JP7486056B2 - 発泡成形用ポリアミド樹脂組成物および発泡成形体 - Google Patents
発泡成形用ポリアミド樹脂組成物および発泡成形体 Download PDFInfo
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- JP7486056B2 JP7486056B2 JP2021526980A JP2021526980A JP7486056B2 JP 7486056 B2 JP7486056 B2 JP 7486056B2 JP 2021526980 A JP2021526980 A JP 2021526980A JP 2021526980 A JP2021526980 A JP 2021526980A JP 7486056 B2 JP7486056 B2 JP 7486056B2
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- polyamide resin
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- copolymer
- foamed
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- 229920006122 polyamide resin Polymers 0.000 title claims description 105
- 239000011342 resin composition Substances 0.000 title claims description 67
- 238000010097 foam moulding Methods 0.000 title claims description 22
- 239000006260 foam Substances 0.000 title description 23
- 229920001577 copolymer Polymers 0.000 claims description 78
- 229920005989 resin Polymers 0.000 claims description 77
- 239000011347 resin Substances 0.000 claims description 77
- 229920006039 crystalline polyamide Polymers 0.000 claims description 28
- 229920001971 elastomer Polymers 0.000 claims description 28
- 239000000806 elastomer Substances 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 27
- 125000000524 functional group Chemical group 0.000 claims description 24
- 229920006020 amorphous polyamide Polymers 0.000 claims description 23
- 239000012779 reinforcing material Substances 0.000 claims description 20
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 15
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 239000004711 α-olefin Substances 0.000 claims description 12
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 7
- 229920002292 Nylon 6 Polymers 0.000 claims description 6
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- -1 aliphatic diamines Chemical class 0.000 description 59
- 238000000034 method Methods 0.000 description 32
- 239000000047 product Substances 0.000 description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 31
- 239000010410 layer Substances 0.000 description 30
- 210000004027 cell Anatomy 0.000 description 29
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 239000004952 Polyamide Substances 0.000 description 25
- 229920002647 polyamide Polymers 0.000 description 25
- 239000000126 substance Substances 0.000 description 22
- 239000004088 foaming agent Substances 0.000 description 21
- 239000000203 mixture Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 239000001569 carbon dioxide Substances 0.000 description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 239000003365 glass fiber Substances 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 11
- 229920005992 thermoplastic resin Polymers 0.000 description 11
- 238000001746 injection moulding Methods 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 238000000465 moulding Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000007822 coupling agent Substances 0.000 description 9
- 230000005484 gravity Effects 0.000 description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 210000000497 foam cell Anatomy 0.000 description 8
- 238000005187 foaming Methods 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 6
- 230000008023 solidification Effects 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 229920001155 polypropylene Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 150000001244 carboxylic acid anhydrides Chemical group 0.000 description 4
- 125000002843 carboxylic acid group Chemical group 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- 230000008719 thickening Effects 0.000 description 4
- 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 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004604 Blowing Agent Substances 0.000 description 3
- 239000005749 Copper compound Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 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
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical class C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 150000001880 copper compounds Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000004985 diamines Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 150000003951 lactams Chemical class 0.000 description 3
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 3
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Natural products OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 3
- 239000013585 weight reducing agent Substances 0.000 description 3
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- MEJAPGGFIJZHEJ-UHFFFAOYSA-N 5-acetamido-1,3,4-thiadiazole-2-sulfonyl chloride Chemical class CC(=O)NC1=NN=C(S(Cl)(=O)=O)S1 MEJAPGGFIJZHEJ-UHFFFAOYSA-N 0.000 description 2
- QNVNLUSHGRBCLO-UHFFFAOYSA-N 5-hydroxybenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC(O)=CC(C(O)=O)=C1 QNVNLUSHGRBCLO-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004593 Epoxy 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 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
- 239000002585 base Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
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- 150000004668 long chain fatty acids Chemical class 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002832 nitroso derivatives Chemical class 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical class O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920006128 poly(nonamethylene terephthalamide) Polymers 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001601 polyetherimide Polymers 0.000 description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 description 2
- 229920000306 polymethylpentene Polymers 0.000 description 2
- 239000011116 polymethylpentene Substances 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
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- 229920006012 semi-aromatic polyamide Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920000428 triblock copolymer Polymers 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- YVPUHRTVWANKKE-UHFFFAOYSA-N 1-(azidomethyl)-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(CN=[N+]=[N-])C=C1 YVPUHRTVWANKKE-UHFFFAOYSA-N 0.000 description 1
- GWWBILGABMLVTN-UHFFFAOYSA-N 1-but-1-enyl-2,3-dimethylbenzene Chemical group CCC=CC1=CC=CC(C)=C1C GWWBILGABMLVTN-UHFFFAOYSA-N 0.000 description 1
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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Description
(2) 前記結晶性ポリアミド樹脂(A)がポリアミド6であり、前記非結晶性ポリアミド樹脂(B)がポリアミド6I/6Tである(1)に記載の発泡成形用ポリアミド樹脂組成物。
(3) 前記エラストマー(D)が酸変性したα―オレフィン系(共)重合体であり、前記ポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)がグリシジル基含有スチレン系共重合体である(1)または(2)に記載の発泡成形用ポリアミド樹脂組成物。
(4) 降温結晶化温度が190℃未満である請求項(1)~(3)のいずれかに記載の発泡成形用ポリアミド樹脂組成物。
(5) 前記ポリアミド樹脂組成物の温度が260℃でせん断速度が60.8sec-1のときの溶融粘度が550Pa・s以上であり、温度が260℃でせん断速度が608sec-1のときの溶融粘度が300Pa・s以下である(1)~(4)のいずれかに記載の発泡成形用ポリアミド樹脂組成物。
(6) (1)~(5)のいずれかに記載の発泡成形用ポリアミド樹脂組成物を構成成分とする発泡成形体。
(7) 樹脂連続相と平均セル径10~300μmの独立した発泡セルから構成される発泡層と、該発泡層の両面に厚み200~500μmの非発泡スキン層が設けられたサンドイッチ構造を有し、該発泡層の樹脂連続相および該非発泡スキン層が、(1)~(5)のいずれかに記載の発泡成形用ポリアミド樹脂組成物からなり、該非発泡スキン層側から測定した光沢度が80以上である発泡成形体。
(ポリアミド樹脂組成物)
本発明のポリアミド樹脂組成物は、発泡成形に適したポリアミド樹脂組成物であって、結晶性ポリアミド樹脂(A)、非結晶性ポリアミド樹脂(B)、無機強化材(C)、エラストマー(D)、およびポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)を含有する。本発明のポリアミド樹脂組成物中の各成分の含有量(配合量)は、特に但し書きをしない限り、結晶性ポリアミド樹脂(A)、非結晶性ポリアミド樹脂(B)、無機強化材(C)、エラストマー(D)、およびポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)の合計が100質量部としたときの量で表す。また、本発明のポリアミド樹脂組成物においては、各成分の配合量が、そのままポリアミド樹脂組成物中の含有量になる。
本発明で用いられる結晶性ポリアミド樹脂(A)は、ラクタムやω-アミノカルボン酸、ジカルボン酸及びジアミンなどを原料とするものであり、このようなアミン成分及び酸成分の重縮合によって得られるポリアミド樹脂、又はこれらの共重合体やブレンド物である。
非結晶性ポリアミド樹脂(B)は、ガラス転移温度が120℃以上、200℃以下の半芳香族ポリアミド樹脂が好ましい。ガラス転移温度が120℃未満であれば、耐熱性が不充分となる虞があり、ガラス転移点が200℃を超えると固化温度が高すぎるため後述する金型を拡張する発泡法が適用しにくくなる。
本発明で用いられる無機強化材(C)は、強度や剛性および耐熱性等の物性を最も効果的に改良するものである。具体的には、ガラス繊維、炭素繊維、アラミド繊維、アルミナ繊維、炭化珪素繊維、ジルコニヤ繊維等の繊維状のもの、ホウ酸アルミニウム、チタン酸カリウム等のウイスカー類、針状ワラストナイト、ミルドフファイバー等を挙げることができる。またこれらのほか、ガラスビーズ、ガラスフレーク、ガラスバルーン、シリカ、タルク、カオリン、ワラストナイト、マイカ、アルミナ、ハイドロタルサイト、モンモリロナイト、グラファイト、カーボンナノチューブ、フラーレン、酸化亜鉛、酸化インジウム、酸化錫、酸化鉄、酸化チタン、酸化マグネシウム、水酸化アルミニウム、水酸化マグネシウム、赤燐、炭酸カルシウム、チタン酸カリウム、チタン酸ジルコン酸鉛、チタン酸バリウム、窒化アルミニウム、窒化ホウ素、ホウ酸亜鉛、ホウ酸アルミニウム、硫酸バリウム、硫酸マグネシウム、層間剥離を目的として有機処理を施した層状ケイ酸塩等の充填材も無機強化材(C)として用いることができる。これらの中でも、ガラス繊維、炭素繊維などが好ましく用いられ、特にガラス繊維が好ましい。これら無機強化材(C)は、1種のみであってもよいし2種以上を組み合わせてもよい。
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本発明において、エラストマー(D)は、ポリアミド樹脂組成物の増粘効果促進のために用いられる。ポリアミド樹脂組成物の粘度が適切でない場合には、樹脂中に含まれているガスの存在により、発泡セルの破れや、成形品の表面にスワールマークなど、外観不良が生じ、光沢度が下がることがある。エラストマー(D)としては、オレフィン系エラストマー、スチレン系エラストマー、エステル系エラストマー、アミド系エラストマー、ウレタン系エラストマー等の公知のエラストマーが使用可能である。中でも、カルボン酸基および/またはカルボン酸無水物基を有するオレフィン系重合体(酸変性ポリオレフィン)が好ましい。この酸変性ポリオレフィンは、カルボン酸基および/またはカルボン酸無水物基を有する単量体を共重合やグラフト重合などによって未変性ポリオレフィンの分子鎖中に結合させたα-オレフィン(共)重合体である。
本発明で用いられるポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)(以降、省略して共重合体(E)と称することがある)としては、ポリアミド樹脂の末端基と反応する官能基を有する各種共重合体であって、前記のエラストマー(D)とは異なる共重合体を用いることができる。ポリアミド樹脂の末端基と反応する官能基としては、グリシジル基(エポキシ基)、カルボキシル基、ヒドロキシ基、アミノ基などが上げられるが、中でもグリシジル基(エポキシ基)が好ましい。本発明では、共重合体(E)を含有させることにより、分子量を増加させて溶融伸張粘度増大効果を発現させることにより、加工条件管理幅を広げ、その結果、耐熱性とともに優れた軽量性および耐荷重性を有する発泡成形体を得るという所期の目的を達成することができるのである。
本発明のポリアミド樹脂組成物には、前述のもの以外に、ポリアミド樹脂に従来から使用されている各種添加剤を含有させることができる。添加剤としては、安定剤、衝撃改良材、難燃剤、離型剤、摺動性改良材、着色剤、可塑剤、結晶核剤などが挙げられる。また添加剤として、金型等の金属腐食を防止する目的でハイドロタルサイト系化合物を用いることもできる。添加剤は1種のみであってもよいし2種以上であってもよい。
本発明のポリアミド樹脂組成物においては、ポリアミド樹脂の末端基と反応する共重合体(E)の反応によってゲルには至らない比較的ゆるやかな架橋や分岐構造が生成する。このためポリアミド樹脂組成物の溶融状態において分子の絡み合い効果を増大させうることができる。この反応生成物は溶融粘度を増大させるだけでなく、溶融状態でひずみを与えられた場合、長時間緩和成分として広いせん断速度領域において緩和挙動を遅くする効果を発現すると考えられる。具体的には、ポリアミド樹脂や共重合体(E)、無機強化材(C)ならびにエラストマー(D)の種類および量にもよるが、好ましくは本発明で示される(A)~(E)の各成分の含有量の範囲とし、ポリアミド樹脂と共重合体(E)との反応に必要な時間、マトリクス組成物に充分に高いせん断応力をかけうるような押出機スクリュー構成、温度設定、スクリュー回転数、時間当たり押し出し量などのコンパウンド条件を選定すればよい。
かくして得られた本発明のポリアミド樹脂組成物は、溶融状態における粘度安定性が高く、特に発泡成形に適した溶融レオロジー特性を有している。
本発明の発泡成形体は、上述した本発明のポリアミド樹脂組成物を用いて得られたものである。かかる本発明の発泡成形体は、表層に存在する非発泡スキン層と内層に存在する発泡層とを備えており、これら非発泡スキン層及び発泡層は上述した本発明のポリアミド樹脂組成物で形成されているので、均一なセル状態の発泡構造を有し、優れた軽量性と耐荷重性を発現できる。
本発明の発泡成形体を得る際に用いることのできる発泡剤は、発泡核となるガス成分もしくはその発生源として成形機の樹脂溶融ゾーンで溶融している樹脂に添加するものである。
なお、実施例に記載された測定値は、以下の方法によって測定したものである。
得られた発泡成形体の表面外観(非発泡スキン層側)を確認し、目視にて、表面にガス浮き模様が確認されなければ「○」、表面にガス浮き模様が確認されれば「×」とした。
JIS Z-8714に準じて、得られた発泡成形体の表面(非発泡スキン層側)において、入射角85度の光沢度を測定した。
まず、可視光硬化型樹脂に包埋後に研磨して発泡断面を露出させるか、あるいは、予めノッチをつけて破壊によって発泡断面が露出するように調製した成形体を液体窒素に10分間浸漬した後に衝撃破壊して発泡断面を露出させることにより、断面観察用サンプルを得た。
可視光硬化型樹脂に包埋後に研磨して発泡断面を露出させるか、あるいは、予めノッチをつけて破壊によって発泡断面が露出するように調製した成形体を液体窒素に10分間浸漬した後に衝撃破壊して発泡断面を露出させることにより、断面観察用サンプルを得た。そして、走査型電子顕微鏡により撮影した上記断面観察用サンプルの発泡断面の写真を画像処理し、表層部分に観られる一体化した非発泡層の厚みをスキン層厚みとして測定した。
105℃で15時間減圧乾燥した試料(ポリアミド樹脂組成物)をアルミニウム製パン(TA Instruments社製「品番900793.901」)に5mg量り取り、アルミニウム製蓋(TA Instruments社製「品番900794.901」)で密封状態にした後、示差走査熱量計(TA Instruments製「DSCQ100」)を用いて室温から265℃まで20℃/分で昇温し、その後室温まで20℃/分で降温させ、その際の発熱ピーク温度を結晶化温度(Tc2)とした。
キャピラリーフローテスターを用いて、温度が260℃、せん断速度が60.8sec-1、温度が260℃、せん断速度が608sec-1のときの溶融粘度を測定した。なお、キャピラリーは長さが10mm、直径1mmのものを使用した。
<結晶性ポリアミド樹脂(A)>
ポリアミド6;Shenma製「TP-4208」、相対粘度2.6
<非結晶性ポリアミド樹脂(B)>
ポリアミド6I/6T;EMS社製「グリボリーG21」、相対粘度2.1
<無機強化材(C)>
ガラス繊維;日東紡株式会社製「CS3PE453」
無水マレイン酸変性エチレン・α―オレフィン系共重合体;三井化学株式会社製「MH5020」、α―オレフィンはブテン-1、酸無水物基含有量100μmol/g
無水マレイン酸変性エチレン・α―オレフィン系共重合体;三井化学株式会社製「MH7020」、α―オレフィンはブテン-1、酸無水物基含有量100μmol/g
無水マレイン酸変性スチレン系共重合体;旭化成株式会社製「M1943」、スチレン/エチレン・ブチレン比=20/80、酸価:10mgCH3ONa/g
グリシジル基含有スチレン系共重合体;東亞合成株式会社製アルフォン「UG4050」、スチレン/グリシジルアクリレート共重合体
安定剤:ソンウォンインターナショナルジャパン「SONGNOX2450」
離型剤:クラリアントジャパン社製「モンタン酸エステルワックスWE40」
黒顔料:日本ピグメント株式会社製「EX3236」
上述した各原料(A)~(E)の配合量(質量部)は表1に示す通りとし、その他の添加剤の配合量については各実施例・比較例とも、安定剤が0.3質量部、離型剤が0.3質量部、黒顔料が1.0質量部とし、これらを35φ二軸押出機(東芝機械社製)にて混合した。詳しくは、まず無機強化材(C)以外の原料をスクリュー回転数100rpmにてホッパーより同時に投入して溶融混練した後、無機強化材(C)をサイドフィードで投入した。このとき、シリンダ温度は250℃に設定した。押出機から吐出されたストランドを水槽で冷却した後、ストランドカッターでペレット化し、125℃で5時間乾燥することにより、ポリアミド樹脂組成物をペレットとして得た。
Claims (7)
- 発泡成形用ポリアミド樹脂組成物であって、該ポリアミド樹脂組成物は、結晶性ポリアミド樹脂(A)40~70質量部、非結晶性ポリアミド樹脂(B)5~15質量部、無機強化材(C)15~50質量部、エラストマー(D)0.1~10質量部、およびポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)0.5~15質量部を含有し、結晶性ポリアミド樹脂(A)、非結晶性ポリアミド樹脂(B)、無機強化材(C)、エラストマー(D)、およびポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)の合計が100質量部であり、前記共重合体(E)の重量平均分子量が4000~25000であることを特徴とする発泡成形用ポリアミド樹脂組成物。
- 前記結晶性ポリアミド樹脂(A)がポリアミド6であり、前記非結晶性ポリアミド樹脂(B)がポリアミド6I/6Tである請求項1に記載の発泡成形用ポリアミド樹脂組成物。
- 前記エラストマー(D)が酸変性したα―オレフィン系(共)重合体であり、前記ポリアミド樹脂の末端基と反応する官能基を有する共重合体(E)がグリシジル基含有スチレン系共重合体である請求項1または2に記載の発泡成形用ポリアミド樹脂組成物。
- 降温結晶化温度が190℃未満である請求項1~3のいずれかに記載の発泡成形用ポリアミド樹脂組成物。
- 前記ポリアミド樹脂組成物の温度が260℃でせん断速度が60.8sec-1のときの溶融粘度が550Pa・s以上であり、温度が260℃でせん断速度が608sec-1のときの溶融粘度が300Pa・s以下である請求項1~4のいずれかに記載の発泡成形用ポリアミド樹脂組成物。
- 請求項1~5のいずれかに記載の発泡成形用ポリアミド樹脂組成物を構成成分とする発泡成形体。
- 樹脂連続相と平均セル径10~300μmの独立した発泡セルから構成される発泡層と、該発泡層の両面に厚み200~500μmの非発泡スキン層が設けられたサンドイッチ構造を有し、該発泡層の樹脂連続相および該非発泡スキン層が、請求項1~5のいずれかに記載の発泡成形用ポリアミド樹脂組成物からなり、該非発泡スキン層側から測定した光沢度が80以上である発泡成形体。
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JP5263370B2 (ja) * | 2010-11-01 | 2013-08-14 | 東洋紡株式会社 | ポリアミド樹脂組成物およびポリアミド樹脂発泡成形体 |
JP5263371B2 (ja) * | 2010-11-01 | 2013-08-14 | 東洋紡株式会社 | ポリアミド樹脂発泡成形体および自動車用樹脂成形品 |
WO2013015111A1 (ja) * | 2011-07-25 | 2013-01-31 | 東レ株式会社 | 衝撃吸収部材用熱可塑性樹脂組成物およびその製造方法 |
JP6513464B2 (ja) * | 2014-05-23 | 2019-05-15 | ユニチカ株式会社 | ポリアミド樹脂組成物およびその成形体 |
RU2682581C1 (ru) * | 2016-03-11 | 2019-03-19 | Тойота Босоку Кабусики Кайся | Формованное изделие из вспененной смолы и способ его изготовления |
CN109423043A (zh) * | 2017-08-24 | 2019-03-05 | 尤尼吉可株式会社 | 发泡成型用聚酰胺树脂组合物、发泡用聚酰胺树脂颗粒混合物和发泡成型体 |
CN108047713A (zh) * | 2017-12-25 | 2018-05-18 | 江苏金发科技新材料有限公司 | 具有良好外观的聚酰胺组合物 |
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