JPWO2012117840A1 - 熱可塑性樹脂組成物およびその成形品 - Google Patents
熱可塑性樹脂組成物およびその成形品 Download PDFInfo
- Publication number
- JPWO2012117840A1 JPWO2012117840A1 JP2012508843A JP2012508843A JPWO2012117840A1 JP WO2012117840 A1 JPWO2012117840 A1 JP WO2012117840A1 JP 2012508843 A JP2012508843 A JP 2012508843A JP 2012508843 A JP2012508843 A JP 2012508843A JP WO2012117840 A1 JPWO2012117840 A1 JP WO2012117840A1
- Authority
- JP
- Japan
- Prior art keywords
- polyphenylene ether
- ether ketone
- thermoplastic resin
- cyclic polyphenylene
- acid
- 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.)
- Granted
Links
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 88
- 239000011342 resin composition Substances 0.000 title claims abstract description 72
- 229920001955 polyphenylene ether Polymers 0.000 claims abstract description 230
- 150000002576 ketones Chemical class 0.000 claims abstract description 217
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 189
- 229920005989 resin Polymers 0.000 claims abstract description 105
- 239000011347 resin Substances 0.000 claims abstract description 105
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 claims abstract description 6
- LUCCIOKYRSXZHQ-UHFFFAOYSA-N bicyclo[4.1.0]hepta-1,3,5-trien-7-one Chemical compound C1=CC=C2C(=O)C2=C1 LUCCIOKYRSXZHQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- -1 ether ketone Chemical class 0.000 claims description 198
- 239000000203 mixture Substances 0.000 claims description 95
- 238000002844 melting Methods 0.000 claims description 46
- 230000008018 melting Effects 0.000 claims description 46
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 38
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- 239000004645 polyester resin Substances 0.000 claims description 24
- 239000000945 filler Substances 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 22
- 229920001225 polyester resin Polymers 0.000 claims description 22
- 229920006122 polyamide resin Polymers 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000003365 glass fiber Substances 0.000 claims description 12
- 229920005668 polycarbonate resin Polymers 0.000 claims description 10
- 239000004431 polycarbonate resin Substances 0.000 claims description 10
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- 239000004917 carbon fiber Substances 0.000 claims description 9
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- 238000000465 moulding Methods 0.000 claims description 9
- 229920005990 polystyrene resin Polymers 0.000 claims description 3
- 239000000835 fiber Substances 0.000 abstract description 26
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- 238000010128 melt processing Methods 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 99
- 238000000034 method Methods 0.000 description 83
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 58
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000002798 polar solvent Substances 0.000 description 35
- 230000000694 effects Effects 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 33
- 229920001577 copolymer Polymers 0.000 description 28
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 27
- 239000002585 base Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 25
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 24
- 239000010408 film Substances 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 24
- 239000000047 product Substances 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229920001707 polybutylene terephthalate Polymers 0.000 description 20
- 239000007787 solid Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 238000012545 processing Methods 0.000 description 19
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- 239000002253 acid Substances 0.000 description 18
- 229920000139 polyethylene terephthalate Polymers 0.000 description 17
- 239000005020 polyethylene terephthalate Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- 238000011282 treatment Methods 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 14
- 150000001491 aromatic compounds Chemical class 0.000 description 14
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 13
- 239000011541 reaction mixture Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 12
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 229920002302 Nylon 6,6 Polymers 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 10
- 229920000412 polyarylene Polymers 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 10
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 9
- 230000018044 dehydration Effects 0.000 description 9
- 238000006297 dehydration reaction Methods 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- QQVIHTHCMHWDBS-UHFFFAOYSA-L isophthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC(C([O-])=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-L 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 239000000178 monomer Substances 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 238000010533 azeotropic distillation Methods 0.000 description 8
- 239000006227 byproduct Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 150000002009 diols Chemical class 0.000 description 8
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 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
- 229920000299 Nylon 12 Polymers 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000009477 glass transition Effects 0.000 description 7
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 230000000737 periodic effect Effects 0.000 description 7
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- PBLZLIFKVPJDCO-UHFFFAOYSA-N 12-aminododecanoic acid Chemical compound NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000005749 Copper compound Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 150000007513 acids Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 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 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001880 copper compounds Chemical class 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000005487 naphthalate group Chemical group 0.000 description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 description 6
- 235000011181 potassium carbonates Nutrition 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
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- 238000009835 boiling Methods 0.000 description 5
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- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 5
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- 239000000126 substance Substances 0.000 description 5
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- 235000011054 acetic acid Nutrition 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 239000007809 chemical reaction catalyst Substances 0.000 description 4
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- 239000008367 deionised water Substances 0.000 description 4
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- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 4
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
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- 238000002347 injection Methods 0.000 description 4
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- IGSBHTZEJMPDSZ-UHFFFAOYSA-N 4-[(4-amino-3-methylcyclohexyl)methyl]-2-methylcyclohexan-1-amine Chemical compound C1CC(N)C(C)CC1CC1CC(C)C(N)CC1 IGSBHTZEJMPDSZ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 206010052428 Wound Diseases 0.000 description 3
- 208000027418 Wounds and injury Diseases 0.000 description 3
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- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
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- 239000004065 semiconductor Substances 0.000 description 1
- 239000002453 shampoo Substances 0.000 description 1
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- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
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- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
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- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical group NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- LOAWHQCNQSFKDK-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC.CC[Sn](CC)CC LOAWHQCNQSFKDK-UHFFFAOYSA-N 0.000 description 1
- OLBXOAKEHMWSOV-UHFFFAOYSA-N triethyltin;hydrate Chemical compound O.CC[Sn](CC)CC OLBXOAKEHMWSOV-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 1
- DOOPOMANTWCTIB-UHFFFAOYSA-M tris(2-methylpropyl)stannanylium;acetate Chemical compound CC([O-])=O.CC(C)C[Sn+](CC(C)C)CC(C)C DOOPOMANTWCTIB-UHFFFAOYSA-M 0.000 description 1
- KLNPWTHGTVSSEU-UHFFFAOYSA-N undecane-1,11-diamine Chemical compound NCCCCCCCCCCCN KLNPWTHGTVSSEU-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000013904 zinc acetate Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
- 150000007934 α,β-unsaturated carboxylic acids Chemical class 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/02—Condensation polymers of aldehydes or ketones only
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
Description
(1)(A)熱可塑性樹脂100重量部に対し、(B)−Ph−CO−で表されるフェニレンケトンおよび−Ph−O−で表されるフェニレンエーテルを繰り返し構造単位に持つ下記一般式(I)で表される環状ポリフェニレンエーテルケトン0.5〜50重量部を配合してなる熱可塑性樹脂組成物、
(2)前記(B)環状ポリフェニレンエーテルケトンが、一般式(I)における繰り返し数m=2〜8の環状ポリフェニレンエーテルケトンの総重量を100%とした場合に、繰り返し数m=2および3のそれぞれの環状ポリフェニレンエーテルケトンをそれぞれ5重量%以上含む混合物であることを特徴とする上記(1)項に記載の熱可塑性樹脂組成物、
(3)前記(B)環状ポリフェニレンエーテルケトンが、少なくとも異なる3つ以上の繰り返し数mからなる環状ポリフェニレンエーテルケトン混合物であることを特徴とする上記(1)または(2)のいずれか1項に記載の熱可塑性樹脂組成物、
(4)前記(B)環状ポリフェニレンエーテルケトンが、下記一般式(II)で表される環状ポリフェニレンエーテルエーテルケトンであることを特徴とする上記(1)〜(3)のいずれか1項に記載の熱可塑性樹脂組成物、
(5)前記(B)環状ポリフェニレンエーテルケトンの融点が270℃以下であることを特徴とする上記(1)〜(4)のいずれか1項に記載の熱可塑性樹脂組成物、
(6)前記(B)環状ポリフェニレンエーテルケトンの融点が250℃以下であることを特徴とする上記(1)〜(5)のいずれか1項に記載の熱可塑性樹脂組成物、
(7)前記(A)熱可塑性樹脂がポリフェニレンエーテルエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂およびポリスチレン系樹脂から選ばれる少なくとも1種であることを特徴とする上記(1)〜(6)のいずれか1項に記載の熱可塑性樹脂組成物、
(8)さらに、(A)熱可塑性樹脂100重量部に対し(C)充填剤0.1〜200重量部を配合してなる上記(1)〜(7)のいずれか1項に記載の熱可塑性樹脂組成物、
(9)前記(C)充填剤が少なくとも繊維状充填剤を含むことを特徴とする上記(1)〜(8)のいずれか1項に記載の熱可塑性樹脂組成物、
(10)前記(C)充填剤がガラス繊維および/または炭素繊維であることを特徴とする上記(9)に記載の熱可塑性樹脂組成物、
(11)上記(1)〜(10)のいずれか1項に記載の樹脂組成物を溶融成形してなる成形品、を提供するものである。
本発明で用いられる熱可塑性樹脂(A)は、溶融成形可能な樹脂であればいずれでもよく、例えば、ポリアミド樹脂、ポリエステル樹脂、ポリアセタール樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ポリフェニレンエーテル樹脂を他の樹脂とブレンドまたはグラフト重合させて変性させた変性ポリフェニレンエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリフェニレンスルフィド樹脂、ポリエーテルスルホン樹脂、ポリケトン樹脂、ポリフェニレンエーテルケトン樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリエーテルイミド樹脂、熱可塑性ポリウレタン樹脂、高密度ポリエチレン樹脂、低密度ポリエチレン樹脂、直鎖状低密度ポリエチレン樹脂、ポリプロピレン樹脂、ポリメチルペンテン樹脂、環状オレフィン系樹脂、ポリ1−ブテン樹脂、ポリ1−ペンテン樹脂、ポリメチルペンテン樹脂、エチレン/α−オレフィン共重合体、(エチレンおよび/またはプロピレン)と(不飽和カルボン酸および/または不飽和カルボン酸エステル)との共重合体、(エチレンおよび/またはプロピレン)と(不飽和カルボン酸および/または不飽和カルボン酸エステル)との共重合体のカルボキシル基の少なくとも一部を金属塩化して得られるポリオレフィン、共役ジエンとビニル芳香族炭化水素のブロック共重合体、共役ジエンとビニル芳香族炭化水素のブロック共重合体の水素化物、ポリ塩化ビニル樹脂、ポリスチレン樹脂、ポリアクリル酸エステル樹脂、ポリメタクリル酸エステル樹脂などのアクリル樹脂、アクリロニトリルを主成分とするアクリロニトリル系共重合体、アクリロニトリル・ブタンジエン・スチレン(ABS)樹脂、アクリロニトリル・スチレン(AS)樹脂、酢酸セルロースなどのセルロース系樹脂、塩化ビニル/エチレン共重合体、塩化ビニル/酢酸ビニル共重合体、エチレン/酢酸ビニル共重合体、およびエチレン/酢酸ビニル共重合体のケン化物などが挙げられ、1種または2種以上併用してポリマーアロイとして用いてもよい。前記熱可塑性樹脂を不飽和カルボン酸、その酸無水物またはその誘導体から選ばれる少なくとも1種類の化合物で変性して用いることもできる。中でも、耐熱性、成形性および機械特性の点で、ポリフェニレンエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、ABS樹脂、ポリオレフィン樹脂が好ましく、特に好ましくはポリフェニレンエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂、ABS樹脂が好ましく用いられる。
η={(t/t0)−1}/C
(ここでのtはサンプル溶液の通過秒数、t0は溶媒(98重量%濃硫酸)の通過秒数、Cは溶液の濃度を表す。)。
(a)583℃で焼成、冷却した白金皿にポリフェニレンスルフィド樹脂5〜6gを秤量する。
(b)白金皿とともにポリフェニレンスルフィド樹脂を450〜500℃で予備焼成する。
(c)583℃にセットしたマッフル炉に白金皿とともに予備焼成したポリフェニレンスルフィド試料を入れ、完全に灰化するまで約6時間焼成する。
(d)デシケーター内で冷却後、秤量する。
(e)式:灰分量(重量%)=(灰分の重量(g)/試料重量(g))×100により灰分量を算出する。
本発明における環状ポリフェニレンエーテルケトンとは、少なくとも1つの式−Ph−CO−で表されるフェニレンケトン、および少なくとも1つの式−Ph−O−で表されるフェニレンエーテルを繰り返し構造単位に持つ、下記一般式(VI)で表される環状化合物である。
本発明の樹脂組成物は、(A)熱可塑性樹脂100重量部に対し、(B)−Ph−CO−で表されるフェニレンケトンおよび−Ph−O−で表されるフェニレンエーテルを繰り返し構造単位に持つ、前記一般式(VI)で表される環状ポリフェニレンエーテルケトン0.5〜50重量部を配合してなる熱可塑性樹脂組成物である。
本発明の熱可塑性樹脂組成物の製造方法は、特に限定されるものではないが、原料の混合物を単軸あるいは二軸の押出機、バンバリーミキサー、ニーダー、ミキシングロールなど通常公知の溶融混合機に供給して200〜400℃の温度で混練する方法などを例として挙げることができる。また、原料の混合順序にも特に制限はなく、熱可塑性樹脂(A)、環状ポリフェニレンエーテルケトン(B)および必要に応じて充填剤およびその他の添加剤等を予めブレンドした後、熱可塑性樹脂と環状ポリフェニレンエーテルケトン(B)の融点以上において、単軸または二軸押出機で均一に溶融混練する方法、溶液中で混合した後に溶媒を除く方法などが用いられる。中でも生産性の点で、単軸または二軸押出機で均一に溶融混練する方法が好ましく、特に二軸押出機を用いて熱可塑性樹脂の融点以上であって、さらに環状ポリフェニレンエーテルケトン(B)の融点以上の温度において均一に溶融混練する方法が好ましく用いられる。
本発明の樹脂組成物は、通常公知の射出成形、押出成形、ブロー成形、プレス成形、紡糸などの任意の方法で成形することができ、各種成形品に加工し利用することができる。成形品としては、射出成形品、押出成形品、ブロー成形品、フィルム、シート、繊維などとして利用できる。フィルムの製造方法としては、公知の溶融製膜方法を採用することができ、例えば、単軸または2軸の押出機中で樹脂組成物を溶融後、フィルムダイより押出し、冷却ドラム上で冷却して未延伸フィルムを作成する方法、あるいは、このようにして作成したフィルムをローラー式の縦延伸装置とテンターと呼ばれる横延伸装置にて適宜縦横に延伸する一軸延伸法、二軸延伸法などが例示できるが、特にこれに限定されるものではない。
本発明において、上記各種成形品は、自動車部品、電気・電子部品、建築部材、各種容器、日用品、生活雑貨および衛生用品など各種用途に利用することができる。具体的な用途としては、エアフローメーター、エアポンプ、サーモスタットハウジング、エンジンマウント、イグニッションホビン、イグニッションケース、クラッチボビン、センサーハウジング、アイドルスピードコントロールバルブ、バキュームスイッチングバルブ、ECUハウジング、バキュームポンプケース、インヒビタースイッチ、回転センサー、加速度センサー、ディストリビューターキャップ、コイルベース、ABS用アクチュエーターケース、ラジエータタンクのトップ及びボトム、クーリングファン、ファンシュラウド、エンジンカバー、シリンダーヘッドカバー、オイルキャップ、オイルパン、オイルフィルター、フューエルキャップ、フューエルストレーナー、ディストリビューターキャップ、ベーパーキャニスターハウジング、エアクリーナーハウジング、タイミングベルトカバー、ブレーキブースター部品、各種ケース、各種チューブ、各種タンク、各種ホース、各種クリップ、各種バルブ、各種パイプなどの自動車用アンダーフード部品、トルクコントロールレバー、安全ベルト部品、レジスターブレード、ウオッシャーレバー、ウインドレギュレーターハンドル、ウインドレギュレーターハンドルのノブ、パッシングライトレバー、サンバイザーブラケット、各種モーターハウジングなどの自動車用内装部品、ルーフレール、フェンダー、ガーニッシュ、バンパー、ドアミラーステー、スポイラー、フードルーバー、ホイールカバー、ホイールキャップ、グリルエプロンカバーフレーム、ランプリフレクター、ランプベゼル、ドアハンドルなどの自動車用外装部品、ワイヤーハーネスコネクター、SMJコネクター、PCBコネクター、ドアグロメットコネクターなど各種自動車用コネクター、リレーケース、コイルボビン、光ピックアップシャーシ、モーターケース、ノートパソコンハウジングおよび内部部品、CRTディスプレーハウジングおよび内部部品、プリンターハウジングおよび内部部品、携帯電話、モバイルパソコン、ハンドヘルド型モバイルなどの携帯端末ハウジングおよび内部部品、記録媒体(CD、DVD、PD、FDDなど)ドライブのハウジングおよび内部部品、コピー機のハウジングおよび内部部品、ファクシミリのハウジングおよび内部部品、パラボラアンテナなどに代表される電気・電子部品を挙げることができる。更に、VTR部品、テレビ部品、アイロン、ヘアードライヤー、炊飯器部品、電子レンジ部品、音響部品、ビデオカメラ、プロジェクターなどの映像機器部品、レーザーディスク(登録商標)、コンパクトディスク(CD)、CD−ROM、CD−R、CD−RW、DVD−ROM、DVD−R、DVD−RW、DVD−RAM、ブルーレイディスクなどの光記録媒体の基板、照明部品、冷蔵庫部品、エアコン部品、タイプライター部品、ワードプロセッサー部品、などに代表される家庭・事務電気製品部品を挙げることができる。また電子楽器、家庭用ゲーム機、携帯型ゲーム機などのハウジングや内部部品、各種ギヤー、各種ケース、センサー、LEPランプ、コネクター、ソケット、抵抗器、リレーケース、スイッチ、コイルボビン、コンデンサー、バリコンケース、光ピックアップ、発振子、各種端子板、変成器、プラグ、プリント配線板、チューナー、スピーカー、マイクロフォン、ヘッドホン、小型モーター、磁気ヘッドベース、パワーモジュール、半導体、液晶、FDDキャリッジ、FDDシャーシ、モーターブラッシュホルダー、トランス部材、コイルボビンなどの電気・電子部品、サッシ戸車、ブラインドカーテンパーツ、配管ジョイント、カーテンライナー、ブラインド部品、ガスメーター部品、水道メーター部品、湯沸かし器部品、ルーフパネル、断熱壁、アジャスター、プラ束、天井釣り具、階段、ドアー、床などの建築部材、釣り糸、漁網、海藻養殖網、釣り餌袋などの水産関連部材、植生ネット、植生マット、防草袋、防草ネット、養生シート、法面保護シート、飛灰押さえシート、ドレーンシート、保水シート、汚泥・ヘドロ脱水袋、コンクリート型枠などの土木関連部材、歯車、ねじ、バネ、軸受、レバー、キーステム、カム、ラチェット、ローラー、給水部品、玩具部品、ファン、テグス、パイプ、洗浄用治具、モーター部品、顕微鏡、双眼鏡、カメラ、時計などの機械部品、マルチフィルム、トンネル用フィルム、防鳥シート、植生保護用不織布、育苗用ポット、植生杭、種紐テープ、発芽シート、ハウス内張シート、農ビの止め具、緩効性肥料、防根シート、園芸ネット、防虫ネット、幼齢木ネット、プリントラミネート、肥料袋、試料袋、土嚢、獣害防止ネット、誘因紐、防風網などの農業部材、紙おむつ、生理用品包材、綿棒、おしぼり、便座ふきなどの衛生用品、医療用不織布(縫合部補強材、癒着防止膜、人工器官補修材)、創傷被服材、キズテープ包帯、貼符材基布、手術用縫合糸、骨折補強材、医療用フィルムなどの医療用品、カレンダー、文具、衣料、食品等の包装用フィルム、トレイ、ブリスター、ナイフ、フォーク、スプーン、チューブ、プラスチック缶、パウチ、コンテナー、タンク、カゴなどの容器・食器類、ホットフィル容器類、電子レンジ調理用容器類化粧品容器、ラップ、発泡緩衝剤、紙ラミ、シャンプーボトル、飲料用ボトル、カップ、キャンディ包装、シュリンクラベル、蓋材料、窓付き封筒、果物かご、手切れテープ、イージーピール包装、卵パック、HDD用包装、コンポスト袋、記録メディア包装、ショッピングバック、電気・電子部品等のラッピングフィルムなどの容器・包装、天然繊維複合、ポロシャツ、Tシャツ、インナー、ユニホーム、セーター、靴下、ネクタイなどの各種衣料、カーテン、イス貼り地、カーペット、テーブルクロス、布団地、壁紙、ふろしきなどのインテリア用品、キャリアーテープ、プリントラミ、感熱孔版印刷用フィルム、離型フィルム、多孔性フィルム、コンテナバッグ、クレジットカード、キャッシュカード、IDカード、ICカード、紙、皮革、不織布等のホットメルトバインダー、磁性体、硫化亜鉛、電極材料等粉体のバインダー、光学素子、導電性エンボステープ、ICトレイ、ゴルフティー、ゴミ袋、レジ袋、各種ネット、歯ブラシ、文房具、水切りネット、ボディタオル、ハンドタオル、お茶パック、排水溝フィルター、クリアファイル、コート剤、接着剤、カバン、イス、テーブル、クーラーボックス、クマデ、ホースリール、プランター、ホースノズル、食卓、机の表面、家具パネル、台所キャビネット、ペンキャップ、ガスライターなどとして有用であり、ワイヤーハーネスコネクター、SMJコネクター、PCBコネクター、ドアグロメットコネクターなど各種自動車用コネクターとして特に有用である。
また、本発明の熱可塑性樹脂組成物およびそれからなる成形品はリサイクルすることが可能である。例えば、樹脂組成物およびそれからなる成形品を粉砕し、好ましくは粉末状とした後、必要に応じて添加剤を配合して得られる樹脂組成物は、本発明の樹脂組成物と同じように使用でき、成形品とすることも可能である。
撹拌装置を備えたオートクレーブ装置に、4,4’−ジフルオロベンゾフェノン1.1kg(5mol)、ヒドロキノン0.55kg(5mol)、無水炭酸カリウム0.69kg(5mol)、N−メチル−2−ピロリドン50Lを仕込んだ。混合物中のベンゼン環成分1.0モルに対するN−メチル−2−ピロリドンの量は3.33リットルである。反応器内を窒素置換した後、145℃まで昇温し、145℃で1時間保持、その後185℃にまで昇温し185℃で3時間保持、さらに250℃にまで昇温し250℃で2時間保持して反応を行った。反応終了後、室温にまで冷却して反応混合物を調製した。
攪拌機、窒素吹き込み管、ディーン・スターク装置、冷却管、温度計を具備した4つ口フラスコに4,4’−ジフルオロベンゾフェノン22.5g(103mmol)、ヒドロキノン11.0g(100mmol)、およびジフェニルスルホン49gを仕込んだ。混合物中のベンゼン環成分1.0モルに対するジフェニルスルホンの量は約0.16リットルである。窒素を通じながら140℃にまで昇温したところ、ほぼ無色の溶液を形成した。この温度で無水炭酸ナトリウム10.6g(100mmol)及び無水炭酸カリウム0.28g(2mmol)を加えた。温度を200℃に上げて1時間保持し、250℃に上げて1時間保持し、次いで315℃に上げて2時間保持した。
装置 :島津株式会社製 LC−10Avpシリーズ
カラム :Mightysil RP−18GP150−4.6
検出器 :フォトダイオードアレイ検出器(UV=270nmを使用)
流速 :1.0mL/min
カラム温度 :40℃
サンプル :0.1重量%THF溶液
移動相 :THF/0.1w%トリフルオロ酢酸水溶液。
粘度計 :オストワルド型粘度計
溶媒 :98重量%硫酸
サンプル濃度 :0.1g/dL(サンプル重量/溶媒容量)
測定温度 :25℃
還元粘度計算式 :η={(t/t0)−1}/C
t :サンプル溶液の通過秒数
t0 :溶媒の通過秒数
C :溶液の濃度。
ポリフェニレンエーテルケトンの融点は、セイコー電子工業製ロボットDSC RDC220を用い、窒素雰囲気下、下記測定条件で測定を行った。
・50℃×1分 ホールド
・50℃から360℃へ昇温,昇温速度20℃/分
各成分を表2〜4に記載の各割合でドライブレンドした後、押出機メインフィーダーより供給し、日本製鋼所社製TEX30型2軸押出機で、表に記載のシリンダー設定温度に設定して、スクリュー回転数200rpmで溶融混練を行い、ダイから吐出されるガットは即座に水浴にて冷却し、ストランドカッターによりペレット化した。実施例7、8、12、16、17および比較例6〜9、16、17、21、22で得られたペレットは、80℃で12時間真空乾燥し、それら以外のペレットは120℃で5時間熱風乾燥した後、下記の評価を行った。
熱可塑性樹脂成分および参考例1または2のポリフェニレンエーテルケトンを表5に記載の各割合でドライブレンドした後、押出機メインフィーダーより供給し、充填剤を押出機サイドフィーダーより供給し、日本製鋼所社製TEX30型2軸押出機で、表に記載のシリンダー設定温度に設定して、スクリュー回転数200rpmで溶融混練を行い、ダイから吐出されるガットは即座に水浴にて冷却し、ストランドカッターによりペレット化した。実施例22、23および比較例28、29で得られたペレットは、80℃で12時間真空乾燥し、それら以外のペレットは120℃で5時間熱風乾燥した後、下記の評価を行った。
B−1:参考例1
B−2:参考例2
A−1:Tm=338℃、Tc=287℃(Tm−Tc=51℃)、Tg=143℃のポリフェニレンエーテルエーテルケトン樹脂(ビクトレックス製450G)
A−2:Tm=278℃、Tc=215℃(Tm−Tc=63℃)、Tg=88℃、MFR=200g/10分(315.5℃、5kg荷重)のポリフェニレンスルフィド樹脂(東レ製M2588)
A−3:Tm=225℃、Tc=177℃(Tm−Tc=48℃)、Tg=58℃、98%硫酸中濃度1g/dlでの相対粘度2.80のナイロン6樹脂(東レ製CM1010)
A−4:Tm=265℃、Tc=227℃(Tm−Tc=38℃)、Tg=63℃、98%硫酸1中濃度g/dlでの相対粘度2.95のナイロン66樹脂(東レ製CM3001N)
A−5:Tm=255℃、Tc=178℃(Tm−Tc=77℃)、Tg=81℃、固有粘度1.15のポリエチレンテレフタレート樹脂(東レ製T704T)
A−6:Tm=226℃、Tc=188℃(Tm−Tc=38℃)、Tg=25℃、固有粘度0.85のポリブチレンテレフタレート樹脂(東レ製1100S)
A−7:ガラス転移温度152℃、全光線透過率89%のポリカーボネート樹脂(出光興産製A2500)
A−8:ガラス転移温度103℃、全光線透過率87%の透明ABS樹脂(東レ製920)(透明ABS樹脂は、ゴム質重合体とスチレン系共重合体からなる樹脂であるため複数のガラス転移温度を有するが、マトリックスであるスチレン系共重合体のガラス転移温度103℃により透明ABS樹脂の溶融加工温度を決定した)。
C−1:ガラス繊維(日本電気硝子製ECS03T−790DE)
C−2:ガラス繊維(日本電気硝子製T−249)
C−3:ガラス繊維(日本電気硝子製T−289)
C−4:ガラス繊維(日東紡績製CS3J948)
C−5:ガラス繊維(日本電気硝子製T−747)
C−6:炭素繊維(東レ製TS12−006)
流動性を評価するため、キャピラリー型溶融粘度測定装置(東洋精機社製CAPIROGRAPH−1C)を用いて、以下の条件で、剪断速度100sec−1の条件下、ペレットをシリンダー部に投入後、5分間溶融させた後に測定した溶融粘度(Pa・s)を流動性評価項目とした。
・ポリフェニレンエーテルエーテルケトン樹脂:シリンダー温度400℃、オリフィスL/D=20mm(内径1mm)
・ポリフェニレンスルフィド樹脂:シリンダー温度300℃、オリフィスL/D=20mm(内径1mm)
・ナイロン6樹脂:シリンダー温度250℃、オリフィスL/D=10mm(内径1mm)
・ナイロン6,6樹脂:シリンダー温度290℃、オリフィスL/D=10mm(内径1mm)
・ポリブチレンテレフタレート樹脂:シリンダー温度250℃、オリフィスL/D=20mm(内径1mm)
・ポリエチレンテレフタレート樹脂:シリンダー温度280℃、オリフィスL/D=20mm(内径1mm)
・ポリカーボネート樹脂:シリンダー温度300℃、オリフィスL/D=10mm(内径1mm)
・ABS樹脂:シリンダー温度220℃、オリフィスL/D=10mm(内径0.5mm)。
TAインスツルメント社製Q200型示差走査熱量測定(DSC)装置を用いて熱的特性を測定した。下記測定条件を用い、降温結晶化温度(Tc)およびガラス転移温度(Tg)は1st Runの値を、融点(Tm)は2nd Runの値を用いた。Tm−Tcの値を結晶化特性を示す指標とし、この値が小さいほど結晶化速度が速い。
First Run
・50℃×1分 ホールド
・50℃から融点+20℃へ昇温,昇温速度20℃/分
・融点+20℃×1分 ホールド
・融点+20℃からガラス転移温度+20℃へ降温,降温速度20℃/分(この時の結晶化ピーク温度をTcとする)
Second Run
・ガラス転移温度+20℃×1分 ホールド
・ガラス転移温度+20℃から融点+20℃へ昇温,昇温速度20℃/分(この時の融解ピーク温度をTmとする)。
得られた熱可塑性樹脂を熱可塑性樹脂のガラス転移温度+100℃〜200℃のシリンダー設定温度、金型設定温度40℃で住友重機社製SG75H−MIVを用いて射出成形し、得られた70mm×70mm×2mmの成形品を東洋精機(株)製直読ヘイズメーターを用いて、23℃の温度条件で全光線透過率を測定した。透過率が大きいほど透明性に優れることを示している。
ASTM D−638に準じて、試験機テンシロンUTA−2.5T(オリエンテック製)により、ASTM1号ダンベル試験片を室温23℃、湿度50%の恒温室内にて、試料評点間距離114mm、歪み速度10mm/minで引張試験を行った。なお、ダンベル試験片は射出成形(住友重機社製SG75H−MIV)により調製した。
Claims (11)
- 前記(B)環状ポリフェニレンエーテルケトンが、一般式(I)における繰り返し数m=2〜8の環状ポリフェニレンエーテルケトンの総重量を100%とした場合に、繰り返し数m=2および3のそれぞれの環状ポリフェニレンエーテルケトンをそれぞれ5重量%以上含む混合物であることを特徴とする請求項1に記載の熱可塑性樹脂組成物。
- 前記(B)環状ポリフェニレンエーテルケトンが、少なくとも異なる3つ以上の繰り返し数mからなる環状ポリフェニレンエーテルケトン混合物であることを特徴とする請求項1または2のいずれか1項に記載の熱可塑性樹脂組成物。
- 前記(B)環状ポリフェニレンエーテルケトンの融点が270℃以下であることを特徴とする請求項1〜4のいずれか1項に記載の熱可塑性樹脂組成物。
- 前記(B)環状ポリフェニレンエーテルケトンの融点が250℃以下であることを特徴とする請求項1〜5のいずれか1項に記載の熱可塑性樹脂組成物。
- 前記(A)熱可塑性樹脂がポリフェニレンエーテルエーテルケトン樹脂、ポリフェニレンスルフィド樹脂、ポリアミド樹脂、ポリエステル樹脂、ポリカーボネート樹脂およびポリスチレン系樹脂から選ばれる少なくとも1種であることを特徴とする請求項1〜6のいずれか1項に記載の熱可塑性樹脂組成物。
- さらに、(A)熱可塑性樹脂100重量部に対し(C)充填剤0.1〜200重量部を配合してなる請求項1〜7のいずれか1項に記載の熱可塑性樹脂組成物。
- 前記(C)充填剤が少なくとも繊維状充填剤を含むことを特徴とする請求項1〜8のいずれか1項に記載の熱可塑性樹脂組成物。
- 前記(C)充填剤がガラス繊維および/または炭素繊維であることを特徴とする請求項9に記載の熱可塑性樹脂組成物。
- 請求項1〜10のいずれか1項に記載の樹脂組成物を溶融成形してなる成形品。
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CN105820453B (zh) * | 2016-03-31 | 2019-05-17 | 广东帝通新材料股份有限公司 | 透明抗静电电子载带片材及制备方法 |
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CN109354858A (zh) * | 2018-10-13 | 2019-02-19 | 孙浩 | 一种玻璃幕墙材料及其制备方法 |
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EP2682255B1 (en) | 2015-12-16 |
TW201241087A (en) | 2012-10-16 |
JP5077500B2 (ja) | 2012-11-21 |
CN103403098B (zh) | 2014-11-12 |
EP2682255A1 (en) | 2014-01-08 |
KR20130102657A (ko) | 2013-09-17 |
US20130331500A1 (en) | 2013-12-12 |
TWI447171B (zh) | 2014-08-01 |
CN103403098A (zh) | 2013-11-20 |
KR101340406B1 (ko) | 2013-12-11 |
AU2012224318B2 (en) | 2015-12-03 |
WO2012117840A1 (ja) | 2012-09-07 |
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AU2012224318A1 (en) | 2013-09-12 |
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