JPH0224121B2 - - Google Patents
Info
- Publication number
- JPH0224121B2 JPH0224121B2 JP13528084A JP13528084A JPH0224121B2 JP H0224121 B2 JPH0224121 B2 JP H0224121B2 JP 13528084 A JP13528084 A JP 13528084A JP 13528084 A JP13528084 A JP 13528084A JP H0224121 B2 JPH0224121 B2 JP H0224121B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- nylon
- copolymer
- ethylene
- polyamide resin
- 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.)
- Expired
Links
- 239000004677 Nylon Substances 0.000 claims description 24
- 229920001778 nylon Polymers 0.000 claims description 24
- 239000004014 plasticizer Substances 0.000 claims description 22
- 229920006122 polyamide resin Polymers 0.000 claims description 22
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 16
- 238000000465 moulding Methods 0.000 claims description 7
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005992 thermoplastic resin Polymers 0.000 claims description 5
- 239000011342 resin composition Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 description 29
- -1 cyclic lactams Chemical class 0.000 description 16
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 11
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 7
- 239000011976 maleic acid Substances 0.000 description 7
- 239000000806 elastomer Substances 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 5
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000001530 fumaric acid Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 2
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 229920003620 Grilon® Polymers 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IPRJXAGUEGOFGG-UHFFFAOYSA-N N-butylbenzenesulfonamide Chemical compound CCCCNS(=O)(=O)C1=CC=CC=C1 IPRJXAGUEGOFGG-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000008064 anhydrides 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
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-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
- 230000000740 bleeding effect Effects 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- JQCXWCOOWVGKMT-UHFFFAOYSA-N diheptyl phthalate Chemical compound CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC JQCXWCOOWVGKMT-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PZWQOGNTADJZGH-SNAWJCMRSA-N (2e)-2-methylpenta-2,4-dienoic acid Chemical class OC(=O)C(/C)=C/C=C PZWQOGNTADJZGH-SNAWJCMRSA-N 0.000 description 1
- XVYUHVUUDRFUNE-UHFFFAOYSA-N 1,3-bis(3-tert-butylperoxypropyl)benzene Chemical compound CC(C)(C)OOCCCC1=CC=CC(CCCOOC(C)(C)C)=C1 XVYUHVUUDRFUNE-UHFFFAOYSA-N 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-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
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- HASUJDLTAYUWCO-UHFFFAOYSA-N 2-aminoundecanoic acid Chemical compound CCCCCCCCCC(N)C(O)=O HASUJDLTAYUWCO-UHFFFAOYSA-N 0.000 description 1
- JVPFOKXICYJJSC-UHFFFAOYSA-N 2-azaniumylnonanoate Chemical compound CCCCCCCC(N)C(O)=O JVPFOKXICYJJSC-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- XDOLZJYETYVRKV-UHFFFAOYSA-N 7-Aminoheptanoic acid Chemical compound NCCCCCCC(O)=O XDOLZJYETYVRKV-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical class NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 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
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- VOWAEIGWURALJQ-UHFFFAOYSA-N Dicyclohexyl phthalate Chemical compound C=1C=CC=C(C(=O)OC2CCCCC2)C=1C(=O)OC1CCCCC1 VOWAEIGWURALJQ-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920003904 Rilsan® BMNO Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical group CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- ROPXFXOUUANXRR-YPKPFQOOSA-N bis(2-ethylhexyl) (z)-but-2-enedioate Chemical compound CCCCC(CC)COC(=O)\C=C/C(=O)OCC(CC)CCCC ROPXFXOUUANXRR-YPKPFQOOSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- ILUAAIDVFMVTAU-UHFFFAOYSA-N cyclohex-4-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CC=CCC1C(O)=O ILUAAIDVFMVTAU-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- JBSLOWBPDRZSMB-BQYQJAHWSA-N dibutyl (e)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C\C(=O)OCCCC JBSLOWBPDRZSMB-BQYQJAHWSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical group C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000008036 rubber plasticizer Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003440 styrenes Chemical group 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QCLBBXWZPNXJBS-UHFFFAOYSA-N tris(2-chloroethyl) phosphate;tris(3,3-dichloropropyl) phosphate Chemical compound ClCCOP(=O)(OCCCl)OCCCl.ClC(Cl)CCOP(=O)(OCCC(Cl)Cl)OCCC(Cl)Cl QCLBBXWZPNXJBS-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
Description
【発明の詳細な説明】
(産業上の利用分野)
本発明は、ナイロン系の熱可塑性弾性樹脂を成
形してなる弾性スキー靴に関するものである。
(従来の技術)
従来、スキー靴の上部外皮および底部は、素材
としてポリウレタン、エチレン−酢酸ビニル共重
合樹脂(以下EVAと略す)系の熱可塑性樹脂が
使用されているが、この用途に要求される諸特性
を必ずしも充分に満たしているものではない。例
えば、低温において脆化し、使用中の衝撃により
ワレが発生することがある。EVAにおいては耐
摩耗性が著しく劣り、長期使用に難点があるとさ
れている。またポリウレタンの比重は比較的大き
いため製品重量が大きくなり、使用上好ましくな
い。更に、成形時の問題としてポリウレタンや
EVAについては、成形時間が長く、成形時に劣
化が生じやすく、一般に原料樹脂から製品に成形
する際の歩留まりが悪いとされている。
(発明が解決しようとする問題点)
本発明者らは、低温衝撃性とりわけウエルド部
分の低温衝撃性、耐摩耗性に優れ、低比重で、し
かも成形性の良好な熱可塑性樹脂製スキー靴を開
発すべく鋭意研究した結果、ポリアミド樹脂が耐
摩耗性に優れ、軽量であり、しかも成形時の劣
化、歩留まりの点でスキー靴用として極めて好ま
しい素材であることを見い出した。しかしなが
ら、ポリアミド樹脂を素材とするスキー靴は低温
衝撃性が悪く、スキー靴として使用に耐えないと
いう欠点を有していたポリアミド樹脂の低温衝撃
性を改良する手段として酸変性オレフイン共重合
体をブレンドすることは知られている。しかしな
がら、酸変性オレフイン重合体をブレンドすると
溶融成形時の流動性が悪くなり、成形したスキー
靴のウエルド部分の低温衝撃性が低下し、しかも
フローマーク、ゲート部のハクリ等が発生し、成
形品の外観を悪化させるという問題点が生ずる。
(問題点を解決するための手段)
本発明者らは、上記の如き欠点のないポリアミ
ド樹脂製スキー靴を得るべく更に研究した結果、
ポリアミド樹脂と酸変性オレフイン共重合体と可
塑剤とを特定の割合で配合してなるポリアミド樹
脂組成物が、かかる要件を満たすことを見い出
し、本発明を完成するに至つた。
すなわち本発明は、熱可塑性樹脂を成形してな
る上部外皮及び/又は底部を有するスキー靴にお
いて、該樹脂がポリアミド樹脂(A)と酸変性オレフ
イン共重合体(B)と可塑剤(C)とを、(A)/(B)=40/60
〜90/10、(C)/{(A)+(B)}=1/100〜20/100の
重量比で配合してなるポリアミド樹脂組成物であ
ることを特徴とする弾性スキー靴を提供するもの
である。
本発明に於て、原料の1つとして使用されるポ
リアミド樹脂としては周知の種々のポリアミド樹
脂が挙げられる。例えば、テレフタル酸、イソフ
タル酸、シユウ酸、アジピン酸、セバシン酸、
1,4―シクロヘキシルジカルボン酸の如きジカ
ルボン酸のとエチレンジアミン、ペンタメチレン
ジアミン、ヘキサメチレンジアミン、デカメチレ
ンジアミン、1,4―シクロヘキシルジアミン、
m―キシリレンジアミンの如きジアミンの重合縮
合;カプロラクタム、ラウロラクタムの如き環状
ラクタムの重合;アミノエナント酸、アミノノナ
ン酸、アミノウンデカン酸の如きアミノカルボン
酸の重縮合、あるいは上記環状ラクタムとジカル
ボン酸とジアミンとの共重合等により得られるも
のであり、6ナイロン、66ナイロン、610ナイロ
ン、612ナイロン、11ナイロン、12ナイロン、
66/610共重合ナイロン、6/66共重合ナイロン
等が挙げられるが、特に好ましいものは6ナイロ
ン、66ナイロン、11ナイロン、12ナイロンであ
る。また本発明において使用されるポリアミド樹
脂としてポリアミドエラストマーもあげることが
できる。ポリアミドエラストマーとは、6ナイロ
ン、66ナイロン、11ナイロン、12ナイロン等のポ
リアミド成分からなるハードセグメントと、ポリ
エステル成分および/又はポリエーテル成分のソ
フトセグメントを持つブロツク共重合体である。
ポリアミドエラストマーの例として、
GRILAMIDELY60(スイス国EMS CHEMIE社
製)、PEBAX(フランス国ATO社製)などが挙
げられる。
本発明において、ポリアミド樹脂の耐衝撃性を
向上させるために添加する酸変性オレフイン共重
合体に関して、これらは少なくとも50モル%、好
適には80モル%の1―オレフイン、例えばエチレ
ン、プロピレン、ブテン―1、イソブテン、ペン
テン―1、ヘキセン―1、デセン―1、4―メチ
ルブテン―1、4―メチルペンテン―1、4,4
―ジメチルペンテン―1、ビニルシクロヘキサ
ン、スチレン、α―メチルスチレン、低級アルキ
ル置換分で置換されたスチレン又は類似物を含有
すべきである。上記オレフインの混合物を使用す
ることもできる。好適にはエチレンとブテン―1
又はプロピレンから得られる共重合体が好まし
く、市販されている製品として、例えばタフマー
A4085、タフマーA4090、タフマーA20090等のタ
フマーAシリーズ〔エチレン―ブテン―1共重合
体、三井石油化学工業(株)製〕及びタフマー
P0280、タフマーP0480、タフマーP0680、タフ
マーP0880等のタフマーPシリーズ〔エチレン―
プロピレン共重合体、三井石油化学工業(株)製〕が
挙げられる。
酸成分は、α,β−不飽和カルボン酸コモノマ
ーと上記オレフインとの直接の共重合や、ポリオ
レフイン及びポリオレフイン共重合体へα,β−
不飽和カルボン酸またはその機能誘導体、もしく
はシス型2重結合を環内に有する脂環式カルボン
酸またはその機能誘導体から選ばれた少なくとも
一種の化合物をグラフト共重合する等、公知の方
法によつて導入される。
α,β−不飽和カルボン酸またはその機能誘導
体の例としては、アクリル酸、メタアクリル酸、
エタアクリル酸、イタコン酸、(無水)マレイン
酸、フマル酸及び上記カルボン酸のモノエステル
等を例示できる。好適にはアクリル酸、メタアク
リル酸及び(無水)マレイン酸を挙げることがで
きる。
シス型2重結合を環内に有する脂環式カルボン
酸の例としては、シス―4―シクロヘキセン―
1,2―ジカルボン酸、エンド−ビシクロ―
〔2,2,1〕―5―ヘプテン―2,3―ジカル
ボン酸、メチル−エンド−シス−ビシクロ―
〔2,2,1〕―5―ヘプテン―2,3―ジカル
ボン酸などが好ましく、その機能誘導体として
は、これらの酸無水物、エステル、酸アミド等が
あげられる。
以下に代表的な酸変性オレフイン共重合体を例
示するが、これらに限定されるものではない。
エチレン−アクリル酸共重合体、エチレン.メ
タクリル酸共重合体、エチレン−イタコン酸共重
合体、エチレン−マレイン酸メチル共重合体、エ
チレン−アクリル酸−メタクリル酸メチル共重合
体、エチレン−メタクリル酸−アクリル酸エチル
共重合体、エチレン−メタクリル酸−酢酸ビニル
共重合体、エチレン−アクリル酸−酢酸ビニル共
重合体、エチレン−アクリル酸−ビニルアルコー
ル共重合体、エチレン−メチルビニルエーテル−
アクリル酸共重合体、エチレン−プロピレン−ア
クリル酸共重合体、エチレン−スチレン−アクリ
ル酸共重合体、エチレン−メタクリル酸−アクリ
ロニトリル共重合体、エチレン−フマル酸、メチ
ルビニルエーテル共重合体、エチレン−塩化ビニ
ル−アクリル酸共重合体、エチレン−塩化ビニリ
デン−アクリル酸共重合体、エチレン−フツ化ビ
ニル−メタクリル酸共重合体、エチレン−クロロ
トリフルオロエチレン−メタクリル酸共重合体、
塩素化エチレン−メタクリル酸共重合体、エチレ
ン−ブテン―1―メタクリル酸共重合体、エチレ
ン−ブテン―1―(無水)マレイン酸共重合体、
エチレン−プロピレン−(無水)マレイン酸共重
合体、プロピレン−アクリル酸共重合体、ブテン
―1―アクリル酸共重合体、エチレン−イソブチ
レン−アクリル酸共重合体、3―メチルブテン―
1―アクリル酸共重合体、4―メチルペンテン―
1―メタクリル酸共重合体、4,4′―ジメチルペ
ンテン―1―アクリル酸共重合体、プロピレン−
ウンデカアクリル酸共重合体、プロピレン―α―
メチル−スチレン−(無水)マレイン酸共重合体、
プロピレン−ブテン−フマル酸共重合体、エチレ
ン−ビニルシクロヘキサン−アクリル酸共重合
体、塩素化エチレン−アクリル酸共重合体、エチ
レン−ブテン―1―(無水)エンド−ビシクロ―
〔2,2,1〕―5―ヘプテン―2,3―ジカル
ボン酸共重合体、エチレン−プロピレン−(無水)
エンド−ビシクロ―〔2,2,1〕―5―ヘプテ
ン―2,3―ジカルボン酸共重合体および類似
物、好適にはエチレン−ブテン―1―(無水)マ
レイン酸共重合体、エチレン−プロピレン−(無
水)マレイン酸共重合体、エチレン−ブテン―1
―(無水)エンド−ビシクロ―〔2,2,1〕―
5―ヘプテン―2,3―ジカルボン酸共重合体、
エチレン−プロピレン−(無水)エンド−ビシク
ロ―〔2,2,1〕―5―ヘプテン―2,3―ジ
カルボン酸共重合体等を挙げることが出来る。
このような酸変性オレフイン共重合体は、酸性
基を有するモノマーを構成成分として、0.01〜20
重量%含有することが重要であり、好適には0.05
〜10重量%である。なお、酸変性オレフイン共重
合体として酸変性ポリエチレンと未変性のオレフ
イン共重体の混合物も含むことができる。
本発明において、ポリアミド樹脂の流動性を向
上させるために添加する可塑剤には、トリクレジ
ルホスフエート、リン酸(トリスイソプロピルフ
エニル)、トリブチルホスフエート、トリエチル
ホスフエート、トリオクチルホスフエート、トリ
ス(β―クロロエチル)ホスフエートリス(ジク
ロロプロピル)ホスフエート、トリブトキシエチ
ルホスフエート、トリス(β―クロロプロピル)
ホスフエート、トリフエニルホスフエート、オク
チルジフエニルホスフエート等のリン酸エステル
系可塑剤や、ポリエステル系可塑剤、エポキシ系
可塑剤、無水ヒドロフタル酸エステル系可塑剤、
ブチルベンジルフタレート、ジラウリルフタレー
ト、ジヘプチルフタレート、ジブチルフタレー
ト、ジメチルフタレート、ジシクロヘキシルフタ
レート、ジエチルフタレート、ジイソデシルフタ
レート、ジオクチルフタレート、ジオクチルアジ
ペート、ジイソデシルアジペート、ジ(ブチルジ
グリコール)アジペート、ジ―2―エチルヘキシ
ルアゼレート等のエステル系可塑剤、ステアリン
酸系可塑剤、ジオクチルセバケート、ジブチルセ
バケート、クエン酸アセチルトリブチル、クエン
酸アセチルトリエチル、ジ―2―エチルヘキシル
マレエート、ジブチルマレエート等のエステル系
可塑剤、トリメリツト酸系可塑剤、ジブチルフマ
レート、ゴム用可塑剤、塩化パラフイン等がある
が、ナイロン用可塑剤として好適なものに芳香族
スルホンアミド系化合物、例えばベンゼンスルホ
ン酸ブチルアミドや安息香酸エステル系可塑剤、
例えば2―エチルヘキシルベンゾエート、p―オ
キシ2―エチルヘキシルベンゾエート等を挙げる
ことができる。
また、本発明の実施に際しては、本発明の目的
を逸脱しない範囲で他の熱可塑性樹脂又はエラス
トマー、例えばポリ塩化ビニル、ポリエステル、
ポリエーテルポリエステル、ウレタン化ポリエス
テル、エチレン−酢酸ビニル共重合体、ポリウレ
タン、スチレン系エラストマー、ポリブチジエ
ン、塩ビ系エラストマー、アクリル系ポリマー、
エチレン−プロピレン共重合体、エチレン−ブテ
ン―1共重合体等を併用することも可能である。
また、エポキシ化合物の添加も可能である。
また、本発明においては、無機及び/又は有機
の充填剤、添加剤、改質剤は必須でないが、必要
に応じて下記充填剤、添加剤、改質剤を使用する
とによつて物性の向上をはかることができる。好
適な充填剤としては、ガラス繊維、炭素繊維、金
属繊維、アラミド繊維、チタン酸カリウム、アス
ベスト、炭化ケイ素、セラミツク繊維、窒化ケイ
素などの繊維状強化剤、硫酸バリウム、硫酸カル
シウム、カオリン、クレー、パイロフイライト、
ベントナイト、セリサイト、ゼオライト、マイ
カ、雲母、ネフエリンシナイト、タルク、アタル
パルジヤイト、ウオラストナイト、PMF、フエ
ライト、硅酸カルシウム、炭酸カルシウム、炭酸
マグネシウム、ドロマイト、三酸化アンモン、酸
化亜鉛、酸化チタン、酸化マグネシウム、酸化
鉄、二硫化モリブテン、黒鉛、石こう、ガラスビ
ーズ、ガラスパウダー、ガラスバルーン、石英、
石英ガラスなどの補強充填剤を挙げることができ
る。他に離型剤、カツプリング剤、着色剤、滑
剤、耐熱安定剤、耐候性安定剤、発泡剤、難燃
剤、三酸化アンチモン等の難燃助剤等を添加して
もよい。
(本発明の効果)
本発明を構成する必須成分は、ポリアミド樹
脂、酸変性オレフイン共重合体および可塑剤であ
る。
ポリアミド樹脂と酸変性オレフイン共重合体に
おいて、酸変性オレフイン共重合体が10重量部未
満では低温衝撃性に劣り、60重量部を越えるので
あれば、素材そのものの低温衝撃性は良好となる
が、溶融成形時の流動性が悪くなり、成形品のウ
エルト部分の低温衝撃性が悪くなり、また成形し
たスキー靴の表面にフローマーク等が発生し外観
上好ましくない。
本発明では、ポリアミド樹脂40〜90重量部、好
ましくは50〜80重量部と酸変性オレフイン共重合
体60〜10重量部、好ましくは50〜20重量部との合
計100重量部に対し、可塑剤が1〜20重量部、好
ましくは2〜15重量部存在するので、素材そのも
のの低温衝撃性と流動性とが良好となり、成形品
のウエルド部分の低温衝撃性が良好で、しかも外
観良好な成形品が得られる。酸変性オレフイン共
重合体が60重量部を越えた系に可塑剤を添加して
も流動性は良好とならず、ウエルド部分の低温衝
撃性および外観は良好とならない。
なお、可塑剤の添加量は1重量部未満では流動
性改良の効果が得られず、20重量部を越えると可
塑剤のブリードが著しく、表面に粉をふいた状態
となり、好ましくない。
(実施例)
次に実施例と比較例をあげて本発明をさらに具
体的に説明するが、本発明はこれら実施例に限定
されるものではない。なお、例中の部はすべて重
量部であり、評価した試験法は次のとおりであ
る。
(1) 曲げ弾性率
ASTM D−790に準拠した方法。
(2) 引張強さ、伸び
JIS K−6301に準拠した方法。
(3) アイゾツト衝撃強度
ASTM D−638に準拠し、試験片にノツチ
をつけて測定。
(4) スキー靴のウエルド部分の落球衝撃テスト
−20℃に1昼夜スキー靴を放置し、5Kgの鋼
球を高さ1mからウエルド部分めがけて3回落
球する。
◎:ウエルド部のワレなし
×: 〃 あり
(5) スキー靴の外観
フローマーク、ゲート部のハクリ等を目視に
より総合的に評価する。
◎:極めて良好
〇:良好
×:不良(フローマーク、ゲート部のハクリ
あり)
(6) 可塑剤のブリード
成形品を23℃、65%RHの条件下で1ケ月間
放置したのち、可塑剤のブリードの状態を目視
により評価する。
◎:ブリードなし
〇: 〃 わずかにある
×: 〃 激しくある
実施例1〜9および比較例1〜7
ポリアミド樹脂としてGRILAMID L20
(EMSCHEMIE社製12ナイロン)又はGRILON
A28(同6ナイロン)、GRILON T300GM(同66
ナイロン)、リルサンBMNO(ATO社製11ナイロ
ン)を、可塑剤としてベンゼンスルホン酸ブチル
アミド又は2―エチルヘキシルベンゾエートを、
酸変性オレフイン共重合体として下記の酸変性共
重合体〔X〕又は〔Y〕を、それぞれ用いた。酸
変性共重合体〔X〕は、エチレン−プロピレン共
重合体〔タフマーP−0280、三井石油化学工業(株)
製〕100部に1,3ビス(tert−ブチルパーオキ
シプロピル)ベンゼン0.5部及び無水マレイン酸
1部をヘンシエルミキサーで均一に混合し、押出
機で230℃で混慮練し、ペレツト化して得られた
ものであり、酸変性オレフイン共重合体〔Y〕
は、原料としてエチレン−ブテン―1共重合体
〔タフマーA4090、三井石油化学工業(株)製〕を用
いたこと以外は同様にして得られたものである。
以上のポリマー及び可塑剤を表−1に示す割合
で配合し、ヘンシエルミキサーで混合し、直径50
m/mの一軸押出機を用いて180〜260℃で混練し
て、ペレツトをつくつた。このペレツトから射出
成形機により物性評価用試片およびスキー靴を作
成した。表−1にその評価結果を示す。
【表】DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an elastic ski boot made of a nylon-based thermoplastic elastic resin. (Prior art) Conventionally, the upper outer skin and sole of ski boots have been made of polyurethane or thermoplastic resin such as ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVA), but the material required for this purpose is It does not necessarily fully satisfy the various characteristics. For example, it becomes brittle at low temperatures and may crack due to impact during use. EVA has extremely poor wear resistance and is said to be difficult to use over a long period of time. Further, since the specific gravity of polyurethane is relatively high, the weight of the product becomes large, which is not preferable in terms of use. Furthermore, problems with polyurethane and molding
EVA takes a long time to mold, tends to deteriorate during molding, and is generally said to have a poor yield when molding raw resin into products. (Problems to be Solved by the Invention) The present inventors have developed a ski shoe made of thermoplastic resin that has excellent low-temperature impact properties, particularly at the weld part, and abrasion resistance, has a low specific gravity, and has good moldability. As a result of extensive research into the development of this product, it was discovered that polyamide resin has excellent abrasion resistance, is lightweight, and is an extremely preferable material for ski boots in terms of deterioration during molding and yield. However, ski shoes made of polyamide resin have poor low-temperature impact properties and cannot be used as ski boots.As a means to improve the low-temperature impact properties of polyamide resin, acid-modified olefin copolymers are blended. is known to do. However, when acid-modified olefin polymers are blended, the fluidity during melt molding deteriorates, the low-temperature impact resistance of the weld part of the molded ski shoe decreases, and flow marks and peeling of the gate part occur, resulting in molded products. A problem arises in that the appearance of the material is deteriorated. (Means for Solving the Problems) As a result of further research by the present inventors in order to obtain ski boots made of polyamide resin that do not have the above-mentioned drawbacks,
The present inventors have discovered that a polyamide resin composition formed by blending a polyamide resin, an acid-modified olefin copolymer, and a plasticizer in a specific ratio satisfies these requirements, and has completed the present invention. That is, the present invention provides a ski shoe having an upper shell and/or a sole made of a thermoplastic resin, wherein the resin comprises a polyamide resin (A), an acid-modified olefin copolymer (B), and a plasticizer (C). , (A)/(B)=40/60
Provided is an elastic ski shoe characterized by being a polyamide resin composition compounded at a weight ratio of ~90/10, (C)/{(A)+(B)}=1/100 to 20/100. It is something to do. In the present invention, the polyamide resin used as one of the raw materials includes various well-known polyamide resins. For example, terephthalic acid, isophthalic acid, oxalic acid, adipic acid, sebacic acid,
dicarboxylic acids such as 1,4-cyclohexyldicarboxylic acid, ethylenediamine, pentamethylenediamine, hexamethylenediamine, decamethylenediamine, 1,4-cyclohexyldiamine,
Polymerization and condensation of diamines such as m-xylylene diamine; Polymerization of cyclic lactams such as caprolactam and laurolactam; Polycondensation of aminocarboxylic acids such as aminoenanthic acid, aminononanoic acid and aminoundecanoic acid, or the combination of the above cyclic lactams and dicarboxylic acids. It is obtained by copolymerization with diamine, etc., and includes 6 nylon, 66 nylon, 610 nylon, 612 nylon, 11 nylon, 12 nylon,
Examples include 66/610 copolymerized nylon and 6/66 copolymerized nylon, but particularly preferred are nylon 6, nylon 66, nylon 11, and nylon 12. Polyamide elastomers can also be mentioned as polyamide resins used in the present invention. A polyamide elastomer is a block copolymer having a hard segment made of a polyamide component such as nylon 6, nylon 66, 11 nylon, or 12 nylon, and a soft segment made of a polyester component and/or a polyether component. As an example of polyamide elastomer,
Examples include GRILAMIDELY60 (manufactured by EMS CHEMIE in Switzerland) and PEBAX (manufactured by ATO in France). In the present invention, with respect to the acid-modified olefin copolymers added to improve the impact resistance of polyamide resins, these contain at least 50 mol%, preferably 80 mol% of 1-olefins, such as ethylene, propylene, butene- 1, isobutene, pentene-1, hexene-1, decene-1, 4-methylbutene-1, 4-methylpentene-1,4,4
-dimethylpentene-1, vinylcyclohexane, styrene, alpha-methylstyrene, styrene substituted with lower alkyl substituents or the like. It is also possible to use mixtures of the abovementioned olefins. Preferably ethylene and butene-1
or copolymers obtained from propylene are preferred, commercially available products such as Tafmer
Tafmer A series such as A4085, Tafmer A4090, Tafmer A20090 [ethylene-butene-1 copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.] and Tafmer
Tafmer P series [ethylene-
propylene copolymer, manufactured by Mitsui Petrochemical Industries, Ltd.]. The acid component can be used for direct copolymerization of an α,β-unsaturated carboxylic acid comonomer with the above olefin, or for copolymerization of α,β-unsaturated carboxylic acid comonomers into polyolefins and polyolefin copolymers.
By a known method such as graft copolymerization of at least one compound selected from unsaturated carboxylic acids or functional derivatives thereof, or alicyclic carboxylic acids having a cis-type double bond in the ring or functional derivatives thereof. be introduced. Examples of α,β-unsaturated carboxylic acids or functional derivatives thereof include acrylic acid, methacrylic acid,
Examples include ethacrylic acid, itaconic acid, maleic acid (anhydride), fumaric acid, and monoesters of the above carboxylic acids. Suitable examples include acrylic acid, methacrylic acid and (anhydrous) maleic acid. An example of an alicyclic carboxylic acid having a cis-type double bond in the ring is cis-4-cyclohexene-
1,2-dicarboxylic acid, endo-bicyclo-
[2,2,1]-5-heptene-2,3-dicarboxylic acid, methyl-endo-cis-bicyclo-
[2,2,1]-5-heptene-2,3-dicarboxylic acid is preferred, and its functional derivatives include acid anhydrides, esters, and acid amides thereof. Typical acid-modified olefin copolymers are illustrated below, but the invention is not limited thereto. Ethylene-acrylic acid copolymer, ethylene. Methacrylic acid copolymer, ethylene-itaconic acid copolymer, ethylene-methyl maleate copolymer, ethylene-acrylic acid-methyl methacrylate copolymer, ethylene-methacrylic acid-ethyl acrylate copolymer, ethylene-methacrylate Acid-vinyl acetate copolymer, ethylene-acrylic acid-vinyl acetate copolymer, ethylene-acrylic acid-vinyl alcohol copolymer, ethylene-methyl vinyl ether
Acrylic acid copolymer, ethylene-propylene-acrylic acid copolymer, ethylene-styrene-acrylic acid copolymer, ethylene-methacrylic acid-acrylonitrile copolymer, ethylene-fumaric acid, methyl vinyl ether copolymer, ethylene-chloride Vinyl-acrylic acid copolymer, ethylene-vinylidene chloride-acrylic acid copolymer, ethylene-vinyl fluoride-methacrylic acid copolymer, ethylene-chlorotrifluoroethylene-methacrylic acid copolymer,
Chlorinated ethylene-methacrylic acid copolymer, ethylene-butene-1-methacrylic acid copolymer, ethylene-butene-1-(anhydride)maleic acid copolymer,
Ethylene-propylene-(anhydride) maleic acid copolymer, propylene-acrylic acid copolymer, butene-1-acrylic acid copolymer, ethylene-isobutylene-acrylic acid copolymer, 3-methylbutene-
1-acrylic acid copolymer, 4-methylpentene-
1-methacrylic acid copolymer, 4,4'-dimethylpentene-1-acrylic acid copolymer, propylene-
Undeca acrylic acid copolymer, propylene-α-
Methyl-styrene-(anhydride)maleic acid copolymer,
Propylene-butene-fumaric acid copolymer, ethylene-vinylcyclohexane-acrylic acid copolymer, chlorinated ethylene-acrylic acid copolymer, ethylene-butene-1-(anhydrous) endo-bicyclo-
[2,2,1]-5-heptene-2,3-dicarboxylic acid copolymer, ethylene-propylene-(anhydrous)
Endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid copolymers and analogs, preferably ethylene-butene-1-(anhydride)maleic acid copolymers, ethylene-propylene - (anhydrous) maleic acid copolymer, ethylene-butene-1
-(Anhydrous) Endo-bicyclo-[2,2,1]-
5-heptene-2,3-dicarboxylic acid copolymer,
Examples include ethylene-propylene-(anhydrous) endo-bicyclo-[2,2,1]-5-heptene-2,3-dicarboxylic acid copolymer. Such an acid-modified olefin copolymer contains a monomer having an acidic group as a constituent component, and has a concentration of 0.01 to 20
It is important to contain 0.05% by weight, preferably 0.05% by weight.
~10% by weight. Note that the acid-modified olefin copolymer may also include a mixture of acid-modified polyethylene and unmodified olefin copolymer. In the present invention, the plasticizers added to improve the fluidity of polyamide resin include tricresyl phosphate, phosphoric acid (trisisopropylphenyl), tributyl phosphate, triethyl phosphate, trioctyl phosphate, tris (β-chloroethyl)phosphate Tris(dichloropropyl)phosphate, tributoxyethylphosphate, tris(β-chloropropyl)
Phosphate ester plasticizers such as phosphate, triphenyl phosphate, octyl diphenyl phosphate, polyester plasticizers, epoxy plasticizers, hydrophthalic anhydride plasticizers,
Butylbenzyl phthalate, dilauryl phthalate, diheptyl phthalate, dibutyl phthalate, dimethyl phthalate, dicyclohexyl phthalate, diethyl phthalate, diisodecyl phthalate, dioctyl phthalate, dioctyl adipate, diisodecyl adipate, di(butyl diglycol) adipate, di-2-ethylhexylase Ester plasticizers such as esters, stearic acid plasticizers, dioctyl sebacate, dibutyl sebacate, acetyl tributyl citrate, acetyl triethyl citrate, di-2-ethylhexyl maleate, dibutyl maleate, There are trimellitic acid plasticizers, dibutyl fumarate, rubber plasticizers, chlorinated paraffin, etc., but aromatic sulfonamide compounds such as benzenesulfonic acid butylamide and benzoate ester plasticizers are suitable as nylon plasticizers. ,
Examples include 2-ethylhexylbenzoate and p-oxy 2-ethylhexylbenzoate. In addition, when carrying out the present invention, other thermoplastic resins or elastomers such as polyvinyl chloride, polyester,
Polyether polyester, urethanized polyester, ethylene-vinyl acetate copolymer, polyurethane, styrene elastomer, polybutidiene, vinyl chloride elastomer, acrylic polymer,
It is also possible to use ethylene-propylene copolymer, ethylene-butene-1 copolymer, etc. in combination.
It is also possible to add epoxy compounds. In addition, in the present invention, inorganic and/or organic fillers, additives, and modifiers are not essential, but physical properties can be improved by using the following fillers, additives, and modifiers as necessary. can be measured. Suitable fillers include glass fibers, carbon fibers, metal fibers, aramid fibers, potassium titanate, asbestos, silicon carbide, ceramic fibers, fibrous reinforcing agents such as silicon nitride, barium sulfate, calcium sulfate, kaolin, clay, pyrofluorite,
Bentonite, sericite, zeolite, mica, mica, nephelinsinite, talc, attalpargite, wollastonite, PMF, ferrite, calcium silicate, calcium carbonate, magnesium carbonate, dolomite, ammonium trioxide, zinc oxide, Titanium oxide, magnesium oxide, iron oxide, molybdenum disulfide, graphite, gypsum, glass beads, glass powder, glass balloon, quartz,
Mention may be made of reinforcing fillers such as quartz glass. In addition, a mold release agent, a coupling agent, a coloring agent, a lubricant, a heat-resistant stabilizer, a weather-resistant stabilizer, a foaming agent, a flame retardant, a flame retardant aid such as antimony trioxide, etc. may be added. (Effects of the present invention) The essential components constituting the present invention are a polyamide resin, an acid-modified olefin copolymer, and a plasticizer. In polyamide resin and acid-modified olefin copolymer, if the acid-modified olefin copolymer is less than 10 parts by weight, the low-temperature impact properties are poor, and if it exceeds 60 parts by weight, the material itself has good low-temperature impact properties, but The fluidity during melt molding becomes poor, the low-temperature impact resistance of the welt part of the molded product becomes poor, and flow marks etc. occur on the surface of the molded ski shoes, which is unfavorable in terms of appearance. In the present invention, a plasticizer is added to a total of 100 parts by weight of 40 to 90 parts by weight, preferably 50 to 80 parts by weight, of a polyamide resin and 60 to 10 parts by weight, preferably 50 to 20 parts by weight, of an acid-modified olefin copolymer. Since 1 to 20 parts by weight, preferably 2 to 15 parts by weight of Goods can be obtained. Even if a plasticizer is added to a system in which the acid-modified olefin copolymer exceeds 60 parts by weight, the fluidity will not be improved, and the low-temperature impact resistance and appearance of the weld portion will not be improved. If the amount of plasticizer added is less than 1 part by weight, the effect of improving fluidity cannot be obtained, and if it exceeds 20 parts by weight, the bleeding of the plasticizer will be significant and the surface will become dusty, which is not preferable. (Examples) Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Note that all parts in the examples are parts by weight, and the test method used for evaluation is as follows. (1) Flexural modulus: Method based on ASTM D-790. (2) Tensile strength and elongation Method according to JIS K-6301. (3) Izot impact strength Measured by notching a test piece in accordance with ASTM D-638. (4) Ball drop impact test on the weld of ski boots The ski boots were left at -20℃ for one day and night, and a 5 kg steel ball was dropped three times from a height of 1 m onto the weld. ◎: No cracks in the weld part ×: 〃 Yes (5) Appearance of ski shoes Comprehensive evaluation by visual inspection of flow marks, peeling of gate parts, etc. ◎: Very good 〇: Good ×: Poor (flow marks, peeling at the gate) (6) Bleeding of plasticizer After leaving the molded product for one month at 23℃ and 65% RH, the plasticizer was removed. Visually evaluate the state of the bleed. ◎: No bleed 〃: 〃 Slightly bleed ×: 〃 Severely Examples 1 to 9 and Comparative Examples 1 to 7 GRILAMID L20 as polyamide resin
(12 nylon manufactured by EMSCHEMIE) or GRILON
A28 (same 6 nylon), GRILON T300GM (same 66
nylon), Rilsan BMNO (11 nylon manufactured by ATO), benzenesulfonic acid butylamide or 2-ethylhexylbenzoate as a plasticizer,
The following acid-modified copolymers [X] or [Y] were used as the acid-modified olefin copolymers, respectively. The acid-modified copolymer [X] is an ethylene-propylene copolymer [Tafmer P-0280, manufactured by Mitsui Petrochemical Industries, Ltd.
100 parts of 1,3-bis(tert-butylperoxypropyl)benzene and 1 part of maleic anhydride were uniformly mixed in a Henschel mixer, mixed and kneaded at 230°C in an extruder, and pelletized. This is the acid-modified olefin copolymer [Y]
was obtained in the same manner except that ethylene-butene-1 copolymer [Tafmer A4090, manufactured by Mitsui Petrochemical Industries, Ltd.] was used as the raw material. The above polymers and plasticizers were blended in the proportions shown in Table 1, mixed in a Henschel mixer, and
Pellets were made by kneading at 180 to 260°C using a m/m single screw extruder. Samples for physical property evaluation and ski shoes were made from the pellets using an injection molding machine. Table 1 shows the evaluation results. 【table】
Claims (1)
又は底部を有するスキー靴において、該樹脂がポ
リアミド樹脂(A)と酸変性オレフイン共重合体(B)と
可塑剤(C)とを、(A)/(B)=40/60〜90/10、(C)/
{(A)+(B)}=1/100〜20/100の重量比で配合して
なるポリアミド樹脂組成物であることを特徴とす
る弾性スキー靴。 2 ポリアミド樹脂(A)が6ナイロン及び/又は66
ナイロンであることを特徴とする特許請求範囲第
1項に記載の弾性スキー靴。 3 ポリアミド樹脂(A)が12ナイロン及び/又は11
ナイロンであることを特徴とする特許請求範囲第
1項に記載の弾性スキー靴。 4 ポリアミド樹脂(A)が6ナイロン及び/又は66
ナイロン1〜99重量部と12ナイロン及び/又は11
ナイロン99〜1重量部とからなることを特徴とす
る特許請求範囲第1項に記載の弾性スキー靴。[Claims] 1. An upper outer skin formed by molding a thermoplastic resin and/or
Or in a ski shoe having a sole, the resin comprises a polyamide resin (A), an acid-modified olefin copolymer (B), and a plasticizer (C), (A)/(B) = 40/60 to 90/10. ,(C)/
An elastic ski shoe characterized by being made of a polyamide resin composition blended at a weight ratio of {(A)+(B)}=1/100 to 20/100. 2 Polyamide resin (A) is 6 nylon and/or 66
The elastic ski boot according to claim 1, characterized in that it is made of nylon. 3 Polyamide resin (A) is 12 nylon and/or 11
The elastic ski boot according to claim 1, characterized in that it is made of nylon. 4 Polyamide resin (A) is 6 nylon and/or 66
1 to 99 parts by weight of nylon and 12 nylon and/or 11
The elastic ski boot according to claim 1, characterized in that it is made of 99 to 1 part by weight of nylon.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13528084A JPS6116701A (en) | 1984-07-02 | 1984-07-02 | Elastic ski boots |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13528084A JPS6116701A (en) | 1984-07-02 | 1984-07-02 | Elastic ski boots |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS6116701A JPS6116701A (en) | 1986-01-24 |
JPH0224121B2 true JPH0224121B2 (en) | 1990-05-28 |
Family
ID=15148011
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13528084A Granted JPS6116701A (en) | 1984-07-02 | 1984-07-02 | Elastic ski boots |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6116701A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0666210U (en) * | 1993-02-22 | 1994-09-16 | 河村電器産業株式会社 | Base mounting bracket for electrical equipment storage box |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS642601A (en) * | 1987-02-03 | 1989-01-06 | Daiwa Seiko Inc | Ski boot |
KR100666457B1 (en) | 2005-06-03 | 2007-01-09 | 권영준 | Manufacturing method of toothbrush having needle-shaped bristle and a toothbrush manufactured in the same method |
-
1984
- 1984-07-02 JP JP13528084A patent/JPS6116701A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0666210U (en) * | 1993-02-22 | 1994-09-16 | 河村電器産業株式会社 | Base mounting bracket for electrical equipment storage box |
Also Published As
Publication number | Publication date |
---|---|
JPS6116701A (en) | 1986-01-24 |
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