JP6722017B2 - Molded product of resin composition and joint structure of molded product of resin composition - Google Patents
Molded product of resin composition and joint structure of molded product of resin composition Download PDFInfo
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- JP6722017B2 JP6722017B2 JP2016063198A JP2016063198A JP6722017B2 JP 6722017 B2 JP6722017 B2 JP 6722017B2 JP 2016063198 A JP2016063198 A JP 2016063198A JP 2016063198 A JP2016063198 A JP 2016063198A JP 6722017 B2 JP6722017 B2 JP 6722017B2
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- molded product
- resin composition
- heat stabilizer
- molded
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- 239000011342 resin composition Substances 0.000 title claims description 67
- 239000012760 heat stabilizer Substances 0.000 claims description 41
- 239000000835 fiber Substances 0.000 claims description 18
- 229920006122 polyamide resin Polymers 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 229920002379 silicone rubber Polymers 0.000 claims description 9
- 239000004945 silicone rubber Substances 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 239000012779 reinforcing material Substances 0.000 claims description 4
- 230000001012 protector Effects 0.000 claims description 3
- 230000004807 localization Effects 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 17
- 239000011347 resin Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
- 150000003254 radicals Chemical class 0.000 description 14
- 230000032683 aging Effects 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- -1 peroxide radicals Chemical class 0.000 description 12
- 238000000576 coating method Methods 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 10
- 239000004677 Nylon Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920001778 nylon Polymers 0.000 description 9
- 239000003566 sealing material Substances 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 8
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 3
- 239000007983 Tris buffer Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 3
- PFEFOYRSMXVNEL-UHFFFAOYSA-N 2,4,6-tritert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 PFEFOYRSMXVNEL-UHFFFAOYSA-N 0.000 description 2
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920002302 Nylon 6,6 Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
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- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229930003799 tocopherol Natural products 0.000 description 2
- 239000011732 tocopherol Substances 0.000 description 2
- WGVKWNUPNGFDFJ-DQCZWYHMSA-N β-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C WGVKWNUPNGFDFJ-DQCZWYHMSA-N 0.000 description 2
- GZIFEOYASATJEH-VHFRWLAGSA-N δ-tocopherol Chemical compound OC1=CC(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-VHFRWLAGSA-N 0.000 description 2
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 1
- HNURKXXMYARGAY-UHFFFAOYSA-N 2,6-Di-tert-butyl-4-hydroxymethylphenol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1O HNURKXXMYARGAY-UHFFFAOYSA-N 0.000 description 1
- UXAFLOLVPHNSNN-UHFFFAOYSA-N 2-(4,6-dimethylheptan-2-yl)-6-[[3-(4,6-dimethylheptan-2-yl)-2-hydroxy-5-methylphenyl]methyl]-4-methylphenol Chemical compound CC(C)CC(C)CC(C)C1=CC(C)=CC(CC=2C(=C(C(C)CC(C)CC(C)C)C=C(C)C=2)O)=C1O UXAFLOLVPHNSNN-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- YFHKLSPMRRWLKI-UHFFFAOYSA-N 2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-6-methylphenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 YFHKLSPMRRWLKI-UHFFFAOYSA-N 0.000 description 1
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 1
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 description 1
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 1
- MQWCQFCZUNBTCM-UHFFFAOYSA-N 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylphenyl)sulfanyl-4-methylphenol Chemical compound CC(C)(C)C1=CC(C)=CC(SC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O MQWCQFCZUNBTCM-UHFFFAOYSA-N 0.000 description 1
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 1
- MRBKEAMVRSLQPH-UHFFFAOYSA-N 3-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C(C(C)(C)C)=C1 MRBKEAMVRSLQPH-UHFFFAOYSA-N 0.000 description 1
- MDWVSAYEQPLWMX-UHFFFAOYSA-N 4,4'-Methylenebis(2,6-di-tert-butylphenol) Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 MDWVSAYEQPLWMX-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- GZIFEOYASATJEH-UHFFFAOYSA-N D-delta tocopherol Natural products OC1=CC(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 GZIFEOYASATJEH-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 229940087168 alpha tocopherol Drugs 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 description 1
- 229940066595 beta tocopherol Drugs 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- GVJHHUAWPYXKBD-UHFFFAOYSA-N d-alpha-tocopherol Natural products OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 1
- 235000010389 delta-tocopherol Nutrition 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009503 electrostatic coating Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 235000010382 gamma-tocopherol Nutrition 0.000 description 1
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N para-hydroxytoluene Natural products CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 238000007789 sealing Methods 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
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 229960000984 tocofersolan Drugs 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 229960001295 tocopherol Drugs 0.000 description 1
- 235000019149 tocopherols Nutrition 0.000 description 1
- 235000004835 α-tocopherol Nutrition 0.000 description 1
- 239000002076 α-tocopherol Substances 0.000 description 1
- 235000007680 β-tocopherol Nutrition 0.000 description 1
- 239000011590 β-tocopherol Substances 0.000 description 1
- 239000002478 γ-tocopherol Substances 0.000 description 1
- QUEDXNHFTDJVIY-UHFFFAOYSA-N γ-tocopherol Chemical class OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-UHFFFAOYSA-N 0.000 description 1
- QUEDXNHFTDJVIY-DQCZWYHMSA-N γ-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1 QUEDXNHFTDJVIY-DQCZWYHMSA-N 0.000 description 1
- 239000002446 δ-tocopherol Substances 0.000 description 1
Images
Landscapes
- Laminated Bodies (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Lining Or Joining Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
Description
本発明は、樹脂組成物の成形品に関し、特に、ポリアミド樹脂を含む、優れた機械的特性及び耐熱性を有する樹脂組成物の成形品及び樹脂組成物の成形品の接合構造に関する。 The present invention relates to a molded article of a resin composition, and more particularly to a molded article of a resin composition containing a polyamide resin and having excellent mechanical properties and heat resistance, and a joint structure of the molded article of the resin composition.
ナイロン６、ナイロン６６等のポリアミド樹脂は優れた機械的特性、耐熱性等の性質を有しており、エンジニアプラスチックとして多くの用途に用いられている。 Polyamide resins such as nylon 6 and nylon 66 have excellent mechanical properties and heat resistance, and are used in many applications as engineering plastics.
しかしながら、優れた耐熱性を有するポリアミド樹脂といえども、自動車部品に用いる場合のように長期に亘り高温に晒され続けるような場合には、樹脂が加熱時に雰囲気酸素と反応して劣化する熱老化が生じる。 However, even though it is a polyamide resin with excellent heat resistance, when it is exposed to high temperatures for a long period of time such as when it is used for automobile parts, heat aging in which the resin deteriorates by reacting with atmospheric oxygen during heating. Occurs.
熱老化は、加熱によって樹脂の骨格炭素上で発生するラジカルと酸素との反応によって形成されるパーオキサイドラジカルがポリマー鎖を連続的に切断するために生じると言われている。 Thermal aging is said to occur because peroxide radicals formed by the reaction of radicals generated on the skeletal carbon of the resin with heating and oxygen continuously cleave the polymer chains.
この樹脂の熱老化の抑制を目的として、樹脂に熱安定剤を添加する技術が特許文献１に開示されている。具体的には、特許文献１には、バイオマス由来の原料を使用したポリアミド樹脂に熱安定剤としてハロゲン化銅を配合したポリアミド樹脂組成物が開示されている。 Patent Document 1 discloses a technique of adding a heat stabilizer to a resin for the purpose of suppressing the heat aging of the resin. Specifically, Patent Document 1 discloses a polyamide resin composition in which a copper halide is blended as a heat stabilizer into a polyamide resin using a biomass-derived raw material.
特許文献１に記載されたハロゲン化銅以外にも、ポリアミド樹脂組成物に熱安定剤としてフェノール化合物を添加することが従来から行われている。 In addition to the copper halide described in Patent Document 1, it has been conventionally practiced to add a phenol compound as a heat stabilizer to a polyamide resin composition.
また、ポリアミド樹脂組成物の成形品が複数部品を組み合わせてなる製品の一部品である場合には、他の部品との良好な接着性能が要求される。かかる接着性能の一例としては、部品相互の接合部に介在するシリコーン系シール部材との接着性能が挙げられる。 Further, when the molded product of the polyamide resin composition is one part of a product obtained by combining a plurality of parts, good adhesion performance with other parts is required. An example of such adhesion performance is the adhesion performance with a silicone-based seal member interposed at the joint between parts.
しかしながら、特許文献１のポリアミド樹脂組成物によれば、ハロゲン化銅により熱老化が抑制されるものの、ポリアミド樹脂組成物を成形してなる成形品の接着性能については何ら触れられていない。熱安定剤として使用されるフェノール系化合物についても同様である。 However, according to the polyamide resin composition of Patent Document 1, although the heat aging is suppressed by the copper halide, there is no mention of the adhesive performance of the molded product obtained by molding the polyamide resin composition. The same applies to the phenolic compound used as the heat stabilizer.
また、ポリアミド樹脂中に上記添加剤を添加することにより、ポリアミド樹脂成形品の強度に影響を与えるおそれもある。 In addition, the addition of the above additives to the polyamide resin may affect the strength of the polyamide resin molded product.
本発明は、上記課題に鑑みてなされたものであり、その目的は、成形後の成形品の強度を損ねることなく、熱安定性及びシリコーン系シール材との良好な接着性能を兼ね備えた樹脂組成物の成形品及びこの樹脂組成物の成形品の接合構造を提供することにある。 The present invention has been made in view of the above problems, and an object thereof is a resin composition having both thermal stability and good adhesive performance with a silicone-based sealing material without impairing the strength of a molded product after molding. An object of the present invention is to provide a molded product and a joint structure for the molded product of the resin composition.
上記目的を達成するための請求項１に記載の発明は、ポリアミド樹脂を含有する樹脂組成物の成形品であって、該成形品は、チェーンカバー、インテークマニホールド、シリンダーヘッドカバー、タイミングベルトカバー、インタークラータンク、オイルリザーバータンク、オイルパン、オイルストレーナー、キャニスター、プロテクター、バンパー、フェンダー及びエンジンフードからなる群から選択される車両部品であるとともに、表面部に、分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上である熱安定剤を局在させたものであり、前記熱安定剤が局在する表面部が、成形品の表面から５０μｍ以上１００μｍ以下の厚さを有することを特徴とする。 The invention according to claim 1 for achieving the above object is a molded product of a resin composition containing a polyamide resin , wherein the molded product is a chain cover, an intake manifold, a cylinder head cover, a timing belt cover, an interface. It is a vehicle part selected from the group consisting of a clar tank, an oil reservoir tank, an oil pan, an oil strainer, a canister, a protector, a bumper, a fender and an engine hood, and has a molecular weight of 300 or more and occupies in the molecule on the surface part. A heat stabilizer having a molar concentration of OH groups of 9% or more is localized, and the surface portion on which the heat stabilizer is localized has a thickness of 50 μm or more and 100 μm or less from the surface of the molded article. Is characterized by.
この構成によれば、外部からの熱が真っ先に伝達され、熱老化の原因となるラジカルが発生する成形品の表面部に分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上である熱安定剤が局在しているので、ラジカル発生の場において効果的なラジカル除去がなされ、成形品の樹脂の熱老化を効果的に抑制することができる。 According to this structure, heat from the outside is transferred first, and radicals that cause heat aging are generated. The surface portion of the molded article has a molecular weight of 300 or more and the molar concentration of OH groups in the molecule is 9%. Since the heat stabilizer described above is localized, the radicals are effectively removed in the place where radicals are generated, and the heat aging of the resin of the molded article can be effectively suppressed.
また、上記所定の熱安定剤によってシリコーン系シール材との接着の場となる成形品の表面部に極性が付与されることで、このシリコーン系シール材との良好な接着性能が付与される。そのうえ、成形品の強度も損なわれることがない。 Further, the predetermined heat stabilizer imparts polarity to the surface portion of the molded product, which serves as a place for adhesion with the silicone-based sealing material, and thus provides good adhesion performance with the silicone-based sealing material. Moreover, the strength of the molded product is not impaired.
本発明の樹脂組成物の好ましい態様は以下の通りである。 Preferred embodiments of the resin composition of the present invention are as follows.
（１）表面部への前記熱安定剤の局在は、成形品の表面部の全面に該熱安定剤が存在するようになされている。
（２）強化材として繊維を樹脂組成物の総質量に対して最大６０質量％の量で含む。
(1) The localization of the heat stabilizer to the surface portion is such that the heat stabilizer is present on the entire surface portion of the molded product.
(2) The fiber is contained as a reinforcing material in an amount of up to 60% by mass based on the total mass of the resin composition.
また、上記目的は、本発明の樹脂組成物の成形品と該成形品と接合される被接合部材とが液状の硬化型シリコーンゴム組成物の硬化物を介して接合されたことを特徴とする樹脂組成物の成形品の接合構造によっても達成される。 Further, the above object is characterized in that a molded product of the resin composition of the present invention and a member to be bonded to the molded product are bonded via a cured product of a liquid curable silicone rubber composition. It is also achieved by the joint structure of a molded article of the resin composition.
本発明によれば、外部からの熱が真っ先に伝達され、熱老化の原因となるラジカルが発生する成形品の表面部に分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上である熱安定剤が局在しているので、ラジカル発生の場において効果的なラジカル除去がなされ、成形品の樹脂の熱老化を効果的に抑制することができる。 According to the present invention, heat from the outside is transferred first, and radicals that cause heat aging are generated. The surface portion of the molded article has a molecular weight of 300 or more and the molar concentration of OH groups in the molecule is 9%. Since the heat stabilizer described above is localized, the radicals are effectively removed in the place where radicals are generated, and the heat aging of the resin of the molded article can be effectively suppressed.
また、上記所定の熱安定剤によってシリコーン系シール材との接着の場となる成形品の表面部に極性が付与されることで、このシリコーン系シール材との良好な接着性能が付与される。また、成形品の強度も損なわれることがない。 Further, the predetermined heat stabilizer imparts polarity to the surface portion of the molded product, which serves as a place for adhesion with the silicone-based sealing material, and thus provides good adhesion performance with the silicone-based sealing material. Moreover, the strength of the molded product is not impaired.
したがって、車両の一部に本発明の樹脂組成物の成形品を用いた場合に、当該成形品自体として耐熱性・強度に優れるだけでなく、シリコーン系シール部材を介して接合された場合に車体骨格部材との良好な接合強度を有する接合構造を提供することができる。 Therefore, when a molded product of the resin composition of the present invention is used for a part of a vehicle, not only the molded product itself has excellent heat resistance and strength, but also when it is bonded via a silicone-based sealing member, the vehicle body A joint structure having good joint strength with a skeleton member can be provided.
以下、本発明を詳細に説明する。
［樹脂組成物の成形品］
本発明の樹脂組成物の成形品は、その表面部に局在する熱安定剤を含む。
Hereinafter, the present invention will be described in detail.
[Molded product of resin composition]
The molded article of the resin composition of the present invention contains a heat stabilizer localized on the surface portion thereof.
熱安定剤は、分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上であるフェノール系化合物である。 The heat stabilizer is a phenolic compound having a molecular weight of 300 or more and a molar concentration of OH groups in the molecule of 9% or more.
フェノール系化合物としては、例えば、ヒンダードフェノール化合物、トコフェロール等が挙げられる。 Examples of the phenol-based compound include hindered phenol compounds and tocopherols.
ヒンダードフェノール化合物の具体例としては、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、１，１，３−トリス（５−ｔ−ブチル−４−ヒドロキシ−２−メチルフェニル）ブタン、２−ｔ−ブチル−４−メトキシフェノール、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２，４，６−トリ−ｔ−ブチルフェノール、４−ヒドロキシメチル−２，６−ジ−ｔ−ブチルフェノール、スチレン化フェノール、２，５−ジ−ｔ−ブチルハイドロキノン、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート、トリエチレングリコールビス［３−（３−ｔ−ブチル−５−メチル−４−ヒドロキシフェニル）プロピオネート］、１，６−ヘキサンジオールビス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、ペンタエリスリトールテトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、２，２'−メチレンビス（６−ｔ−ブチル−４−エチルフェノール）、２，２'−メチレンビス［４−メチル−６−（１，３，５−トリメチルヘキシル）フェノール］、４，４'−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、４，４'−ブチリデンビス（３−メチル−６−ｔ−ブチルフェノール）、２，６−ビス（２−ヒドロキシ−３−ｔ−ブチル−５−メチルベンジル）−４−メチルフェノール、１，１，３−トリス［２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル］ブタン、１，３，５−トリメチル−２，４，６−トリス［３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル］ベンゼン、トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）イソシアヌレート、トリス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオニルオキシエチル］イソシアヌレート、４，４'−チオビス（３−メチル−６−ｔ−ブチルフェノール）、２，２'−チオビス（４−メチル−６−ｔ−ブチルフェノール）、４，４'−チオビス（２−メチル−６−ｔ−ブチルフェノール）、チオビス（β−ナフトール）が挙げられる。 Specific examples of the hindered phenol compound include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane and 2,2'-methylenebis(4-methyl-6-t-). Butylphenol), 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane, 2-t-butyl-4-methoxyphenol, 2,6-di-t-butyl-p. -Cresol, 2,4,6-tri-t-butylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, styrenated phenol, 2,5-di-t-butylhydroquinone, octadecyl-3-( 3,5-di-t-butyl-4-hydroxyphenyl)propionate, triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2 '-Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(1,3,5-trimethylhexyl)phenol], 4,4'-methylenebis(2 ,6-Di-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 2,6-bis(2-hydroxy-3-t-butyl-5-methylbenzyl)- 4-methylphenol, 1,1,3-tris[2-methyl-4-hydroxy-5-t-butylphenyl]butane, 1,3,5-trimethyl-2,4,6-tris[3,5- Di-t-butyl-4-hydroxybenzyl]benzene, tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[3-(3,5-di-t-butyl-4-) Hydroxyphenyl)propionyloxyethyl]isocyanurate, 4,4′-thiobis(3-methyl-6-t-butylphenol), 2,2′-thiobis(4-methyl-6-t-butylphenol), 4,4′ -Thiobis(2-methyl-6-t-butylphenol) and thiobis(β-naphthol).
トコフェロールの具体例としては、α−トコフェロール、β−トコフェロール、γ−トコフェロール、δ−トコフェロールが挙げられる。 Specific examples of tocopherol include α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol.
フェノール系化合物は、ヒンダードフェノール化合物であることが好ましく、特に好ましくは、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、１，１，３−トリス（５−ｔ−ブチル−４−ヒドロキシ−２−メチルフェニル）ブタンである。 The phenolic compound is preferably a hindered phenol compound, and particularly preferably 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 2,2′-methylenebis. (4-methyl-6-t-butylphenol) and 1,1,3-tris(5-t-butyl-4-hydroxy-2-methylphenyl)butane.
なお、フェノール化合物はこれらのみに限定されるものではなく、本発明の目的を達成し得る限りどのようなものであってもよい。 The phenol compound is not limited to these, and may be any compound as long as the object of the present invention can be achieved.
熱安定剤が局在する表面部は、成形品の表面から１０μｍ以上２００μｍ以下の厚さを有する。すなわち、熱安定剤は、成形品の表面から１０μｍ以上２００μｍ以下の範囲、好ましくは、５０μｍ以上１００μｍ以下の範囲に局在する。 The surface portion where the heat stabilizer is localized has a thickness of 10 μm or more and 200 μm or less from the surface of the molded product. That is, the heat stabilizer is localized in the range of 10 μm or more and 200 μm or less, preferably in the range of 50 μm or more and 100 μm or less from the surface of the molded product.
熱安定剤が、成形品の表面から１０μｍ未満の範囲にしか存在しない場合、熱により表面部において樹脂の炭化水素鎖上に発生したラジカルの成形品内部への侵入防止が不十分となり、樹脂組成物の成形品の熱老化を十分に抑制することができない。 When the heat stabilizer is present only within the range of less than 10 μm from the surface of the molded product, the radicals generated on the hydrocarbon chains of the resin on the surface due to heat are insufficiently prevented from entering the molded product, resulting in a resin composition. It is not possible to sufficiently suppress the heat aging of the molded product.
熱安定剤が成形品の表面から２００μｍ以上の範囲に存在する場合には、樹脂組成物中に繊維が添加されていると樹脂内部の熱安定剤が樹脂組成物中の樹脂と繊維の各ネットワークを分断し、その状態で高温放置されることで各界面相互作用が低下し、強度維持率が低下することとなる。 When the heat stabilizer is present in the range of 200 μm or more from the surface of the molded article, when the fiber is added to the resin composition, the heat stabilizer inside the resin causes each network of the resin and the fiber in the resin composition. When the steel is divided into pieces and left at that temperature for a long time, the interfacial interaction is reduced and the strength retention rate is reduced.
熱安定剤は、成形品の表面部の全面に存在することが好ましい。しかし、必ずしも成形品の表面部の全面に存在することが必須というわけではない。成形品の表面部のうち、後述する液状ガスケット（ＦＩＰＧ）との接着面に存在してＦＩＰＧとの接着性能を向上し、且つこれらの面のみ（上記接着面及び熱による影響を受ける部位となる面のみ）に局在させることも可能である。 The heat stabilizer is preferably present on the entire surface of the molded product. However, it does not necessarily have to exist on the entire surface of the molded product. Among the surface parts of the molded product, it exists on the adhesion surface with the liquid gasket (FIPG) described later to improve the adhesion performance with the FIPG, and only these surfaces (the above-mentioned adhesion surface and the area that is affected by heat are formed. Surface only).
成形品の内部は、樹脂組成物の固化物により形成される。樹脂組成物は、ポリアミド樹脂を含む。ポリアミド樹脂は、ω−アミノ酸の重縮合反応により合成されるｎ−ナイロン、ジアミンとジカルボン酸の共縮合重合反応で合成されるｎ，ｍ−ナイロンを用いることができる。 The inside of the molded product is formed by a solidified product of the resin composition. The resin composition contains a polyamide resin. As the polyamide resin, n-nylon synthesized by polycondensation reaction of ω-amino acid and n,m-nylon synthesized by co-condensation polymerization reaction of diamine and dicarboxylic acid can be used.
ｎ−ナイロンとしては、例えば、ナイロン−６、ナイロン−１１、ナイロン１２を挙げることができる。ｎ，ｍ−ナイロンとしては、例えば、ナイロン６６、ナイロン６１０、ナイロン６Ｔ、ナイロン６Ｉ、ナイロン９Ｔ、ナイロンＭ５Ｔを挙げることができる。 Examples of n-nylon include nylon-6, nylon-11, and nylon-12. Examples of the n,m-nylon include nylon 66, nylon 610, nylon 6T, nylon 6I, nylon 9T, nylon M5T.
樹脂組成物には、さらに強化材として繊維を含ませることができる。繊維としては、ガラス繊維、カーボン繊維、セラミック繊維（アルミナ繊維、炭化ケイ素繊維等）、石綿繊維、金属繊維（ステンレス繊維、アルミニウム繊維、黄銅繊維等）を挙げることができる。好ましくは、ガラス繊維、カーボン繊維である。 The resin composition may further contain fibers as a reinforcing material. Examples of the fiber include glass fiber, carbon fiber, ceramic fiber (alumina fiber, silicon carbide fiber, etc.), asbestos fiber, metal fiber (stainless fiber, aluminum fiber, brass fiber, etc.). Of these, glass fiber and carbon fiber are preferable.
繊維は、樹脂組成物の総質量に対して最大６０質量％の量で含ませることができる。６０質量％を超えると、射出成形による成形品の製造が困難となる。 The fibers can be included in an amount of up to 60% by weight, based on the total weight of the resin composition. If it exceeds 60% by mass, it becomes difficult to manufacture a molded product by injection molding.
また、樹脂組成物の成形品の初期強度向上の観点から、繊維は、樹脂組成物の総質量に対して１５質量％以上の量で含ませることが好ましい。 Further, from the viewpoint of improving the initial strength of the molded article of the resin composition, the fibers are preferably contained in an amount of 15% by mass or more based on the total mass of the resin composition.
さらに、本発明の樹脂組成物には、本発明の効果を損なわない範囲において、各種添加材を含ませることも可能である。各種添加材としては、有機又は無機の顔料、染料、可塑剤、脂肪酸、脂肪酸塩、脂肪酸アミド等の滑剤、発泡剤、リン酸エステル等の難燃剤、紫外線吸収剤、モノグリセライド等の帯電防止剤、有機リン化合物等の結晶核剤、シリコーン系化合物等の離型剤、フェノール系化合物等の熱安定剤が挙げられる。これらは、１種のみ添加してもよく、２種以上を添加してもよい。 Furthermore, the resin composition of the present invention may contain various additives within a range that does not impair the effects of the present invention. As various additives, organic or inorganic pigments, dyes, plasticizers, fatty acids, fatty acid salts, lubricants such as fatty acid amides, foaming agents, flame retardants such as phosphoric acid esters, ultraviolet absorbers, antistatic agents such as monoglycerides, Examples thereof include a crystal nucleating agent such as an organic phosphorus compound, a releasing agent such as a silicone compound, and a heat stabilizer such as a phenol compound. These may be added alone or in combination of two or more.
次に、本発明の樹脂組成物の成形品の製造方法について説明する。本発明の樹脂組成物の成形品は、樹脂組成物の成形物の表面を、熱安定剤を含むフィルム又は塗料で被覆することにより製造し得る。 Next, a method for producing a molded product of the resin composition of the present invention will be described. The molded article of the resin composition of the present invention can be produced by coating the surface of the molded article of the resin composition with a film or paint containing a heat stabilizer.
熱安定剤を含むフィルムは、例えば、本発明の樹脂組成物と同じ組成物に熱安定剤を添加して溶融混練したものをＴダイ法により押し出して得ることができる。なお、必要により延伸加工を行うことができる。また、フィルムの製造に用いる樹脂組成物は、本発明の樹脂組成物と全く同じ組成物とする必要はなく、例えば、繊維（強化剤）を除いたものとしてもよい。 The film containing the heat stabilizer can be obtained by, for example, extruding a melt-kneaded product obtained by adding the heat stabilizer to the same composition as the resin composition of the present invention by the T-die method. In addition, a stretching process can be performed if necessary. Further, the resin composition used for producing the film does not need to be the same composition as the resin composition of the present invention, and may be, for example, one in which fibers (reinforcing agent) are removed.
熱安定剤を添加する樹脂組成物から繊維（強化材）を除いたものとしてもよい。 A fiber (reinforcing material) may be removed from the resin composition to which the heat stabilizer is added.
また、熱安定剤を含む塗料は、例えば、極性を付与した、光硬化型（例えば、紫外線硬化型）の変性ナイロン塗料に熱安定剤を添加することで得ることができる。このような変性ナイロン塗料は市販されているものを用いることができる。 Further, the coating material containing the heat stabilizer can be obtained, for example, by adding a heat stabilizer to a light-curing (for example, ultraviolet-curing type) modified nylon coating to which polarity is imparted. As such a modified nylon coating, a commercially available one can be used.
上記樹脂組成物の成形物の表面を、熱安定剤を含むフィルム又は塗料で被覆する方法としては、（ｉ）樹脂組成物の成形物を形成し、当該成形物の表面を熱安定剤を含むフィルム又は塗料で被覆する方法、又は（ｉｉ）フィルムと樹脂組成物を金型内に入れ、樹脂組成物の表面をフィルムで被覆すると同時に成形する方法が挙げられる。 The method of coating the surface of the molded product of the resin composition with a film or a paint containing a heat stabilizer includes (i) forming a molded product of the resin composition and containing the heat stabilizer on the surface of the molded product. Examples thereof include a method of coating with a film or a paint, or (ii) a method of putting the film and the resin composition in a mold, coating the surface of the resin composition with the film, and simultaneously molding.
前者（ｉ）は二次加飾、後者（ｉｉ）は一次加飾と呼ばれる。 The former (i) is called secondary decoration, and the latter (ii) is called primary decoration.
（ｉ）について、樹脂組成物の成形物の形成は、従来公知の成形法（例えば、射出成形法、押出成形法、プレス成形法、真空成形法、ブロー成形法）を用いることができる。成形物の形成後、フィルムによる成形物表面の被覆を行う場合、オーバーレイ成形、ＴＯＭ工法（Ｔｈｒｒｅｅ−ｄｉｍｅｎｓｉｏｎ Ｏｖｅｒ−ｌａｙ Ｍｅｔｈｏｄ）により成形物表面にフィルムを適用することができる。成形物の形成後、塗料による成形物表面の被覆を行う場合、吹付け塗装、ローラー塗り、ロールコーター、静電塗装、粉体塗装、紫外線硬化塗装等、種々の塗布方法を適用することができる。なお、塗布された塗料は硬化処理等により固定される。 Regarding (i), the molding of the resin composition can be formed by a conventionally known molding method (for example, injection molding method, extrusion molding method, press molding method, vacuum molding method, blow molding method). When the surface of the molded product is covered with a film after the molded product is formed, the film can be applied to the surface of the molded product by overlay molding or the TOM method (Three-dimension Over-lay Method). When coating the surface of the molded product with a paint after forming the molded product, various coating methods such as spray coating, roller coating, roll coater, electrostatic coating, powder coating, and ultraviolet curing coating can be applied. .. The applied paint is fixed by a curing treatment or the like.
（ｉｉ）については、金型内に熱安定剤を含むフィルムをインサートし、その後に樹脂組成物を金型内に射出する射出成形、あるいは、樹脂組成物を金型内に射出した後にプレスする射出プレス成形等により、樹脂組成物の成形品を得ることができる。 Regarding (ii), a film containing a heat stabilizer is inserted into a mold, and then injection molding is performed in which the resin composition is injected into the mold, or the resin composition is injected into the mold and then pressed. A molded product of the resin composition can be obtained by injection press molding or the like.
本発明の樹脂組成物の成形品によれば、外部からの熱が真っ先に伝達され、熱老化の原因となるラジカルが発生する成形品の表面部に分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上である熱安定剤が局在しているので、ラジカル発生の場において効果的なラジカル除去がなされ、成形品の樹脂の熱老化を効果的に抑制することができる。 According to the molded article of the resin composition of the present invention, heat from the outside is first transmitted, and radicals that cause heat aging are generated. The surface portion of the molded article has a molecular weight of 300 or more and OH in the molecule. Since the heat stabilizer having a molar concentration of the group of 9% or more is localized, effective radical removal is performed in the field of radical generation, and heat aging of the resin of the molded product can be effectively suppressed. ..
また、上記所定の熱安定剤によってシリコーン系シール材との接着の場となる成形品の表面部に極性が付与されることで、このシリコーン系シール材との良好な接着性能が付与される。また、成形品の強度も損なわれることがない。 Further, the predetermined heat stabilizer imparts polarity to the surface portion of the molded product, which serves as a place for adhesion with the silicone-based sealing material, and thus provides good adhesion performance with the silicone-based sealing material. Moreover, the strength of the molded product is not impaired.
本発明の樹脂組成物の成形品としては、車両部品として、例えば、チェーンカバー、インテークマニホールド、シリンダーヘッドカバー、タイミングベルトカバー、インタークラータンク、オイルリザーバータンク、オイルパン、オイルストレーナー、キャニスター、プロテクター、バンパー、フェンダー、エンジンフード等を挙げることができる。 The molded product of the resin composition of the present invention includes, as vehicle parts, for example, a chain cover, an intake manifold, a cylinder head cover, a timing belt cover, an intercooler tank, an oil reservoir tank, an oil pan, an oil strainer, a canister, a protector, a bumper. , Fenders, engine hoods and the like.
［樹脂組成物の成形品の接合構造］
また、本発明は、本発明の樹脂組成物の成形品とこの成形品と接合される被接合部材とが液状の硬化型シリコーンゴム組成物の硬化物を介して接合されたことを特徴とする樹脂組成物の成形品の接合構造を提供する。
[Joining structure of molded product of resin composition]
Further, the present invention is characterized in that a molded product of the resin composition of the present invention and a member to be bonded to the molded product are bonded via a cured product of a liquid curable silicone rubber composition. Provided is a joint structure of a molded article of a resin composition.
本発明の成形品と接合される被接合部材としては、樹脂からなる成形品に限らず、金属成形品等が含まれる。金属成形品に含まれる金属としては、鋳鉄、アルミニウム、マグネシウム合金等を挙げることができる。 The member to be joined with the molded product of the present invention is not limited to the molded product made of resin, but includes metal molded products and the like. Examples of the metal contained in the metal molded product include cast iron, aluminum, magnesium alloy and the like.
液状の硬化型シリコーンゴム組成物としては、液状ガスケット（ＦＩＰＧ：Ｆｏｒｍｅｄ Ｉｎ Ｐｌａｃｅ Ｇａｓｋｅｔ）として市販されている公知のものを用いることができる。ＦＩＰＧは、互いに接合される部材の一方の接合面に塗布され、接合面を介して両者を圧接して養生硬化されるガスケットである。例えば、湿気硬化性シリコーンや２液混合硬化型シリコーンが挙げられる。 As the liquid curable silicone rubber composition, a publicly known liquid gasket (FIPG: Formed In Place Gasket) can be used. The FIPG is a gasket that is applied to one joint surface of the members to be joined to each other and is cured by curing the two members under pressure through the joint surface. For example, moisture-curable silicone and two-component mixed curable silicone can be used.
次に、本発明の樹脂組成物の成形品の接合構造の製造方法について説明する。 Next, a method for manufacturing a joint structure of a molded product of the resin composition of the present invention will be described.
まず、本発明の樹脂組成物の成形品の接合面及び被接合部材の少なくとも一方に液状の硬化型シリコーンゴム組成物を塗布し、この液状の硬化型シリコーンゴム組成物を介して両者を圧接する。その状態で液状のシリコーンゴム組成物を硬化させることで、上記樹脂組成物の成形品及び被接合部材とが接合され、本発明の樹脂組成物の成形品の接合構造を得ることができる。 First, a liquid curable silicone rubber composition is applied to at least one of a joint surface and a member to be joined of a molded product of the resin composition of the present invention, and both are pressure-contacted via the liquid curable silicone rubber composition. .. By curing the liquid silicone rubber composition in that state, the molded product of the resin composition and the member to be bonded are bonded, and the bonded structure of the molded product of the resin composition of the present invention can be obtained.
この樹脂組成物の成形品の接合構造によれば、外部からの熱が真っ先に伝達され、熱老化の原因となるラジカルが発生する成形品の表面部に上記所定の熱安定剤が局在しているので、ラジカル発生の場において効果的なラジカル除去がなされ、成形品の樹脂の熱老化が効果的に抑制され、且つ液状のシリコーンゴム組成物の硬化物との接着性が向上し、より強固な成形品と被接着部材との接合構造を得ることができる。 According to the joint structure of the molded article of this resin composition, the heat from the outside is first transferred, and the predetermined heat stabilizer is localized on the surface portion of the molded article where radicals causing heat aging are generated. Therefore, effective radical removal is performed in the field of radical generation, heat aging of the resin of the molded product is effectively suppressed, and the adhesiveness with the cured product of the liquid silicone rubber composition is improved, It is possible to obtain a strong joint structure between the molded product and the adherend member.
また、上記所定の熱安定剤によってシリコーン系シール材（液状のシリコーンゴム組成物の硬化物）との接着の場となる成形品の表面部に極性が付与されることで、このシリコーン系シール材との良好な接着性能が付与される。また、成形品の強度も損なわれることがない。 In addition, the predetermined heat stabilizer imparts polarity to the surface portion of the molded product, which serves as a place of adhesion with the silicone-based sealing material (cured product of liquid silicone rubber composition), so that the silicone-based sealing material Good adhesion performance with Moreover, the strength of the molded product is not impaired.
本発明の樹脂組成物の成形品の接合構造としては、例えば、上記例示の車両部品と車両骨格部材との接合構造を挙げることができる。 Examples of the joint structure of the molded product of the resin composition of the present invention include the joint structure between the vehicle component and the vehicle frame member exemplified above.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to examples.
［実施例１〜４及び比較例１］
１−１．樹脂組成物
ポリアミド樹脂を含有する樹脂組成物としては、ガラス繊維３０質量％添加ポリアミド６樹脂であるＰＡ−６−ＧＦ３０−０１（ダイセルポリマー株式会社製）を用いた。
[Examples 1 to 4 and Comparative Example 1]
1-1. Resin composition As a resin composition containing a polyamide resin, PA-6-GF30-01 (manufactured by Daicel Polymer Ltd.), which is a polyamide 6 resin containing 30% by mass of glass fiber, was used.
１−２．成形品の表面部作成用のフィルム
ポリアミド樹脂１００質量部に対して１,１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタンを２０質量部の割合で配合し、２軸混練押出機（株式会社パーカーコーポレーション製ＨＫ２５Ｄ−４１）を用いてＴダイ押出成型（株式会社創研製）により溶融混練後の樹脂を押出し、厚さ１０μｍ、５０μｍ、１００μｍ及び２００μｍのフィルムをそれぞれ作成した。
1-2. Film for forming surface part of molded article 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane was mixed in a ratio of 20 parts by mass with respect to 100 parts by mass of polyamide resin. The resin after melt-kneading is extruded by T-die extrusion molding (manufactured by Soken Co., Ltd.) using a twin-screw kneading extruder (HK25D-41 manufactured by Parker Corporation) to form films having thicknesses of 10 μm, 50 μm, 100 μm and 200 μm. Created respectively.
１−３．成形品の製造
「１．樹脂組成物」のＰＡ−６−ＧＦ３０−０１を８０℃、減圧下で４時間乾燥し、射出成型機（日精樹脂工業株式会社製ＰＮＸ−ＩＩＩ）、シリンダー温度；Ｃ１＝２３０℃、Ｃ２＝２４０℃、Ｃ３＝２５０℃、ノズル＝２４０℃、樹脂＝２５０℃、金型＝６０℃）を用いて射出成型を行い、ＪＩＳ Ｋ７１６１に準拠した試験片及びＩＳＯ１９０９５−３に準拠した試験片を得た。
1-3. Manufacture of molded article PA-6-GF30-01 of "1. Resin composition" is dried at 80°C under reduced pressure for 4 hours, and then injection molding machine (PNX-III manufactured by Nissei Plastic Co., Ltd.), cylinder temperature; C1 =230° C., C2=240° C., C3=250° C., nozzle=240° C., resin=250° C., mold=60° C.), injection molding is performed, and a test piece and ISO 19095-3 in accordance with JIS K7161 are obtained. A compliant test piece was obtained.
次に、射出成形後のそれぞれの試験片を、真空チャンバー内においてオーバーレイ成形を行い、図１に示すように、底面１０ａａの一部を除いて表面部１０ａが厚さ１０μｍのフィルムで被覆された成形品１０（実施例１）を得た。
Next, each test piece after injection molding was subjected to overlay molding in a vacuum chamber, and as shown in FIG. 1, the
同様に、実施例１からフィルムの厚さのみを５０μｍ（実施例２）、１００μｍ（実施例３）及び２００μｍ（実施例４）にそれぞれ変更した成形品１０を得た。
Similarly, a molded
［比較例４］
２−１．樹脂組成物
ガラス繊維３０質量％添加ポリアミド６樹脂であるＰＡ−６−ＧＦ３０−０１（ダイセルポリマー株式会社製）１００質量部に対して１,１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタンを１質量部の割合で配合し、２軸混練押出機（株式会社パーカーコーポレーション製ＨＫ２５Ｄ−４１）を用いて溶融混練し、ペレット化した。
[Comparative Example 4]
2-1. Resin composition 1,6-tris(2-methyl-4-hydroxy-)-based on 100 parts by mass of PA-6-GF30-01 (manufactured by Daicel Polymer Ltd.), which is polyamide 6 resin containing 30% by mass of glass fiber. 5-t-Butylphenyl)butane was blended in a proportion of 1 part by mass, melt-kneaded using a twin-screw kneading extruder (HK25D-41 manufactured by Parker Corporation), and pelletized.
２−２．成形品の製造
「２−１．樹脂組成物」で得られたペレットを８０℃、減圧下で４時間乾燥し、射出成型機（日精樹脂工業株式会社製ＰＮＸ−ＩＩＩ、シリンダー温度；Ｃ１＝２３０℃、Ｃ２＝２４０℃、Ｃ３＝２５０℃、ノズル＝２４０℃、樹脂＝２５０℃、金型＝６０℃）を用いて射出成型を行い、ＪＩＳ Ｋ７１６１に準拠した試験片及びＩＳＯ１９０９５に準拠した試験片を得た。これらの試験片が、比較例４に係る成形品とした。
2-2. Manufacture of molded product The pellets obtained in "2-1. Resin composition" are dried at 80°C under reduced pressure for 4 hours, and then injection molding machine (PNX-III manufactured by Nissei Plastic Co., Ltd., cylinder temperature; C1 = 230). C, C2=240° C., C3=250° C., nozzle=240° C., resin=250° C., mold=60° C.), injection molding is performed, and a test piece according to JIS K7161 and a test piece according to ISO19095. Got These test pieces were molded articles according to Comparative Example 4.
３．評価試験
３−１．プラスチック−引張特性の試験
「１−３．成形品の製造」及び「２−２．成形品の製造」で得られた成形品（ＪＩＳ Ｋ７１６１に準拠した試験片）を用い、ＪＩＳ Ｋ７１６１に準拠したプラスチック−引張特性の試験を行った。
3. Evaluation test 3-1. Plastic-Tensile property test Using the molded products (test pieces according to JIS K7161) obtained in "1-3. Manufacture of molded products" and "2-2. Manufacture of molded products", JIS K7161 was compliant. The plastic-tensile properties were tested.
試験は、上記成形品のそれぞれの区分につき、成形直後の未被熱成形品及び成形後、１５０℃で３０００時間の熱劣化試験を行った被熱成形品の双方について行った。 The test was carried out for each of the above-mentioned molded articles for both the unheated molded article immediately after molding and the thermally molded article that was subjected to a heat deterioration test at 150° C. for 3000 hours after molding.
表１中、初期強度比（％）は、熱安定剤含有フィルムにより被覆されていない未被熱成形品（比較例１）の引張強さ（引張試験中に加わった最大引張応力）を１００％としたときの、熱安定剤含有フィルムにより被覆した未被熱成形品（実施例１〜４）及び熱安定剤を成形品全体に分散させた未被熱成形品（比較例２）の引張強さの比を示している。 In Table 1, the initial strength ratio (%) is 100% of the tensile strength (maximum tensile stress applied during the tensile test) of the unheated molded product (Comparative Example 1) not covered with the heat stabilizer-containing film. The tensile strengths of the unheated molded articles (Examples 1 to 4) coated with the heat stabilizer-containing film and the unheated molded article (Comparative Example 2) in which the heat stabilizer is dispersed throughout the molded article. It shows the ratio of the height.
また、表１中、強度維持率（％）は、各区分において、未被熱成形品の引張強さ（引張試験中に加わった最大引張応力）を１００％としたときの、被熱成形品の引張強さの比を示している。 Further, in Table 1, the strength retention rate (%) is the heat-molded product when the tensile strength (maximum tensile stress applied during the tensile test) of the non-heat-molded product is 100% in each category. Shows the ratio of the tensile strength of.
３−２．樹脂−金属複合体の接合界面特性評価
「１−３．成形品の製造」及び「２−２．成形品の製造」で得られた成形品（ＩＳＯ１９０９５に準拠）の一端面１０ｂ（図１参照）にシリコーン系材料の液状ガスケット（ＦＩＰＧ）を塗布し、この塗布面にアルミニウム片を接触させた後に液状ガスケットを硬化し、接合界面特性評価用の突合せ接着試験体を作成した。
3-2. Evaluation of joining interface characteristics of resin-metal composite body One
この試験体に対してＩＳＯ１９０９５に準拠した方法により、試験体の接合強度を求めた。接合強度は、接合部分の破断が生じたときの接合部の単位体積あたりの荷重（ＭＰａ）として求めた。求められた値を、表１中のＦＩＰＧ接着性（ＭＰａ）として示す。 The joint strength of the test body was determined by a method according to ISO19095. The joint strength was determined as a load (MPa) per unit volume of the joint when the joint was broken. The obtained value is shown as FIPG adhesiveness (MPa) in Table 1.
Claims (4)
該成形品は、チェーンカバー、インテークマニホールド、シリンダーヘッドカバー、タイミングベルトカバー、インタークラータンク、オイルリザーバータンク、オイルパン、オイルストレーナー、キャニスター、プロテクター、バンパー、フェンダー及びエンジンフードからなる群から選択される車両部品であるとともに、
表面部に、分子量が３００以上で且つ分子中に占めるＯＨ基のモル濃度が９％以上である熱安定剤を局在させたものであり、
前記熱安定剤が局在する表面部が、成形品の表面から５０μｍ以上１００μｍ以下の厚さを有することを特徴とする樹脂組成物の成形品。 A molded article of a resin composition containing a polyamide resin ,
The molded product is a vehicle selected from the group consisting of a chain cover, an intake manifold, a cylinder head cover, a timing belt cover, an intercooler tank, an oil reservoir tank, an oil pan, an oil strainer, a canister, a protector, a bumper, a fender, and an engine hood. with a component,
A heat stabilizer having a molecular weight of 300 or more and a molar concentration of OH groups in the molecule of 9% or more is localized on the surface portion,
A molded product of a resin composition, wherein the surface portion where the heat stabilizer is localized has a thickness of 50 μm or more and 100 μm or less from the surface of the molded product.
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