component of polypropylene resin composition (1) Polypropylene resin (A)
The polypropylene resin (A) used in the polypropylene resin composition of the present invention is a propylene homopolymer, a copolymer of propylene and an α-olefin other than propylene having 2 to 10 carbon atoms, such as propylene / α-olefin random copolymer. It is a resin selected from a polymer, a propylene / α-olefin block copolymer, and the like. The α-olefin used in the copolymer is, for example, selected from ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and the like. Among them, ethylene, 1-butene, 1-octene Hexene is preferred, and ethylene is particularly preferred.
ポリプロピレン樹脂(A)のメルトフローレート(MFR)は、10〜200g/10分が好ましく、30〜150g/10分がより好ましく、50〜120g/10分がさらに好ましい。MFRが10g/10分未満では成形性が劣り、200g/10分を超えると衝撃強度、引張り伸びが低下する。
ここで、MFRは、JIS K 7210に準拠し、230℃、2.16kg荷重で測定する値である。
The melt flow rate (MFR) of the polypropylene resin (A) is preferably 10 to 200 g / 10 minutes, more preferably 30 to 150 g / 10 minutes, and further preferably 50 to 120 g / 10 minutes. When the MFR is less than 10 g / 10 minutes, the moldability is inferior, and when it exceeds 200 g / 10 minutes, the impact strength and the tensile elongation are lowered.
Here, MFR is a value measured at 230 ° C. and a 2.16 kg load in accordance with JIS K 7210.
ポリプロピレン樹脂(A)が、プロピレンとα−オレフィンランダム共重合体である場合、共重合体中のα−オレフィン含量は、0.1〜20重量%が好ましく、0.5〜12重量%がより好ましく、1〜8重量%がさらに好ましい。 When the polypropylene resin (A) is propylene and an α-olefin random copolymer, the α-olefin content in the copolymer is preferably 0.1 to 20% by weight, more preferably 0.5 to 12% by weight. Preferably, 1 to 8% by weight is more preferable.
ポリプロピレン樹脂(A)が、プロピレン単独重合体部分である結晶性ポリプロピレン部分とプロピレン・α−オレフィン共重合体部分からなるプロピレン・α−オレフィンブロック共重合体である場合、プロピレン・α−オレフィン共重合体部分の含有量は、2〜35重量%が好ましく、プロピレン・α−オレフィン共重合体部分のα−オレフィン含有量は、70重量%以下が好ましく、30〜60重量%がより好ましい。また、結晶性ポリプロピレン部分のMFRは、30〜400g/10分が好ましく、50〜300g/10分がより好ましく、100〜200g/10分がさらに好ましい。結晶性ポリプロピレン部分のMFRとブロック共重合体全体のMFRの組合せが上記範囲を逸脱した場合、流動性や耐衝撃性、引張伸びが不良となる。 When the polypropylene resin (A) is a propylene / α-olefin block copolymer comprising a crystalline polypropylene portion which is a propylene homopolymer portion and a propylene / α-olefin copolymer portion, propylene / α-olefin copolymer The content of the coalescence part is preferably 2 to 35% by weight, and the content of the α-olefin in the propylene / α-olefin copolymer part is preferably 70% by weight or less, more preferably 30 to 60% by weight. The MFR of the crystalline polypropylene portion is preferably 30 to 400 g / 10 minutes, more preferably 50 to 300 g / 10 minutes, and further preferably 100 to 200 g / 10 minutes. When the combination of the MFR of the crystalline polypropylene portion and the MFR of the entire block copolymer is out of the above range, fluidity, impact resistance, and tensile elongation become poor.
ポリプロピレン樹脂(A)は、高立体規則性触媒を用いてスラリー重合、バルク重合、気相重合により製造することが好ましい。高立体規則性触媒としては、塩化マグネシウムに四塩化チタン、有機ハイドライド、及び有機シラン化合物を接触させて形成した固体成分に有機アルミニウム化合物を組み合わせた触媒が挙げられる。重合方式としては、バッチ重合、連続重合のどちらの方式でも採用される。 The polypropylene resin (A) is preferably produced by slurry polymerization, bulk polymerization, or gas phase polymerization using a highly stereoregular catalyst. Examples of the highly stereoregular catalyst include a catalyst in which an organic aluminum compound is combined with a solid component formed by bringing magnesium chloride into contact with titanium tetrachloride, an organic hydride, and an organic silane compound. As the polymerization method, either batch polymerization or continuous polymerization can be employed.
(2)エチレン・酢酸ビニル共重合体(B)
本発明のポリプロピレン樹脂組成物に用いるエチレン・酢酸ビニル共重合体(B)は、酢酸ビニル重合単位の比率が5〜25重量%であり、7〜20重量%が好ましく、10〜15重量%が特に好ましい。酢酸ビニル重合単位の比率が5重量%未満であると耐汚れ性が劣り、25重量%を超えると耐熱性、剛性が低下したり、層状剥離等の成形品の外観不良が発生したりするので好ましくない。
(2) Ethylene / vinyl acetate copolymer (B)
The ethylene / vinyl acetate copolymer (B) used in the polypropylene resin composition of the present invention has a vinyl acetate polymer unit ratio of 5 to 25% by weight, preferably 7 to 20% by weight, and 10 to 15% by weight. Particularly preferred. If the ratio of the vinyl acetate polymer units is less than 5% by weight, the stain resistance will be inferior. If it exceeds 25% by weight, the heat resistance and rigidity will be lowered, or the appearance of the molded product such as delamination will occur. It is not preferable.
また、エチレン・酢酸ビニル共重合体(B)は、メルトインデックス(190℃、2.16kg荷重で測定)の値が1〜10g/10分が好ましく、1.5〜9g/10分がより好ましく、2〜8g/10分がさらに好ましい。メルトインデックスがこの範囲にあると、耐汚れ性がより向上するので好ましい。
ここで、メルトインデックスは、JIS−K7210に準拠し、190℃、2.16kg荷重で測定する値である。
The ethylene / vinyl acetate copolymer (B) preferably has a melt index (measured at 190 ° C. under a load of 2.16 kg) of 1 to 10 g / 10 minutes, more preferably 1.5 to 9 g / 10 minutes. 2 to 8 g / 10 min is more preferable. When the melt index is within this range, the stain resistance is further improved, which is preferable.
Here, the melt index is a value measured according to JIS-K7210 at 190 ° C. and a 2.16 kg load.
(3)脂肪酸アミド又はその誘導体(C)
本発明のポリプロピレン樹脂組成物に用いる脂肪酸アミドおよびその誘導体としては、ステアリン酸アミド、オレイン酸アミド、ベヘニン酸アミド、エルカ酸アミド、エチレンビスステアリン酸アミド、ヘキサメチレンビスステアリン酸アミド、ラウリン酸アミド、m−キシリレンビスステアリン酸アミド、N、N’−ジステアリルイソフタル酸アミド、N、N’−ジステアリルセバシン酸アミド、N、N’−ジステアリルアジピン酸アミド、m−キシリレンビスステアリン酸アミド、N、N’−ジステアリルイソフタル酸アミド、N、N’−ジステアリルセバシン酸アミド、N、N’−ジステアリルアジピン酸アミド、ヘキサメチレンビスべヘン酸アミド、エチレンビスべヘン酸アミド、エチレンビスラウリン酸アミド、エチレンビスカプリン酸アミド、エチレンビスカプリル酸アミド、メチレンビスラウリン酸アミド、メチレンビスステアリン酸アミド、12−ヒドロキシステアリン酸アミド、ヒドロキシステアリン酸ビスアミド、ブチレンビスヒドロキシステアリン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、ブチレンビスヒドロキシステアリン酸アミド、ヘキサメチレンビスヒドロキシステアリン酸アミド、エチレンビスヒドロキシステアリン酸アミド、メチレンビスヒドロキシステアリン酸アミド等が挙げられる。これらの中から選ばれる一種又は二種以上を併用して使用することができ、なかでも、オレイン酸アミドが好ましい。
(3) Fatty acid amide or its derivative (C)
Examples of fatty acid amides and derivatives thereof used in the polypropylene resin composition of the present invention include stearic acid amide, oleic acid amide, behenic acid amide, erucic acid amide, ethylene bis stearic acid amide, hexamethylene bis stearic acid amide, lauric acid amide, m-xylylene bis-stearic acid amide, N, N′-distearylisophthalic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl adipic acid amide, m-xylylene bis-stearic acid amide N, N′-distearylisophthalic acid amide, N, N′-distearyl sebacic acid amide, N, N′-distearyl adipic acid amide, hexamethylene bisbehenic acid amide, ethylene bisbehenic acid amide, ethylene Bislauric acid amide, ethylene biscapric acid Ethylene biscaprylic amide, methylene bis lauric acid amide, methylene bis stearic acid amide, 12-hydroxy stearic acid amide, hydroxy stearic acid bisamide, butylene bishydroxy stearic acid amide, hexamethylene bishydroxy stearic acid amide, butylene bishydroxy Examples include stearic acid amide, hexamethylene bishydroxystearic acid amide, ethylene bishydroxystearic acid amide, and methylene bishydroxystearic acid amide. One or two or more selected from these can be used in combination, and among these, oleic acid amide is preferable.
(4)熱可塑性エラストマー(D)
本発明のポリプロピレン樹脂組成物に用いる熱可塑性エラストマー(D)は、耐衝撃性、成形性の向上、収縮特性の調整等を目的に用いられる。熱可塑性エラストマーとしては、具体的には、エチレン−プロピレン共重合体エラストマー、エチレン−ブテン−1共重合体エラストマー、エチレン−オクテン−1共重合体エラストマー、エチレン−プロピレン−ジエン共重合体エラストマー、ポリブタジエン、スチレン−ジエン共重合体、アクリロニトリル−ブタジエン共重合体、ポリイソプレン等のジエン系ゴム、スチレン−ブタジエンブロック共重合体、水素化スチレン−ブタジエンブロック共重合体、エチレン系アイオノマー樹脂、水素化スチレン−イソプレンブロック共重合体等が挙げられる。これらの熱可塑性エラストマーは、1種又は2種以上を混合して使用することができる。
(4) Thermoplastic elastomer (D)
The thermoplastic elastomer (D) used in the polypropylene resin composition of the present invention is used for the purpose of improving impact resistance, moldability, adjusting shrinkage characteristics, and the like. Specific examples of the thermoplastic elastomer include ethylene-propylene copolymer elastomer, ethylene-butene-1 copolymer elastomer, ethylene-octene-1 copolymer elastomer, ethylene-propylene-diene copolymer elastomer, polybutadiene. Styrene-diene copolymer, acrylonitrile-butadiene copolymer, diene rubber such as polyisoprene, styrene-butadiene block copolymer, hydrogenated styrene-butadiene block copolymer, ethylene ionomer resin, hydrogenated styrene- Examples include isoprene block copolymers. These thermoplastic elastomers can be used alone or in combination of two or more.
(5)無機充填材(E)
本発明のポリプロピレン樹脂組成物に用いる無機充填材(E)は、剛性の向上、寸法安定性の調整等を目的に用いられる。無機充填材としては、タルク、ワラストナイト、炭酸カルシウム、硫酸バリウム、マイカ、ガラス繊維、カーボンファイバーなどが挙げられ、特にタルクが好ましい。
(5) Inorganic filler (E)
The inorganic filler (E) used in the polypropylene resin composition of the present invention is used for the purpose of improving rigidity and adjusting dimensional stability. Examples of the inorganic filler include talc, wollastonite, calcium carbonate, barium sulfate, mica, glass fiber, and carbon fiber, and talc is particularly preferable.
タルクは、外観や衝撃強度の点で、好ましくは平均粒径が1.5〜15μm、特に好ましくは2〜8μmのものである。該タルクは、例えば、先ずタルク原石を衝撃式粉砕機やミクロンミル型粉砕機で粉砕して製造したり、更にジェットミルなどで粉砕した後、サイクロンやミクロンセパレータ等で分級調整する等の方法で製造する。タルクの平均粒径は、レーザ回折散乱方式粒度分布計(例えば、堀場製作所LA−920型)を用いて測定することができる。
また、見かけ比容を2.50ml/g以下にしたいわゆる圧縮タルクを用いても良く、さらに、無機充填材は、金属石鹸、パラフィンワックス、ポリエチレンワックスまたはそれらの変性物、有機シラン、有機ボラン、有機チタネ−ト等を使用して表面処理されたものであってもよい。
Talc preferably has an average particle size of 1.5 to 15 μm, particularly preferably 2 to 8 μm, in terms of appearance and impact strength. The talc is produced, for example, by first pulverizing raw talc with an impact pulverizer or micron mill type pulverizer, further pulverizing with a jet mill or the like, and then adjusting the classification with a cyclone or micron separator. To manufacture. The average particle diameter of talc can be measured using a laser diffraction / scattering particle size distribution analyzer (for example, Horiba LA-920 type).
In addition, so-called compression talc having an apparent specific volume of 2.50 ml / g or less may be used. Further, the inorganic filler may be metal soap, paraffin wax, polyethylene wax or a modified product thereof, organic silane, organic borane, The surface treatment may be performed using organic titanate or the like.
(6)着色剤(F)
本発明のポリプロピレン樹脂組成物には、必要に応じて、着色剤(F)を配合することができる。着色剤(F)としては、白色系の酸化チタン、亜鉛華、リトボン、鉛白、赤色系の弁柄、鉛炭、モリブデンレッド、カドミウムレッド、レーキレッドC、レーキレッドD、ブリリアントカーミン6B、リソールレッド、パーマネントレッド4R、ウォッチングレッド、チオインジゴレッド、アリザリンレッド、キナクリドンレッド、ローダミンレーキ、オレンジレーキ、ベンズイミダゾロンレッド、ピラゾロンレッド、縮合アゾレッド、ペリレンレッド、パーマネントカーミンFB、キナクリドンマゼンダ、黄色系の黄鉛、カドミウムイエロー、チタンイエロー、鉄黄、イソインドリノンイエロー、ベンジジンイエロー、ファーストイエロー、フラボンスロンイエロー、ナフトールイエロー、キノリンイエロー、ベンズイミダゾロンイエロー、HRイエロー、縮合アゾイエロー、橙色系のクロムオレンジ、カドミウムオレンジ、ベンズイミダゾロンオレンジ、ペリノンオレンジ、緑色系のクロムグリーン、酸化クロム、ギネグリーン、スピネルグリーン、フタロシアニングリーン、ピグメントグリーンB、ナフトールグリーン、アシッドグリーンレーキ、マラカイトグリーンレーキ、茶系の亜鉛フェライト、青色系の紺青、群青、コバルトブルー、フタロシアニンブルー、インダンスレンブルーRS、ファーストスカイブルーレーキ、アルカリブルーレーキ、ビクトリアブルーレーキ、紫色系のマンガン紫、コバルト紫、紫弁柄、ファーストバイオレットB、メチルバイオレットレーキ、ジオキサジンバイオレット、黒色系のカーボンブラック、鉄黒等を挙げることができる。
(6) Colorant (F)
A colorant (F) can be blended with the polypropylene resin composition of the present invention as needed. As the colorant (F), white titanium oxide, zinc white, lithobon, lead white, red petal, lead charcoal, molybdenum red, cadmium red, lake red C, lake red D, brilliant carmine 6B, resol Red, Permanent Red 4R, Watching Red, Thioindigo Red, Alizarin Red, Quinacridone Red, Rhodamine Lake, Orange Lake, Benzimidazolone Red, Pyrazolone Red, Condensed Azo Red, Perylene Red, Permanent Carmine FB, Quinacridone Magenta, Yellow Yellow Lead, cadmium yellow, titanium yellow, iron yellow, isoindolinone yellow, benzidine yellow, first yellow, flavonthrone yellow, naphthol yellow, quinoline yellow, benzimidazolone yellow HR yellow, condensed azo yellow, orange chrome orange, cadmium orange, benzimidazolone orange, perinone orange, green chrome green, chromium oxide, guinea green, spinel green, phthalocyanine green, pigment green B, naphthol green, Acid Green Lake, Malachite Green Lake, Brown Zinc Ferrite, Blue Bitumen, Ultramarine Blue, Cobalt Blue, Phthalocyanine Blue, Indanthrene Blue RS, First Sky Blue Lake, Alkaline Blue Lake, Victoria Blue Lake, Purple Manganese Purple, cobalt purple, purple petals, first violet B, methyl violet lake, dioxazine violet, black carbon black, iron black and the like can be mentioned.
(7)その他の配合成分(任意成分)
本発明のポリプロピレン樹脂組成物においては、本発明の効果を損なわない範囲で、或いは、更に性能の向上をはかるために、上記成分以外に、以下に示す任意成分を配合することができる。具体的には、酸化防止剤、帯電防止剤、光安定剤、紫外線吸収剤、核剤、難燃剤、分散剤、顔料、発泡剤などをあげることが出来る。
(7) Other ingredients (arbitrary ingredients)
In the polypropylene resin composition of the present invention, the following optional components can be blended in addition to the above components in order not to impair the effects of the present invention or to further improve the performance. Specific examples include antioxidants, antistatic agents, light stabilizers, ultraviolet absorbers, nucleating agents, flame retardants, dispersants, pigments, foaming agents, and the like.
(8)成分の配合割合
本発明のポリプロピレン樹脂組成物に配合される各成分の割合は、(A)ポリプロピレン樹脂40〜99.45重量%、(B)エチレン・酢酸ビニル共重合体0.5〜8重量%、(C)脂肪酸アミド又はその誘導体0.05〜2.5重量%、(D)熱可塑性エラストマー0〜35重量%、(E)無機充填材0〜35重量%であり、好ましくは、(A)ポリプロピレン樹脂45〜97.9重量%、(B)エチレン・酢酸ビニル共重合体2〜7重量%、(C)脂肪酸アミド又はその誘導体0.1〜1.5重量%、(D)熱可塑性エラストマー0〜35重量%、(E)無機充填材0〜35重量%であり、さらに好ましくは、(A)ポリプロピレン樹脂50〜96重量%、(B)エチレン・酢酸ビニル共重合体3〜7重量%、(C)脂肪酸アミド又はその誘導体0.2〜1重量%、(D)熱可塑性エラストマー0〜35重量%、(E)無機充填材0〜35重量%である。
(B)エチレン・酢酸ビニル共重合体の割合が0.5重量%未満であると、汚れ性が悪化し、8重量%を超えると剛性が低くなる。(C)脂肪酸アミド又はその誘導体の割合が0.05重量%未満であると、汚れ性が悪化し、2.5重量%を超えると剛性が低くなる。
(8) Mixing ratio of component The ratio of each component mix | blended with the polypropylene resin composition of this invention is (A) polypropylene resin 40-99.45 weight%, (B) ethylene * vinyl acetate copolymer 0.5. -8 wt%, (C) fatty acid amide or derivative thereof 0.05-2.5 wt%, (D) thermoplastic elastomer 0-35 wt%, (E) inorganic filler 0-35 wt%, preferably (A) 45 to 97.9% by weight of polypropylene resin, (B) 2 to 7% by weight of ethylene / vinyl acetate copolymer, (C) 0.1 to 1.5% by weight of fatty acid amide or derivative thereof, ( D) 0 to 35% by weight of thermoplastic elastomer, (E) 0 to 35% by weight of inorganic filler, more preferably (A) 50 to 96% by weight of polypropylene resin, and (B) ethylene / vinyl acetate copolymer. 3-7% by weight, ( C) Fatty acid amide or derivative thereof 0.2 to 1% by weight, (D) Thermoplastic elastomer 0 to 35% by weight, (E) Inorganic filler 0 to 35% by weight.
(B) When the proportion of the ethylene / vinyl acetate copolymer is less than 0.5% by weight, the soiling property is deteriorated, and when it exceeds 8% by weight, the rigidity is lowered. (C) When the ratio of fatty acid amide or a derivative thereof is less than 0.05% by weight, the soiling property is deteriorated, and when it exceeds 2.5% by weight, the rigidity is lowered.
また、(F)着色剤を用いる場合は、用いる着色剤により一概には決められないが、成分(A)〜(E)の合計100重量部に対して、0.1〜50重量部が好ましく、例えば、酸化チタンを用いる場合は、好ましくは0.5〜3重量部であり、より好ましくは0.8〜2重量部である。0.1重量部以下では、着色力、隠蔽度におとり、50重量部を超えると剛性などを下げるために好ましくない。 Moreover, when (F) a coloring agent is used, it is not generally determined depending on the coloring agent to be used, but 0.1 to 50 parts by weight is preferable with respect to a total of 100 parts by weight of components (A) to (E). For example, when using titanium oxide, it is preferably 0.5 to 3 parts by weight, and more preferably 0.8 to 2 parts by weight. If it is 0.1 parts by weight or less, the coloring power and the concealment degree are not preferable, and if it exceeds 50 parts by weight, the rigidity and the like are lowered.
2.ポリプロピレン樹脂組成物の製造と成形
本発明で用いるポリプロピレン樹脂組成物は、上記成分(A)〜(F)を、従来公知の方法で、各配合成分を上記配合割合で配合・混合し、溶融混練することにより製造でき、特に、成分(B)と成分(C)を混合した後、他の成分を混合する方法が好ましい。
溶融混練は、一軸押出機、二軸押出機、バンバリーミキサー、ロールミキサー、ブラベンダープラストグラフ、ニーダー等の通常の混練機を用いて混練・造粒することによって、本発明のプロピレン樹脂組成物が得られる。
この場合、各成分の分散を良好にすることができる混練・造粒方法を選択することが好ましく、通常は二軸押出機を用いて行われる。この混練・造粒の際には、上記各成分の配合物を同時に混練してもよく、また性能向上をはかるべく各成分を分割して混練する、すなわち、例えば先ずプロピレン系重合体の一部又は全部とエラストマーとを混練し、その後に残りの成分を混練・造粒するといった方法を採用することもできる。
2. Production and Molding of Polypropylene Resin Composition The polypropylene resin composition used in the present invention is prepared by blending and mixing the above components (A) to (F) with the above-mentioned blending ratios by blending the above-mentioned blending components in the conventionally known methods. In particular, a method of mixing the component (B) and the component (C) and then mixing other components is preferable.
In the melt-kneading, the propylene resin composition of the present invention is obtained by kneading and granulating using a normal kneader such as a single-screw extruder, a twin-screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader. can get.
In this case, it is preferable to select a kneading and granulating method capable of improving the dispersion of each component, and it is usually performed using a twin-screw extruder. In this kneading and granulation, the above-mentioned components may be kneaded at the same time, and each component may be divided and kneaded in order to improve the performance, that is, for example, first part of the propylene polymer. Alternatively, a method of kneading the whole and the elastomer and then kneading and granulating the remaining components may be employed.
また、本発明のポリプロピレン樹脂組成物は、公知の各種方法による成形に用いることができる。例えば、射出成形(ガス射出成形も含む)、射出圧縮成形(プレスインジェクション)、押出成形、中空成形、カレンダー成形、インフレーション成形、一軸延伸フィルム成形、二軸延伸フィルム成形等にて成形することによって各種成形品を得ることができる。このうち、射出成形、射出圧縮成形がより好ましい。 Moreover, the polypropylene resin composition of this invention can be used for shaping | molding by a well-known various method. For example, various types by molding by injection molding (including gas injection molding), injection compression molding (press injection), extrusion molding, hollow molding, calendar molding, inflation molding, uniaxially stretched film molding, biaxially stretched film molding, etc. A molded product can be obtained. Of these, injection molding and injection compression molding are more preferable.
3.ポリプロピレン樹脂組成物の用途
本発明のポリプロピレン樹脂組成物は、耐汚れ性、物性バランスに優れ、かつ成形加工性に優れるため、掃除機、冷蔵庫などの各種家電製品、便座、便蓋などのトイレタリー製品、各種工業部品分野、例えば、バンパー、ロッカーモール、サイドモール、オーバーフェンダー、バックドア、ガーニッシュなどの自動車部品用成形材料として、実用に十分な性能を有している。
3. Applications of the polypropylene resin composition The polypropylene resin composition of the present invention is excellent in dirt resistance, balance of physical properties, and excellent in moldability. Therefore, various household appliances such as vacuum cleaners and refrigerators, and toiletry products such as toilet seats and toilet lids. As a molding material for automobile parts such as various industrial parts, such as bumpers, rocker moldings, side moldings, over fenders, back doors, garnishes, etc., it has sufficient performance for practical use.
以下に、本発明のポリプロピレン系樹脂組成物を実施例および比較例を示して具体的に説明するが、本発明はこれらの実施例および比較例に限定されるものではない。なお、実施例、比較例において使用した原材料および試験法・評価方法は以下のとおりである。 EXAMPLES The polypropylene resin composition of the present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited to these examples and comparative examples. The raw materials and test methods / evaluation methods used in Examples and Comparative Examples are as follows.
1.評価方法
(1)MFR:JIS−K7210に準拠して、行った。
(2)密度(単位:g/cm3):JIS−K7112に準拠して23℃で測定した。
(3)曲げ弾性率(単位:MPa):JIS−K7203に準拠して23℃で測定した。
(4)アイゾット(IZOD)衝撃強度(単位:J/m):JIS−K7110に準拠し、−30℃で測定した。
(5)外観:100×100×3mmtのシートを射出成形にて成形し、シート表面の成形不良の有無を目視にて観察した。
(6)耐汚れ性:射出成形機にて成形した100×100×3mmtのシートを、JIS−B7753に準拠したサンシャインカーボンアーク灯式耐候性試験機に取り付け、JIS−K7350−4に準拠したブラックパネル63℃、降雨時間12分/60分、の条件で1000時間暴露して、汚れ付着シートを作成した。得られた汚れ付着シートを流水下にて市販のスポンジにて洗浄し、汚れ度合いを目視にて2段階で評価した。
○:汚れがほとんど目立たない
×:汚れが目立つ
1. Evaluation method (1) MFR: Performed according to JIS-K7210.
(2) Density (unit: g / cm 3 ): measured at 23 ° C. according to JIS-K7112.
(3) Flexural modulus (unit: MPa): Measured at 23 ° C. according to JIS-K7203.
(4) Izod (IZOD) impact strength (unit: J / m): measured at −30 ° C. according to JIS-K7110.
(5) Appearance: A sheet of 100 × 100 × 3 mmt was molded by injection molding, and the presence or absence of molding defects on the sheet surface was visually observed.
(6) Stain resistance: A 100 × 100 × 3 mmt sheet molded by an injection molding machine is attached to a sunshine carbon arc lamp type weather resistance tester conforming to JIS-B7753, and black conforming to JIS-K7350-4 The panel was exposed to 1000 hours under conditions of 63 ° C. and a rain time of 12 minutes / 60 minutes to prepare a soiled sheet. The obtained dirt adhesion sheet was washed with a commercially available sponge under running water, and the degree of dirt was visually evaluated in two stages.
○: Dirt is hardly noticeable ×: Dirt is noticeable
2.原材料
(A)プロピレン・エチレンブロック共重合体(PP)
表1に示すA−1〜A−3のプロピレン・エチレンブロック共重合体を用いた。
(B)エチレン・酢酸ビニル共重合体(EVA)
表2に示すB−1〜B−3のエチレン・酢酸ビニル共重合体を用いた。
(C)脂肪酸誘導体
C−1:オレイン酸アミド(市販品)
C−2:ステアリン酸亜鉛(市販品)
(D)エチレン・α−オレフィン系エラストマー(エラストマー)
表3に示したD−1〜D−2のエチレン・α−オレフィン共重合体系エラストマーを用いた。
(E)無機充填材
E−1:タルク(富士タルク製LMS200、LA920により求めた平均粒径:6μm)を用いた。
(F)顔料
F−1:酸化チタン(石原産業製タイベークCR−90)
F−2:赤色顔料(チバガイギー製クロムフタルレッドBR)
F−3:青色顔料(東洋インキ製リオノールブルーFG−7350)
2. Raw material (A) Propylene / ethylene block copolymer (PP)
The propylene / ethylene block copolymers A-1 to A-3 shown in Table 1 were used.
(B) Ethylene / vinyl acetate copolymer (EVA)
B-1 to B-3 ethylene / vinyl acetate copolymers shown in Table 2 were used.
(C) Fatty acid derivative C-1: Oleic acid amide (commercially available product)
C-2: Zinc stearate (commercially available)
(D) Ethylene / α-olefin elastomer (elastomer)
D-1 to D-2 ethylene / α-olefin copolymer elastomers shown in Table 3 were used.
(E) Inorganic filler E-1: Talc (average particle diameter determined by LMS200, LA920 manufactured by Fuji Talc: 6 μm) was used.
(F) Pigment F-1: Titanium oxide (Taibak CR-90 manufactured by Ishihara Sangyo)
F-2: Red pigment (Chromium phthalred BR manufactured by Ciba Geigy)
F-3: Blue pigment (Lionol Blue FG-7350 manufactured by Toyo Ink)
(実施例1〜8、比較例1〜6)
表4に示す成分を、表4に示す割合にて、スーパーミキサーにてドライブレンドした後、押出し温度200℃、吐出量35kg/hの条件で2軸押出し機(神戸製鋼社製、KTX44)を用いて溶融混練した。なお、溶融混練時の熱安定剤として、イルガノックス1010を組成物100重量部に対して0.1重量部添加した。溶融混練後、射出成型(220℃、金型温度40℃)にて試験片を作製し、評価を行った。その結果を表5に示す。
(Examples 1-8, Comparative Examples 1-6)
After the components shown in Table 4 were dry-blended with a super mixer at the ratio shown in Table 4, a twin screw extruder (KTX44, manufactured by Kobe Steel) was used under the conditions of an extrusion temperature of 200 ° C. and a discharge rate of 35 kg / h. Used and melt-kneaded. In addition, as a heat stabilizer at the time of melt-kneading, 0.1 part by weight of Irganox 1010 was added with respect to 100 parts by weight of the composition. After melt-kneading, a test piece was prepared by injection molding (220 ° C., mold temperature 40 ° C.) and evaluated. The results are shown in Table 5.
表4及び5より明らかなように、実施例1〜8は、各成分の要件を満たしており、物性、外観が良好、かつ耐汚れ性に優れる成形品が得られた。
一方、比較例1は、EVAが無添加のため、耐汚れ性が低下する。比較例2は、EVAの添加量が多いため、剛性が低下し物性のバランスが大幅に悪くなる。比較例3は、オレイン酸アミドが無添加であり、耐汚れ性が低下する。比較例4は、EVAの酢酸ビニル重合単位が低く、耐汚れ性が低下する。比較例5は、EVAの酢酸ビニル重合単位が高いため、層状剥離が発生し、外観が悪く、耐汚れ性の評価は実施しなかった。比較例6は、オレイン酸アミドをステアリン酸亜鉛に変更したものであり、耐汚れ性が低下する。
As is apparent from Tables 4 and 5, Examples 1 to 8 satisfied the requirements of each component, and molded articles having good physical properties and appearance and excellent stain resistance were obtained.
On the other hand, in Comparative Example 1, since the EVA is not added, the stain resistance is lowered. In Comparative Example 2, since the amount of EVA added is large, the rigidity is lowered and the balance of physical properties is greatly deteriorated. In Comparative Example 3, oleic amide is not added, and the stain resistance is lowered. In Comparative Example 4, the vinyl acetate polymerized unit of EVA is low, and the stain resistance is lowered. In Comparative Example 5, since EVA has a high vinyl acetate polymer unit, delamination occurred, the appearance was poor, and the stain resistance was not evaluated. In Comparative Example 6, oleic amide is changed to zinc stearate, and the stain resistance is lowered.
本発明のポリプロピレン樹脂組成物は、耐汚れ性に優れ、かつ機械物性および射出成形性にすぐれ、特に射出成形による特に各種工業部品、家電用部品、自動車部品として好適な樹脂組成物であり、例えば、掃除機、冷蔵庫などの各種家電製品、便座、便蓋などのトイレタリー製品、バンパー、ロッカーモール、サイドモール、オーバーフェンダー、バックドア、ガーニッシュなどの自動車部品用成形材料として、実用に十分な性能を有し、工業的に用いることができる。 The polypropylene resin composition of the present invention is excellent in stain resistance and excellent in mechanical properties and injection moldability, and is particularly a resin composition suitable for various industrial parts, parts for home appliances, automobile parts by injection molding, for example. As a molding material for automotive parts such as various household appliances such as vacuum cleaners, refrigerators, toiletries such as toilet seats and toilet lids, bumpers, locker moldings, side moldings, over fenders, back doors, garnishes, etc. And can be used industrially.
Claims (3)
(A)ポリプロピレン樹脂 40〜99.45重量%
(B)酢酸ビニル重合単位の比率が5〜25重量%であるエチレン・酢酸ビニル共重合体 0.5〜8重量%
(C)脂肪酸アミドまたはその誘導体 0.05〜2.5重量%
(D)熱可塑性エラストマー 0〜35重量%
(E)無機充填材 0〜35重量% A polypropylene resin composition comprising the following components (A) to (E):
(A) Polypropylene resin 40 to 99.45% by weight
(B) Ethylene / vinyl acetate copolymer having a vinyl acetate polymer unit ratio of 5 to 25% by weight 0.5 to 8% by weight
(C) Fatty acid amide or derivative thereof 0.05 to 2.5% by weight
(D) Thermoplastic elastomer 0 to 35% by weight
(E) Inorganic filler 0 to 35% by weight
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JPH06248127A (en) * | 1993-02-26 | 1994-09-06 | Nippon Petrochem Co Ltd | Polyethylene resin composition |
JPH0873678A (en) * | 1994-09-02 | 1996-03-19 | Nippon Petrochem Co Ltd | Sheet pallet for distributing vegetables and fruits |
JPH10287778A (en) * | 1997-04-15 | 1998-10-27 | Nippon Porikemu Kk | Polypropylene resin composition for component of toilet stool |
JP2004035622A (en) * | 2002-06-28 | 2004-02-05 | Japan Polychem Corp | Propylenic resin composition, and its molded product |
JP2004083889A (en) * | 2002-06-28 | 2004-03-18 | Japan Polychem Corp | Automotive propylene-based resin composition, method for producing the same and molded product of the same |
JP2005000524A (en) * | 2003-06-13 | 2005-01-06 | Toto Ltd | Component for toilet seat and method of manufacturing the same |
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JPH06248127A (en) * | 1993-02-26 | 1994-09-06 | Nippon Petrochem Co Ltd | Polyethylene resin composition |
JPH0873678A (en) * | 1994-09-02 | 1996-03-19 | Nippon Petrochem Co Ltd | Sheet pallet for distributing vegetables and fruits |
JPH10287778A (en) * | 1997-04-15 | 1998-10-27 | Nippon Porikemu Kk | Polypropylene resin composition for component of toilet stool |
JP2004035622A (en) * | 2002-06-28 | 2004-02-05 | Japan Polychem Corp | Propylenic resin composition, and its molded product |
JP2004083889A (en) * | 2002-06-28 | 2004-03-18 | Japan Polychem Corp | Automotive propylene-based resin composition, method for producing the same and molded product of the same |
JP2005000524A (en) * | 2003-06-13 | 2005-01-06 | Toto Ltd | Component for toilet seat and method of manufacturing the same |
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