JP5713807B2 - Thermoplastic resin composition and molded body - Google Patents
Thermoplastic resin composition and molded body Download PDFInfo
- Publication number
- JP5713807B2 JP5713807B2 JP2011129001A JP2011129001A JP5713807B2 JP 5713807 B2 JP5713807 B2 JP 5713807B2 JP 2011129001 A JP2011129001 A JP 2011129001A JP 2011129001 A JP2011129001 A JP 2011129001A JP 5713807 B2 JP5713807 B2 JP 5713807B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- metal salt
- resin composition
- thermoplastic resin
- mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 35
- 239000011342 resin composition Substances 0.000 title claims description 31
- -1 aliphatic monocarboxylic acid Chemical class 0.000 claims description 55
- 150000003839 salts Chemical class 0.000 claims description 36
- 229910052751 metal Inorganic materials 0.000 claims description 35
- 239000002184 metal Substances 0.000 claims description 35
- 150000002148 esters Chemical class 0.000 claims description 30
- 125000001931 aliphatic group Chemical group 0.000 claims description 29
- 239000002253 acid Substances 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 238000000465 moulding Methods 0.000 claims description 25
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 22
- 229920006122 polyamide resin Polymers 0.000 claims description 21
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- 159000000000 sodium salts Chemical group 0.000 claims description 6
- 159000000007 calcium salts Chemical class 0.000 claims description 5
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000000835 fiber Substances 0.000 description 11
- 239000011256 inorganic filler Substances 0.000 description 11
- 229910003475 inorganic filler Inorganic materials 0.000 description 11
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 8
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 229920002302 Nylon 6,6 Polymers 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000000454 talc Substances 0.000 description 5
- 229910052623 talc Inorganic materials 0.000 description 5
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- QCNWZROVPSVEJA-UHFFFAOYSA-N Heptadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCC(O)=O QCNWZROVPSVEJA-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- QXGVRGZJILVMDF-UHFFFAOYSA-N Tetracosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCC(O)=O QXGVRGZJILVMDF-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- NOPFSRXAKWQILS-UHFFFAOYSA-N docosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCO NOPFSRXAKWQILS-UHFFFAOYSA-N 0.000 description 4
- DGXRZJSPDXZJFG-UHFFFAOYSA-N docosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCC(O)=O DGXRZJSPDXZJFG-UHFFFAOYSA-N 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- CBFCDTFDPHXCNY-UHFFFAOYSA-N icosane Chemical compound CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 4
- JJOJFIHJIRWASH-UHFFFAOYSA-N icosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCC(O)=O JJOJFIHJIRWASH-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 4
- BNJOQKFENDDGSC-UHFFFAOYSA-N octadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCC(O)=O BNJOQKFENDDGSC-UHFFFAOYSA-N 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- BEOUGZFCUMNGOU-UHFFFAOYSA-N tuberculostearic acid Chemical compound CCCCCCCCC(C)CCCCCCCCC(O)=O BEOUGZFCUMNGOU-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- QQHJDPROMQRDLA-UHFFFAOYSA-N hexadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCC(O)=O QQHJDPROMQRDLA-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 2
- QIKKFTUQKYGBLZ-UHFFFAOYSA-N 1,1,3,3,3-pentafluoropropane-1,2,2-triol Chemical compound OC(F)(F)C(O)(O)C(F)(F)F QIKKFTUQKYGBLZ-UHFFFAOYSA-N 0.000 description 2
- WMYINDVYGQKYMI-UHFFFAOYSA-N 2-[2,2-bis(hydroxymethyl)butoxymethyl]-2-ethylpropane-1,3-diol Chemical compound CCC(CO)(CO)COCC(CC)(CO)CO WMYINDVYGQKYMI-UHFFFAOYSA-N 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
- 235000021357 Behenic acid Nutrition 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 235000021353 Lignoceric acid Nutrition 0.000 description 2
- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- IFAWYXIHOVRGHQ-UHFFFAOYSA-N Nonadecandioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCC(O)=O IFAWYXIHOVRGHQ-UHFFFAOYSA-N 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- BTZVDPWKGXMQFW-UHFFFAOYSA-N Pentadecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCC(O)=O BTZVDPWKGXMQFW-UHFFFAOYSA-N 0.000 description 2
- 229920006121 Polyxylylene adipamide Polymers 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 150000004984 aromatic diamines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 159000000009 barium salts Chemical class 0.000 description 2
- 229940116226 behenic acid Drugs 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 229960000735 docosanol Drugs 0.000 description 2
- TVIDDXQYHWJXFK-UHFFFAOYSA-N dodecanedioic acid Chemical compound OC(=O)CCCCCCCCCCC(O)=O TVIDDXQYHWJXFK-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- FARYTWBWLZAXNK-WAYWQWQTSA-N ethyl (z)-3-(methylamino)but-2-enoate Chemical compound CCOC(=O)\C=C(\C)NC FARYTWBWLZAXNK-WAYWQWQTSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HMSWAIKSFDFLKN-UHFFFAOYSA-N hexacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC HMSWAIKSFDFLKN-UHFFFAOYSA-N 0.000 description 2
- JJWZFUFNJNGKAF-UHFFFAOYSA-N hexacosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCC(O)=O JJWZFUFNJNGKAF-UHFFFAOYSA-N 0.000 description 2
- 229920005669 high impact polystyrene Polymers 0.000 description 2
- 239000004797 high-impact polystyrene Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000006082 mold release agent Substances 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- ZYURHZPYMFLWSH-UHFFFAOYSA-N octacosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC ZYURHZPYMFLWSH-UHFFFAOYSA-N 0.000 description 2
- WHTKRYWWSTYDNH-UHFFFAOYSA-N octacosanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O WHTKRYWWSTYDNH-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 229920005672 polyolefin resin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- HQHCYKULIHKCEB-UHFFFAOYSA-N tetradecanedioic acid Chemical compound OC(=O)CCCCCCCCCCCCC(O)=O HQHCYKULIHKCEB-UHFFFAOYSA-N 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N triacontane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- LWBHHRRTOZQPDM-UHFFFAOYSA-N undecanedioic acid Chemical compound OC(=O)CCCCCCCCCC(O)=O LWBHHRRTOZQPDM-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052882 wollastonite Inorganic materials 0.000 description 2
- 239000010456 wollastonite Substances 0.000 description 2
- GWHCXVQVJPWHRF-KTKRTIGZSA-N (15Z)-tetracosenoic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCCCC(O)=O GWHCXVQVJPWHRF-KTKRTIGZSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- QFGCFKJIPBRJGM-UHFFFAOYSA-N 12-[(2-methylpropan-2-yl)oxy]-12-oxododecanoic acid Chemical compound CC(C)(C)OC(=O)CCCCCCCCCCC(O)=O QFGCFKJIPBRJGM-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 description 1
- LWWFHQGUVMZXML-UHFFFAOYSA-L C(CCCCCCCCC(=O)[O-])CCCCCCCC(=O)[O-].[Ca+2] Chemical compound C(CCCCCCCCC(=O)[O-])CCCCCCCC(=O)[O-].[Ca+2] LWWFHQGUVMZXML-UHFFFAOYSA-L 0.000 description 1
- SWOLIUXDPQKTFN-UHFFFAOYSA-L C(CCCCCCCCC(=O)[O-])CCCCCCCCC(=O)[O-].[Ca+2] Chemical compound C(CCCCCCCCC(=O)[O-])CCCCCCCCC(=O)[O-].[Ca+2] SWOLIUXDPQKTFN-UHFFFAOYSA-L 0.000 description 1
- KCSXVTDVHQQZGH-UHFFFAOYSA-N C(CCCCCCCCCCC)CCCCCCCCCCCCCCCC.[Na] Chemical compound C(CCCCCCCCCCC)CCCCCCCCCCCCCCCC.[Na] KCSXVTDVHQQZGH-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004713 Cyclic olefin copolymer Substances 0.000 description 1
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical class [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 1
- 101000576320 Homo sapiens Max-binding protein MNT Proteins 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- XJXROGWVRIJYMO-SJDLZYGOSA-N Nervonic acid Natural products O=C(O)[C@@H](/C=C/CCCCCCCC)CCCCCCCCCCCC XJXROGWVRIJYMO-SJDLZYGOSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
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- 239000005642 Oleic acid Substances 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- 239000007788 liquid Substances 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- LFRNUEDQVSUMGB-UHFFFAOYSA-N octadeca-2,4,6-trienedioic acid Chemical compound OC(=O)CCCCCCCCCCC=CC=CC=CC(O)=O LFRNUEDQVSUMGB-UHFFFAOYSA-N 0.000 description 1
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- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、熱可塑性樹脂組成物および成形体に関し、詳しくは、離型性に優れ、成形時に発生するガス量が少なく、成形体の外観性状に優れる熱可塑性樹脂組成物およびそれを用いた成形体に関する。 TECHNICAL FIELD The present invention relates to a thermoplastic resin composition and a molded body, and more specifically, a thermoplastic resin composition having excellent release properties, a small amount of gas generated during molding, and excellent appearance characteristics of the molded body, and molding using the same. About the body.
熱可塑性樹脂は、機械的性質、電気的性質、軽量性、成形加工性等の優れた特性により、電気・電子機器、OA機器、車輌用部品、建築用部材、農業用資材、雑貨等の広範な分野で使用されている。熱可塑性樹脂は、生産性の高い溶融成形加工(押出成形や射出成形等)に適用でき、各種の成形体に成形され、利用されている。 Thermoplastic resins have a wide range of electrical and electronic equipment, OA equipment, vehicle parts, building materials, agricultural materials, miscellaneous goods, etc. due to excellent properties such as mechanical properties, electrical properties, light weight, and moldability. Used in various fields. Thermoplastic resins can be applied to highly productive melt molding processes (extrusion molding, injection molding, etc.), and are molded into various molded bodies and used.
そして、近年、OA機器、電気・電子機器等の形状の多様化や複雑化、精密化及び高度化に伴い、それらの部品やハウジング(筐体)等においては、形状が高度に複雑化しており、成形体を金型から脱型することが困難となる場合があり、さらに、脱型ができず、成形体に穴があいたり、脱型できても、成形体に変形を生じたり、白化や歪みが残留して、成形体の寸法精度、強度、外観が低下する等の問題がある。
また、成形時における成形体の離型性の良し悪しが、成形体の生産性に大きな影響を及ぼすこととなり、離型性向上の要求は非常に高いものがある。
In recent years, with the diversification, complexity, precision and sophistication of the shapes of OA equipment, electrical / electronic equipment, etc., the shapes of these parts and housings (housings) have become highly complex. In some cases, it may be difficult to remove the molded body from the mold. In addition, the molded body cannot be removed, and even if the molded body is perforated or removed, the molded body may be deformed or whitened. There is a problem that the dimensional accuracy, strength, and appearance of the molded body are deteriorated due to residual or distortion.
In addition, the quality of the mold release during molding has a great influence on the productivity of the molded article, and there is a very high demand for mold release improvement.
熱可塑性樹脂の成形時の離型性を改善するためには、離型剤(滑剤)を配合するのが一般的であり、従来より、脂肪族カルボン酸の金属塩等の各種の離型剤が知られている。しかしながら、従来の通常のモノカルボン酸塩で十分な離型性を発揮させようとすると、発生ガス量が多くなり、また、押出の際にはストランドの安定性に悪影響を及ぼし、また、成形体の外観が悪化するという問題がある。 In order to improve the mold releasability at the time of molding a thermoplastic resin, it is common to add a mold release agent (lubricant). Conventionally, various mold release agents such as metal salts of aliphatic carboxylic acids. It has been known. However, if the conventional ordinary monocarboxylic acid salt exhibits sufficient releasability, the amount of gas generated increases, and the extrusion stability adversely affects the strand stability. There is a problem that the appearance of deteriorates.
特許文献1には、ポリアミド樹脂に、炭素数10〜20の脂肪族カルボン酸の塩および炭素数22以上の脂肪族カルボン酸またはその誘導体(具体的には2価のアルコールとのエステル)を配合することが提案されているが、複雑な形状の成形体においては充分でないことがあり、成形体形状設計の制約や冷却時間を長くする等の成形条件での対応が必要となる場合があり、また、離型性と発生ガスの両方を十分満足できるとはいい難い。
このように、特に複雑な射出成形体においても、外観不良、剥離不良、物性低下等の問題を引き起こさず、少量添加で、離型性とガス発生の両方をバランスよく満足し、良好な外観性状の成形体を提供できるものは、未だ提案されていないというのが現状である。
Patent Document 1 includes a polyamide resin containing a salt of an aliphatic carboxylic acid having 10 to 20 carbon atoms and an aliphatic carboxylic acid having 22 or more carbon atoms or a derivative thereof (specifically, an ester with a divalent alcohol). However, it may not be sufficient for a molded product with a complicated shape, and it may be necessary to deal with molding conditions such as restrictions on the shape design of the molded product and increasing the cooling time. Moreover, it is difficult to say that both the releasability and the generated gas can be sufficiently satisfied.
In this way, even in complex injection molded products, it does not cause problems such as poor appearance, poor peeling, and poor physical properties, and with a small amount of addition, it satisfies both the mold release property and gas generation in a well-balanced manner, and has good appearance properties. The present condition is that the thing which can provide the molded object of has not been proposed yet.
本発明の目的は、上記従来技術の問題点に鑑み、少量添加で、離型性とガス発生の両方をバランスよく満足し、良好な外観性状の成形体を提供できる熱可塑性樹脂組成物およびそれを用いた成形体を提供することにある。 An object of the present invention is to provide a thermoplastic resin composition that can provide a molded article having a good appearance property that satisfies both the releasability and gas generation in a balanced manner by adding a small amount in view of the above-mentioned problems of the prior art. An object of the present invention is to provide a molded body using the above.
本発明者らは、上記課題を達成すべく、鋭意検討を重ねた結果、特定の脂肪族モノカルボン酸金属塩(又はエステル)に特定の脂肪族ジカルボン酸金属塩(又はエステル)を組み合わせて使用することにより、少量添加で、離型性とガス発生の両方をバランスよく満足し、良好な外観性状の成形体を提供できる熱可塑性樹脂組成物を提供できることができることを見出し、本発明を完成させるに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have used a specific aliphatic dicarboxylic acid metal salt (or ester) in combination with a specific aliphatic dicarboxylic acid metal salt (or ester). Thus, it is found that a thermoplastic resin composition capable of providing a molded article having a good appearance property can be provided by adding a small amount and satisfying both a releasability and gas generation in a well-balanced manner, thereby completing the present invention. It came to.
すなわち、本発明によれば、ポリアミド樹脂100質量部に対し、(A)炭素数が12以上の脂肪族モノカルボン酸の金属塩又はエステル、及び(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩又はエステルを(A)と(B)の合計で0.1〜5質量部含有することを特徴とする熱可塑性樹脂組成物が提供される。 That is, according to the present invention, with respect to 100 parts by mass of the polyamide resin , (A) a metal salt or ester of an aliphatic monocarboxylic acid having 12 or more carbon atoms, and (B) an aliphatic dicarboxylic acid having 12 or more carbon atoms. A thermoplastic resin composition comprising 0.1 to 5 parts by mass of the total of (A) and (B) is provided.
本発明の熱可塑性樹脂組成物は、離型性とガス発生の低減の両方をバランスよく満足することができる。モノカルボン酸金属塩(エステル)のみでは離型性が不十分であるが、ジカルボン酸金属塩(エステル)と併用することで、発生ガス量と離型性のバランスが良好となり、またジカルボン酸金属塩は沸点が高く、遊離しにくいので揮発しにくく、また添加しやすくなるので、可塑化効果を享受しやすいという効果も有する。
そして本発明の熱可塑性樹脂組成物は、外観性状の成形体を提供することができ、外観性状が重視される電気電子機器部品、家電製品、自動車内外装用部品、住宅設備用部材等に好適な成形体を生産性良く提供することを可能にする。
The thermoplastic resin composition of the present invention can satisfy both the releasability and the reduction of gas generation in a balanced manner. Although the releasability is insufficient only with a monocarboxylic acid metal salt (ester), when used in combination with a dicarboxylic acid metal salt (ester), the balance between the amount of gas generated and releasability is improved, and the dicarboxylic acid metal Since the salt has a high boiling point and is not easily liberated, it is difficult to volatilize, and since it is easy to add, it has an effect of easily enjoying the plasticizing effect.
The thermoplastic resin composition of the present invention can provide a molded article having an appearance property, and is suitable for electrical and electronic equipment parts, home appliances, automotive interior / exterior parts, housing equipment members, etc. where appearance characteristics are important. It is possible to provide a molded body with high productivity.
以下、本発明について実施形態および例示物を示して詳細に説明するが、本発明は当該実施形態及び例示物等に限定して解釈されるものではない。
なお、本願明細書において、「〜」とは、特に断りのない限り、その前後に記載される数値を下限値および上限値として含む意味で使用される。
Hereinafter, although an embodiment and an example thing are shown and explained in detail about the present invention, the present invention is limited to the embodiment, an example thing, etc., and is not interpreted.
In the specification of the present application, “to” is used in the sense of including the numerical values described before and after the lower limit and the upper limit unless otherwise specified.
本発明は、ポリアミド樹脂100質量部に対し、(A)炭素数が12以上の脂肪族モノカルボン酸の金属塩又はエステル、及び(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩又はエステルを(A)と(B)の合計で0.1〜5質量部含有することを特徴とする。 The present invention relates to (A) a metal salt or ester of an aliphatic monocarboxylic acid having 12 or more carbon atoms and (B) a metal salt of an aliphatic dicarboxylic acid having 12 or more carbon atoms, relative to 100 parts by mass of the polyamide resin. It is characterized by containing 0.1-5 mass parts of ester in the sum total of (A) and (B).
[熱可塑性樹脂]
本発明の熱可塑性樹脂組成物に用いられる熱可塑性樹脂としては、ポリエチレンテレフタレート樹脂、ポリトリメチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂ポリアリレート、液晶性ポリエステル等の熱可塑性ポリエステル樹脂;
ポリスチレン樹脂、高衝撃ポリスチレン樹脂(HIPS)、アクリロニトリル−スチレン共重合体(AS樹脂)、アクリロニトリル−ブタジエン−スチレン共重合体(ABS樹脂)、アクリロニトリル−スチレン−アクリルゴム共重合体(ASA樹脂)、アクリロニトリル−エチレンプロピレン系ゴム−スチレン共重合体(AES樹脂)等のスチレン系樹脂;
[Thermoplastic resin]
Examples of the thermoplastic resin used in the thermoplastic resin composition of the present invention include thermoplastic polyester resins such as polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin polyarylate, and liquid crystalline polyester;
Polystyrene resin, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene-acrylic rubber copolymer (ASA resin), acrylonitrile -Styrene resin such as ethylene propylene rubber-styrene copolymer (AES resin);
ポリエチレン樹脂、ポリプロピレン樹脂、環状オレフィン樹脂、環状オレフィン共重合体樹脂等のポリオレフィン樹脂;
ポリアミド樹脂;ポリイミド樹脂;ポリエーテルイミド樹脂;ポリウレタン樹脂;ポリフェニレンエーテル樹脂;ポリフェニレンサルファイド樹脂;ポリスルホン樹脂;ポリカーボネート樹脂;ポリオキシメチレン樹脂、ポリメタクリレート樹脂;ポリ塩化ビニル樹脂、ポリテトラフルオロエチレン樹脂、各種エラストマー等が挙げられる。
また、これらは単独使用だけでなく、ポリマーブレンドや共重合したものを使用しても良い。
Polyolefin resins such as polyethylene resins, polypropylene resins, cyclic olefin resins, cyclic olefin copolymer resins;
Polyamide resin; Polyimide resin; Polyetherimide resin; Polyurethane resin; Polyphenylene ether resin; Polyphenylene sulfide resin; Polysulfone resin; Polycarbonate resin; Polyoxymethylene resin, Polymethacrylate resin; Polyvinyl chloride resin, Polytetrafluoroethylene resin, Various elastomers Etc.
These may be used not only alone but also as a polymer blend or copolymer.
熱可塑性樹脂としては、これらの中でも、ポリアミド樹脂、ポリフェニレンエーテル樹脂、ポリエステル樹脂、ポリオキシメチレン樹脂、ポリカーボネート樹脂が好ましく、特にはポリアミド樹脂が好ましい。 Among these, polyamide resins, polyphenylene ether resins, polyester resins, polyoxymethylene resins, and polycarbonate resins are preferable as the thermoplastic resin, and polyamide resins are particularly preferable.
ポリアミド樹脂としては、ポリアミド66、ポリアミド6、ポリアミド46、ポリアミド6/66、ポリアミド10、ポリアミド612、ポリアミド11、ポリアミド12、メタキシリレンジアミン、パラキシリレンジアミン、アジピン酸およびテレフタル酸からなるポリアミドMP6/6T、ヘキサメチレンジアミン、アジピン酸およびテレフタル酸からなるポリアミド66/6T、ヘキサメチレンジアミン、イソフタル酸およびテレフタル酸からなるポリアミド6I/6T等が挙げられ、各種のポリアミド樹脂を使用することができ、2種以上を併用してもよい。 The polyamide resin includes polyamide 66, polyamide 6, polyamide 46, polyamide 6/66, polyamide 10, polyamide 612, polyamide 11, polyamide 12, metaxylylenediamine, paraxylylenediamine, adipic acid and terephthalic acid. / 6T, hexamethylene diamine, polyamide 66 / 6T composed of adipic acid and terephthalic acid, polyamide 6I / 6T composed of hexamethylene diamine, isophthalic acid and terephthalic acid, and various polyamide resins can be used. Two or more kinds may be used in combination.
本発明の熱可塑性樹脂として、特に好ましいポリアミド樹脂は、キシリレンジアミンとα,ω−直鎖脂肪族二塩基酸との重縮合反応により得られるキシリレンジアミン系ポリアミド樹脂である。
キシリレンジアミン系ポリアミド樹脂の縮合原料であるキシリレンジアミンとしては、メタキシリレンジアミンまたはパラキシリレンジアミンを単独またはこれらを混合して用いてもよく、メタキシリレンジアミン50〜100モル%とパラキシリレンジアミン50〜0モル%の範囲で用いるのが好ましい。パラキシリレンジアミンが50モル%を越えると得られるキシリレンジアミン系ポリアミド樹脂の融点が高くなりすぎ、成形時の加熱による熱劣化を引き起こしやすく、成形が困難になりやすい。
A particularly preferred polyamide resin as the thermoplastic resin of the present invention is a xylylenediamine-based polyamide resin obtained by a polycondensation reaction between xylylenediamine and an α, ω-linear aliphatic dibasic acid.
As the xylylenediamine, which is a condensation raw material of the xylylenediamine-based polyamide resin, metaxylylenediamine or paraxylylenediamine may be used alone or as a mixture thereof. Xylylenediamine is preferably used in the range of 50 to 0 mol%. If the amount of paraxylylenediamine exceeds 50 mol%, the melting point of the xylylenediamine-based polyamide resin obtained becomes too high, which tends to cause thermal deterioration due to heating during molding, and molding tends to be difficult.
メタキシリレンジアミンとパラキシリレンジアミンを混合して使用する場合は、好ましくは、パラキシリレンジアミンを10〜50モル%、メタキシリレンジアミンを90〜50モル%の割合で、より好ましくはパラキシリレンジアミンを15〜45モル%、メタキシリレンジアミンを85〜55モル%の割合で使用する。最も好ましくは、パラキシリレンジアミンを20〜40モル%、メタキシリレンジアミンを80〜60モル%の割合で使用する。パラキシリレンジアミンの量が、10モル%未満では十分な融点の向上が見られにくい場合があり、50モル%を越えると融点が高くなりすぎ、重合時および成形時に熱劣化等の不都合を生じるおそれがあるので好ましくない。混合ジアミンにおけるジアミンとしては、パラキシリレンジアミンとメタキシリレンジアミン以外に、脂肪族ジアミン、芳香族ジアミンおよび脂環族ジアミン等の他のジアミンを混合して使用してもよく、他のジアミンの使用割合は、好ましくは全ジアミンの10モル%以下であり、より好ましくは全ジアミンの5モル%以下である。脂肪族ジアミンとしては、例えばテトラメチレンジアミン、ペンタメチレンジアミン、ヘキサメチレンジアミン、オクタメチレンジアミン、ノナメチレンジアミン等が挙げられ、芳香族ジアミンとしては、例えば、メタフェニレンジアミン、パラフェニレンジアミン等が挙げられ、脂環族ジアミンとしては、1,3−ビスアミノメチルシクロヘキサン、1,4−ビスアミノメチルシクロヘキサン等が挙げられる。 When mixing and using metaxylylenediamine and paraxylylenediamine, preferably 10 to 50 mol% of paraxylylenediamine and 90 to 50 mol% of metaxylylenediamine, more preferably Xylylenediamine is used in a proportion of 15 to 45 mol% and metaxylylenediamine in a proportion of 85 to 55 mol%. Most preferably, paraxylylenediamine is used in a proportion of 20 to 40 mol% and metaxylylenediamine is used in a proportion of 80 to 60 mol%. If the amount of paraxylylenediamine is less than 10 mol%, it may be difficult to improve the melting point sufficiently, and if it exceeds 50 mol%, the melting point becomes too high, causing problems such as thermal degradation during polymerization and molding. This is not preferable because of fear. As the diamine in the mixed diamine, in addition to paraxylylenediamine and metaxylylenediamine, other diamines such as aliphatic diamine, aromatic diamine and alicyclic diamine may be mixed and used. The use ratio is preferably 10 mol% or less of the total diamine, and more preferably 5 mol% or less of the total diamine. Examples of the aliphatic diamine include tetramethylene diamine, pentamethylene diamine, hexamethylene diamine, octamethylene diamine, and nonamethylene diamine. Examples of the aromatic diamine include metaphenylene diamine and paraphenylene diamine. Examples of the alicyclic diamine include 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane.
もう一方の縮合原料であるα,ω−直鎖脂肪族二塩基酸としては、好ましくは炭素原子数6〜12の脂肪族二塩基酸であり、具体例としては、アジピン酸、コハク酸、グルタル酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸、ウンデカン二酸、ドデカン二酸等が挙げられ、このうち特に好ましいのは、アジピン酸である。また、α,ω−直鎖脂肪族二塩基酸以外に少量の芳香族二塩基酸を使用することもでき、芳香族二塩基酸としては、1,5−ナフタレンジカルボン酸等が挙げられ、芳香族二塩基酸を使用する場合の使用量は、好ましくは、全二塩基酸の10モル%以下であり、より好ましくは5モル%以下である。 The α, ω-linear aliphatic dibasic acid that is the other condensation raw material is preferably an aliphatic dibasic acid having 6 to 12 carbon atoms. Specific examples include adipic acid, succinic acid, and glutar Examples include acids, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and the like, and among these, adipic acid is particularly preferable. In addition to the α, ω-linear aliphatic dibasic acid, a small amount of aromatic dibasic acid can be used. Examples of the aromatic dibasic acid include 1,5-naphthalenedicarboxylic acid and the like. When the group dibasic acid is used, the amount used is preferably 10 mol% or less, more preferably 5 mol% or less of the total dibasic acid.
キシリレンジアミン系ポリアミド樹脂の相対粘度は、好ましくは1.6〜3であり、より好ましくは1.7〜2.9であり、最も好ましくは1.8〜2.8である。相対粘度が低すぎると機械的強度が不十分であり、高すぎると成形性が低下し、また表面外観が低下しやすい。
なお、本発明における相対粘度とは、96%硫酸中、濃度1g/100ml、温度25℃の条件で測定される値である。
The relative viscosity of the xylylenediamine-based polyamide resin is preferably 1.6 to 3, more preferably 1.7 to 2.9, and most preferably 1.8 to 2.8. If the relative viscosity is too low, the mechanical strength is insufficient, and if it is too high, the moldability is lowered and the surface appearance tends to be lowered.
The relative viscosity in the present invention is a value measured in 96% sulfuric acid under conditions of a concentration of 1 g / 100 ml and a temperature of 25 ° C.
[(A)炭素数が12以上の脂肪族モノカルボン酸の金属塩又はエステル]
炭素数が12以上の脂肪族モノカルボン酸としては、飽和または不飽和の、直鎖または分岐の、いずれの脂肪族モノカルボン酸でもよく、例えば、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、パルミトレイン酸、マルガリン酸、ステアリン酸、オレイン酸、リノール酸、リノレン酸、ツベルクロステアリン酸、アラキジン酸、アラキドン酸、ベヘン酸、リグノセリン酸、ネルボン酸、セロチン酸、モンタン酸、メリシン酸等を挙げることができる。
前記脂肪族モノカルボン酸の中で、炭素数が16〜32の飽和脂肪族モノカルボン酸であり、パルミチン酸、マルガリン酸、ステアリン酸、ツベルクロステアリン酸、アラキジン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸等を好ましく挙げることができる。
[(A) Metal salt or ester of aliphatic monocarboxylic acid having 12 or more carbon atoms]
The aliphatic monocarboxylic acid having 12 or more carbon atoms may be any saturated or unsaturated, linear or branched aliphatic monocarboxylic acid, such as lauric acid, myristic acid, pentadecylic acid, palmitic acid, List palmitoleic acid, margaric acid, stearic acid, oleic acid, linoleic acid, linolenic acid, tuberculostearic acid, arachidic acid, arachidonic acid, behenic acid, lignoceric acid, nervonic acid, serotic acid, montanic acid, melicic acid, etc. Can do.
Among the aliphatic monocarboxylic acids, a saturated aliphatic monocarboxylic acid having 16 to 32 carbon atoms such as palmitic acid, margaric acid, stearic acid, tuberculostearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic Preferred examples include acid, montanic acid, melicic acid and the like.
脂肪族モノカルボン酸の金属塩としては、アルカリ金属塩またはアルカリ土類金属塩が好ましく、アルカリ金属塩としては、例えばナトリウム塩、カリウム塩が好ましく挙げられ、また、アルカリ土類金属塩としては、例えばカルシウム塩、マグネシウム塩、バリウム塩が好ましく挙げられる。これらのうち、特に好ましいものは、ナトリウム塩、カルシウム塩である。 As the metal salt of the aliphatic monocarboxylic acid, an alkali metal salt or an alkaline earth metal salt is preferable, and as the alkali metal salt, for example, a sodium salt and a potassium salt are preferable, and as the alkaline earth metal salt, For example, calcium salts, magnesium salts, and barium salts are preferred. Of these, sodium salts and calcium salts are particularly preferable.
一方、脂肪族モノカルボン酸のエステルとしては、アルコールとのエステルが好ましく、アルコールとしては、飽和または不飽和の一価または多価アルコールが挙げられ、これらの中では、炭素数30以下の一価または多価の飽和アルコールが好ましく、炭素数30以下の脂肪族又は脂環式飽和一価アルコールまたは脂肪族飽和多価アルコールがさらに好ましい。 On the other hand, the ester of an aliphatic monocarboxylic acid is preferably an ester with an alcohol, and examples of the alcohol include saturated or unsaturated monohydric or polyhydric alcohols. Alternatively, polyvalent saturated alcohol is preferable, and aliphatic or alicyclic saturated monohydric alcohol or aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.
このようなアルコールの具体例としては、メタノール、エタノール、イソプロピルアルコールオクタノール、デカノール、ドデカノール、ステアリルアルコール、ベヘニルアルコール、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、2,2−ジヒドロキシペルフルオロプロパノール、ネオペンチレングリコール、ジトリメチロールプロパン、ソルビタン、ジペンタエリスリトール等が挙げられる。 Specific examples of such alcohols include methanol, ethanol, isopropyl alcohol octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol. , Neopentylene glycol, ditrimethylolpropane, sorbitan, dipentaerythritol and the like.
炭素数が12以上の脂肪族モノカルボン酸の金属塩もしくはエステル(A)として、より好ましい化合物の具体例としては、ステアリン酸カルシウム、ステアリン酸バリウム、ベヘン酸カルシウム、ベヘン酸ナトリウム、リグノセリン酸カルシウム、リグノセリン酸ナトリウム、リグノセリン酸エチル、セロチン酸カルシウム、セロチン酸ナトリウム、セロチン酸エチル、モンタン酸カルシウム、モンタン酸ナトリウム、モンタン酸エチル、メリシン酸カルシウム、メリシン酸ナトリウム、メリシン酸エチル等が挙げられる。 Specific examples of more preferable compounds as the metal salt or ester (A) of an aliphatic monocarboxylic acid having 12 or more carbon atoms include calcium stearate, barium stearate, calcium behenate, sodium behenate, calcium lignocerate, lignoserine. Examples thereof include sodium acid, ethyl lignocerate, calcium serotate, sodium serotic acid, ethyl serotic acid, calcium montanate, sodium montanate, ethyl montanate, calcium melicinate, sodium melicinate, ethyl melicate and the like.
[(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩又はエステル]
炭素数が12以上の脂肪族ジカルボン酸としては、飽和または不飽和の、直鎖または分岐の、いずれの脂肪族ジカルボン酸でもよく、例えば、ドデカン二酸、テトラデカン二酸、ペンタデカン二酸、ヘキサデカン二酸、ヘキサデセン二酸、ヘプタデカン二酸、オクタデカン二酸、オクタデセン二酸、オクタデカジエン二酸、オクタデカントリエン二酸、ノナデカン二酸、エイコサン二酸、エイコサジエン二酸、エイコサトリエン二酸、エイコサテトラエン二酸、ドコサン二酸、テトラコサン二酸、ヘキサコサン二酸、オクタコサン二酸、トリアコンタンサン二酸等を挙げることができる。
前記脂肪族ジカルボン酸の中で、炭素数が16〜32の飽和脂肪族ジカルボン酸であり、ヘキサデカン二酸、ヘプタデカン二酸、オクタデカン二酸、ノナデカン二酸、エイコサン二酸、ドコサン二酸、テトラコサン二酸、ヘキサコサン二酸、オクタコサン二酸、トリアコンタン二酸等を好ましく挙げることができる。
[(B) Metal salt or ester of aliphatic dicarboxylic acid having 12 or more carbon atoms]
The aliphatic dicarboxylic acid having 12 or more carbon atoms may be any saturated or unsaturated, linear or branched aliphatic dicarboxylic acid, such as dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanediic acid. Acid, hexadecenedioic acid, heptadecanedioic acid, octadecanedioic acid, octadecenedioic acid, octadecadienedioic acid, octadecanetrienedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosadienedioic acid, eicosatrienedioic acid, eicosatetraic acid Examples thereof include enedioic acid, docosanedioic acid, tetracosanedioic acid, hexacosanedioic acid, octacosanedioic acid, and triacontanesandioic acid.
Among the aliphatic dicarboxylic acids, a saturated aliphatic dicarboxylic acid having 16 to 32 carbon atoms, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid. Preferable examples include acid, hexacosane diacid, octacosane diacid, triacontane diacid and the like.
脂肪族ジカルボン酸の金属塩としては、アルカリ金属塩またはアルカリ土類金属塩が好ましく、アルカリ金属塩としては、例えばナトリウム塩、カリウム塩が好ましく挙げられ、また、アルカリ土類金属塩としては、例えばカルシウム塩、マグネシウム塩、バリウム塩が好ましく挙げられる。これらのうち、特に好ましいものは、ナトリウム塩、カルシウム塩である。
脂肪族ジカルボン酸の金属塩は、両方のカルボン酸が金属塩になっていてもよく、また片方のみが金属塩となっていてもよい。
As the metal salt of the aliphatic dicarboxylic acid, an alkali metal salt or an alkaline earth metal salt is preferable. Examples of the alkali metal salt preferably include a sodium salt and a potassium salt. Examples of the alkaline earth metal salt include Preferred examples include calcium salts, magnesium salts, and barium salts. Of these, sodium salts and calcium salts are particularly preferable.
In the metal salt of the aliphatic dicarboxylic acid, both carboxylic acids may be metal salts, or only one of them may be a metal salt.
一方、脂肪族ジカルボン酸のエステルとしては、アルコールとのエステルが好ましく、アルコールとしては、飽和または不飽和の一価または多価アルコールが挙げられ、これらの中では、炭素数30以下の一価または多価の飽和アルコールが好ましく、炭素数30以下の脂肪族又は脂環式飽和一価アルコールまたは脂肪族飽和多価アルコールがさらに好ましい。 On the other hand, as an ester of an aliphatic dicarboxylic acid, an ester with an alcohol is preferable, and examples of the alcohol include saturated or unsaturated monovalent or polyhydric alcohols. A polyvalent saturated alcohol is preferable, and an aliphatic or alicyclic saturated monohydric alcohol or an aliphatic saturated polyhydric alcohol having 30 or less carbon atoms is more preferable.
このようなアルコールの具体例としては、メタノール、エタノール、イソプロピルアルコールオクタノール、デカノール、ドデカノール、ステアリルアルコール、ベヘニルアルコール、エチレングリコール、プロピレングリコール、ブチレングリコール、ジエチレングリコール、グリセリン、ペンタエリスリトール、2,2−ジヒドロキシペルフルオロプロパノール、ネオペンチレングリコール、ジトリメチロールプロパン、ソルビタン、ジペンタエリスリトール等が挙げられる。 Specific examples of such alcohols include methanol, ethanol, isopropyl alcohol octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol. , Neopentylene glycol, ditrimethylolpropane, sorbitan, dipentaerythritol and the like.
(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩又はエステルとして、より好ましい化合物の具体例としては、オクタデカン二酸カルシウム、オクタデカン二酸ナトリウム、ノナデカン二酸カルシウム、ノナデカン二酸ナトリウム、エイコサン二酸カルシウム、エイコサン二酸ナトリウム、ドコサン二酸カルシウム、ドコサン二酸ナトリウム、テトラコサン二酸カルシウム、テトラコサン二酸ナトリウム、ヘキサコサン二酸カルシウム、ヘキサコサン二酸ナトリウム、オクタコサン二酸カルシウム、オクタコサン二酸ナトリウム、トリアコンタン二酸カルシウム、トリアコンタン二酸ジナトリウム等が挙げられる。なお、この例示におけるナトリウム塩は、ジナトリウム塩、モノナトリウム塩またこれらの混合物を意味する。 (B) Specific examples of more preferable compounds as the metal salt or ester of an aliphatic dicarboxylic acid having 12 or more carbon atoms include calcium octadecanedioate, sodium octadecanedioate, calcium nonadecanedioate, sodium nonadecanedioate, and eicosane. Calcium diacid, sodium eicosane diacid, calcium docosane diacid, sodium docosane diacid, calcium tetracosane diacid, sodium tetracosane diacid, calcium hexacosane diacid, sodium hexacosane diacid, calcium octacosane diacid, sodium octacosane diacid, tria Examples include calcium contandioate and disodium triacontanedioate. In addition, the sodium salt in this illustration means a disodium salt, a monosodium salt, or a mixture thereof.
上記(A)炭素数が12以上の脂肪族モノカルボン酸の金属塩又はエステル、及び(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩又はエステルの含有量は、両者の合計で、熱可塑性樹脂100質量部に対し、0.1〜5質量部の範囲である。含有量が0.1質量部未満で離型性向上効果が充分に発揮されず、金型からの離型性の不良等で成型加工性が低下する。また、5質量部を超えると成形時のガス発生量が多くなり、樹脂組成物の外観に悪影響を及ぼす。さらに金属塩またはエステル化合物の可塑化効果により物性に影響を及ぼす場合もある。好ましい含有量は0.15〜4質量部、さらに好ましくは0.2〜3質量部である。 The content of (A) a metal salt or ester of an aliphatic monocarboxylic acid having 12 or more carbon atoms and (B) a metal salt or ester of an aliphatic dicarboxylic acid having 12 or more carbon atoms is the sum of both. It is the range of 0.1-5 mass parts with respect to 100 mass parts of thermoplastic resins. If the content is less than 0.1 part by mass, the effect of improving the releasability is not sufficiently exerted, and the moldability is deteriorated due to the poor releasability from the mold. Moreover, when it exceeds 5 mass parts, the amount of gas generation at the time of shaping | molding will increase and it will have a bad influence on the external appearance of a resin composition. Furthermore, physical properties may be affected by the plasticizing effect of the metal salt or ester compound. A preferable content is 0.15 to 4 parts by mass, and more preferably 0.2 to 3 parts by mass.
また、(A)炭素数が12以上の脂肪族モノカルボン酸の金属塩またはエステルと(B)炭素数が12以上の脂肪族ジカルボン酸の金属塩またはエステルは、その質量比率が、(A)と(B)の合計100質量%基準で、(A)が60〜95質量%、(B)が40〜5質量%であることが好ましい。 Further, (A) a metal salt or ester of an aliphatic monocarboxylic acid having 12 or more carbon atoms and (B) a metal salt or ester of an aliphatic dicarboxylic acid having 12 or more carbon atoms have a mass ratio of (A) It is preferable that (A) is 60 to 95% by mass and (B) is 40 to 5% by mass on the basis of the total of 100% by mass of (B) and (B).
[その他成分]
また、本発明の熱可塑性樹脂組成物は、強度と剛性、寸法安定性を向上させる目的で、無機充填材を含有することも好ましい。
無機充填材の形状は、繊維状、針状、板状、粒状または不定形状など任意である。無機充填材の具体例としては、ガラス繊維(チョップドストランド)、ガラス短繊維(ミルドファイバー)、ガラスフレーク、ガラスビーズ等のガラス系フィラー;炭素繊維、炭素短繊維、カーボンナノチューブ、黒鉛などの炭素系フィラー;チタン酸カリウム、ホウ酸アルミニウム等のウィスカー;タルク、マイカ、ウォラストナイト、カオリナイト、ゾノトライト、セピオライト、アタバルジャイト、モンモリロナイト、ベントナイト、スメクタイトなどの珪酸塩化合物;シリカ、アルミナ、炭酸カルシウム等が挙げられる。
これらの中では良好な表面意匠性を得る目的で、タルク、マイカ、ウォラストナイト、カオリナイト、ガラス繊維が好ましく、タルク、マイカ、ガラス繊維がより好ましい。
また、無機充填材は、2種以上を併用してもよい。
[Other ingredients]
The thermoplastic resin composition of the present invention preferably contains an inorganic filler for the purpose of improving strength, rigidity, and dimensional stability.
The shape of the inorganic filler is arbitrary such as a fiber shape, a needle shape, a plate shape, a granular shape or an indefinite shape. Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), glass short fibers (milled fibers), glass flakes, and glass beads; carbon fibers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. Fillers: Whiskers such as potassium titanate and aluminum borate; Silicate compounds such as talc, mica, wollastonite, kaolinite, zonotolite, sepiolite, attabargite, montmorillonite, bentonite, smectite; silica, alumina, calcium carbonate, etc. It is done.
Among these, talc, mica, wollastonite, kaolinite, and glass fiber are preferable for the purpose of obtaining good surface design properties, and talc, mica, and glass fiber are more preferable.
Two or more inorganic fillers may be used in combination.
無機充填材の含有量は、好ましくは、熱可塑性樹脂100質量部に対して、1〜250質量部である。無機充填材の効果を発現させるためには、少なくとも1質量部は含有させるべきである。無機充填材の含有量が1質量部未満の場合は補強効果が十分でない場合がある。また250質量部を超える場合は、表面外観や耐衝撃性が劣り、流動性が十分でない場合がある。無機充填材のより好ましい含有量は10〜200質量部、特には30〜180質量部である。 The content of the inorganic filler is preferably 1 to 250 parts by mass with respect to 100 parts by mass of the thermoplastic resin. In order to express the effect of the inorganic filler, at least 1 part by mass should be contained. When the content of the inorganic filler is less than 1 part by mass, the reinforcing effect may not be sufficient. Moreover, when it exceeds 250 mass parts, surface appearance and impact resistance may be inferior, and fluidity | liquidity may not be enough. The more preferable content of the inorganic filler is 10 to 200 parts by mass, particularly 30 to 180 parts by mass.
熱可塑性樹脂としてポリアミド樹脂組成物を使用する場合において、無機充填材が、ガラス繊維、炭素繊維等の繊維状である場合、その平均繊維径は、1〜100μmが好ましく、2〜50μmがより好ましく、3〜30μmがさらに好ましく、5〜20μmが特に好ましい。このような繊維径のものを採用することにより、機械的特性をより優れたものとすることができる。また、平均繊維長は、特に制限されないが、0.01〜20mmが好ましく、0.03〜10mmがより好ましく、0.05〜6mmがさらに好ましい。平均繊維長が0.01mm未満では、繊維状無機充填材による補強効果が不十分な場合があり、平均繊維長が20mmを超えると、特にキシリレンジアミン系ポリアミド樹脂を使用した場合、溶融混練や強化ポリアミド樹脂組成物の成形が困難になる場合がある。 In the case of using a polyamide resin composition as the thermoplastic resin, when the inorganic filler is in a fibrous form such as glass fiber or carbon fiber, the average fiber diameter is preferably 1 to 100 μm, more preferably 2 to 50 μm. 3 to 30 μm is more preferable, and 5 to 20 μm is particularly preferable. By adopting such a fiber diameter, the mechanical properties can be further improved. Moreover, especially average fiber length is although it does not restrict | limit, 0.01-20 mm is preferable, 0.03-10 mm is more preferable, 0.05-6 mm is further more preferable. When the average fiber length is less than 0.01 mm, the reinforcing effect by the fibrous inorganic filler may be insufficient. When the average fiber length exceeds 20 mm, particularly when a xylylenediamine-based polyamide resin is used, Molding of the reinforced polyamide resin composition may be difficult.
さらに、本発明の熱可塑性樹脂脂組成物は、必要に応じて、他の成分、例えば、樹脂添加剤等を含有してもよい。例えば、熱安定剤、酸化防止剤、紫外線吸収剤、染顔料、難燃剤、滴下防止剤、帯電防止剤、防曇剤、アンチブロッキング剤、流動性改良剤、可塑剤、分散剤、抗菌剤などが挙げられる。 Furthermore, the thermoplastic resin fat composition of the present invention may contain other components, for example, a resin additive or the like, if necessary. For example, heat stabilizers, antioxidants, UV absorbers, dyes and pigments, flame retardants, anti-dripping agents, antistatic agents, antifogging agents, antiblocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, etc. Is mentioned.
[組成物の製造方法]
本発明の熱可塑性樹脂組成物の製造方法に制限はなく、公知の熱可塑性樹脂組成物の製造方法を広く採用できる。
具体例を挙げると、本発明に係る熱可塑性樹脂、(A)脂肪族モノカルボン酸の金属塩(又はエステル)、及び(B)脂肪族ジカルボン酸の金属塩(又はエステル)、そして、必要に応じて配合されるその他の成分を、例えばタンブラーやヘンシェルミキサーなどの各種混合機を用い予め混合した後、バンバリーミキサー、ロール、ブラベンダー、単軸混練押出機、二軸混練押出機、ニーダーなどの混合機で溶融混練する方法が挙げられる。
[Method for producing composition]
There is no restriction | limiting in the manufacturing method of the thermoplastic resin composition of this invention, The manufacturing method of a well-known thermoplastic resin composition can be employ | adopted widely.
Specific examples include the thermoplastic resin according to the present invention, (A) a metal salt (or ester) of an aliphatic monocarboxylic acid, and (B) a metal salt (or ester) of an aliphatic dicarboxylic acid, and Other ingredients to be blended in accordance with, for example, various mixers such as a tumbler and Henschel mixer, after pre-mixing, such as Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader The method of melt-kneading with a mixer is mentioned.
また、例えば、各成分を予め混合せずに、または、一部の成分のみを予め混合し、フィーダーを用いて押出機に供給して溶融混練して、本発明の熱可塑性樹脂組成物を製造することもできる。
また、例えば、一部の成分を予め混合し押出機に供給して溶融混練することで得られる樹脂組成物をマスターバッチとし、このマスターバッチを再度残りの成分と混合し、溶融混練することによって本発明の熱可塑性樹脂組成物を製造することもできる。
また、例えば、分散し難い成分を混合する際には、その分散し難い成分を予め水や有機溶剤等の溶媒に溶解又は分散させ、その溶液又は分散液と混練するようにすることで、分散性を高めることもできる。
In addition, for example, the thermoplastic resin composition of the present invention is manufactured without mixing each component in advance or by mixing only a part of the components in advance and supplying the mixture to an extruder using a feeder and melt-kneading. You can also
Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The thermoplastic resin composition of the present invention can also be produced.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.
[成形体]
本発明の熱可塑性樹脂組成物は、通常、任意の形状に成形して成形体(樹脂組成物成形体)として用いる。この成形体の形状、模様、色彩、寸法などに制限はなく、その成形体の用途に応じて任意に設定すればよい。
成形体の例を挙げると、電気電子機器、OA機器、情報端末機器、機械部品、家電製品、車輌部品、建築部材、各種容器、レジャー用品・雑貨類、照明機器等の部品が挙げられる。これらの中でも、電気電子機器、OA機器、情報端末機器、家電製品、照明機器等の部品へ用いて好適である。
[Molded body]
The thermoplastic resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.
Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment.
前記の電気電子機器としては、例えば、パソコン、ゲーム機、テレビなどのディスプレイ装置、プリンター、コピー機、スキャナー、ファックス、電子手帳やPDA、電子式卓上計算機、電子辞書、カメラ、ビデオカメラ、携帯電話、電池パック、記録媒体のドライブや読み取り装置、マウス、テンキー、CDプレーヤー、MDプレーヤー、携帯ラジオ・オーディオプレーヤー等が挙げられる。 Examples of the electric and electronic devices include display devices such as personal computers, game machines, and televisions, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, video cameras, and mobile phones. Battery pack, recording medium drive and reader, mouse, numeric keypad, CD player, MD player, portable radio / audio player, and the like.
成形体の製造方法は、特に限定されず、熱可塑性樹脂組成物について一般に採用されている成形法を任意に採用できる。その例を挙げると、射出成形法、超高速射出成形法、射出圧縮成形法、二色成形法、ガスアシスト等の中空成形法、断熱金型を使用した成形法、急速加熱金型を使用した成形法、発泡成形(超臨界流体も含む)、インサート成形、IMC(インモールドコーティング成形)成形法、押出成形法、シート成形法、熱成形法、回転成形法、積層成形法、プレス成形法などが挙げられる。また、ホットランナー方式を使用した成形法を用いることも出来る。 The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the thermoplastic resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.
以下、実施例を示して本発明について更に具体的に説明する。ただし、本発明は以下の実施例に限定して解釈されるものではない。
実施例および比較例において用いた原料成分は次のとおりである。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
The raw material components used in Examples and Comparative Examples are as follows.
(1)ポリアミド樹脂
・ポリメタキシリレンジアジパミド (以下、「MXD6」という。)
三菱瓦斯化学社製、商品名「ポリアミドMXD6#6000」
融点243℃、相対粘度2.14(98%硫酸中、濃度1重量%、測定温度25℃)
・ポリアミド66 (以下、「PA66」という。)
東レ社製、商品名「アミラン CM3001N」
相対粘度2.95(上記と同様の方法で測定)
(1) Polyamide resin / polymetaxylylene adipamide (hereinafter referred to as “MXD6”)
Product name “Polyamide MXD6 # 6000” manufactured by Mitsubishi Gas Chemical Company, Inc.
Melting point 243 ° C., relative viscosity 2.14 (98% sulfuric acid, concentration 1% by weight, measuring temperature 25 ° C.)
Polyamide 66 (hereinafter referred to as “PA66”)
Product name “Amilan CM3001N” manufactured by Toray Industries, Inc.
Relative viscosity 2.95 (measured in the same manner as above)
(2)無機充填材
・ガラス繊維 (以下、「GF」という。)
日本電気硝子製、商品名「CS03T−296GH」
平均繊維径9.5μm、繊維長3mm、表面処理あり
・タルク (以下、「タルク」という。)
林化成社製、商品名「ミクロンホワイト#5000S」
(2) Inorganic filler / glass fiber (hereinafter referred to as “GF”)
Product name "CS03T-296GH", manufactured by Nippon Electric Glass
Average fiber diameter 9.5 μm, fiber length 3 mm, with surface treatment and talc (hereinafter referred to as “talc”)
Product name “Micron White # 5000S” manufactured by Hayashi Kasei Co., Ltd.
(3)脂肪族モノカルボン酸金属塩又はエステル(A)および脂肪族ジカルボン酸金属塩又はエステル(B)
後記表1及び表2に記載のものを使用した。
(3) Aliphatic monocarboxylic acid metal salt or ester (A) and Aliphatic dicarboxylic acid metal salt or ester (B)
Those described in Tables 1 and 2 below were used.
(実施例1〜11および比較例1〜4)
<樹脂組成物の調製>
上記原料成分を使用し、表1又は表2に示す割合で含有するポリアミド樹脂組成物を以下のように調製した。
すなわち、表1又は表2に示すGF以外の各成分を同表に示す割合にて、タンブラーミキサーで均一に混合した後、二軸押出機(東芝機械社製「TEM26SS」)のホッパに投入し、GFはサイドからフィードし、温度280℃で溶融混練した。溶融樹脂組成物のストランドを、水槽にて冷却し、ペレタイザーを用いてペレット化し、樹脂組成物のペレットを得た。
上記で得られた各ペレットを使用し、以下の方法により、離型性と発生ガス量の評価を行った。
(Examples 1-11 and Comparative Examples 1-4)
<Preparation of resin composition>
A polyamide resin composition containing the raw material components and contained in the proportions shown in Table 1 or Table 2 was prepared as follows.
That is, after each component other than GF shown in Table 1 or Table 2 is uniformly mixed with a tumbler mixer in the ratio shown in the same table, it is put into a hopper of a twin screw extruder (“TEM26SS” manufactured by Toshiba Machine Co., Ltd.). GF was fed from the side and melt kneaded at a temperature of 280 ° C. The strand of the molten resin composition was cooled in a water bath and pelletized using a pelletizer to obtain a resin composition pellet.
Each pellet obtained above was used, and the releasability and the amount of generated gas were evaluated by the following methods.
(1)離型性の評価
以下の離型評価型による試験を行った。
上記で得られた各ペレットを、住友重機械工業製「SE50D」射出成形機を使用して、シリンダー温度295℃にて、外寸が52×32×16mmで厚みが1.5mmの箱型の評価用金型を用い、金型温度130℃、充填時間0.3秒、保圧50MPa/7秒、冷却時間は10秒で成形し、その際エジェクターピンに感圧センサーを取り付け、突き出し圧力を測定し、以下の基準で評価を行った。
×:8MPa以上 △:5〜8MPa ○:3〜5MPa ◎:3MPa以下
(1) Evaluation of releasability A test using the following releasability evaluation mold was performed.
Each pellet obtained above is a box type having an outer dimension of 52 × 32 × 16 mm and a thickness of 1.5 mm at a cylinder temperature of 295 ° C. using an “SE50D” injection molding machine manufactured by Sumitomo Heavy Industries. Using an evaluation mold, molding was performed at a mold temperature of 130 ° C., a filling time of 0.3 seconds, a holding pressure of 50 MPa / 7 seconds, and a cooling time of 10 seconds. At that time, a pressure sensor was attached to the ejector pin, and the ejection pressure was Measurements were made and evaluated according to the following criteria.
×: 8 MPa or more Δ: 5-8 MPa ○: 3-5 MPa ◎: 3 MPa or less
(2)発生ガス量の評価
上記(1)と同様に、住友重機械工業製「SE50D」射出成形機を使用して、シリンダー温度295℃にて、外寸が52×32×16mmで厚みが1.5mmの箱型の評価用金型を用いて、金型温度130℃、充填時間0.2秒、保圧50MPa/7秒、冷却時間は10秒にて成形した箱型の成形体について、ガス焼けと充填不良の度合いを以下の基準で判定した。
○:外観不良なし。 △:外観不良あり。 ×:未充填
なお、外観不良とは、ガスによる転写不良やガス焼けが見られる場合とした。
以上の評価結果を下記表1および表2に示す。
(2) Evaluation of amount of generated gas As in (1) above, using an “SE50D” injection molding machine manufactured by Sumitomo Heavy Industries, the cylinder temperature is 295 ° C., the outer dimensions are 52 × 32 × 16 mm, and the thickness is Using a 1.5 mm box-shaped evaluation mold, a box-shaped molded body molded at a mold temperature of 130 ° C., a filling time of 0.2 seconds, a holding pressure of 50 MPa / 7 seconds, and a cooling time of 10 seconds. The degree of gas burning and filling failure was determined according to the following criteria.
○: No appearance defect. Δ: Appearance is poor. X: Unfilled In addition, it was set as the case where the transfer defect by a gas and gas burn were seen with the external appearance defect.
The above evaluation results are shown in Tables 1 and 2 below.
以上の実施例と比較例を対比すれば明らかなように、本発明の(A)脂肪族モノカルボン酸の金属塩又はエステルと、(B)脂肪族ジカルボン酸の金属塩又はエステルを0.1〜5質量部含有する組成物は、離型性とガス発生の低減の両方をバランスよく満足し、優れたものであることがわかった。 As is clear from comparison of the above Examples and Comparative Examples, (A) a metal salt or ester of an aliphatic monocarboxylic acid and (B) a metal salt or ester of an aliphatic dicarboxylic acid of the present invention are 0.1 It was found that the composition containing ˜5 parts by mass satisfied both the releasability and the reduction of gas generation in a well-balanced manner and was excellent.
本発明の熱可塑性樹脂組成物は、離型性とガス発生の低減の両方をバランスよく満足し、良好な外観性状の成形体を提供することができ、外観性状が重視される電気電子機器部品、家電製品、自動車内外装用部品、住宅設備用部材等に好適な成形体を生産性良く提供することを可能にするので、産業上の利用性は非常に高いものがある。 The thermoplastic resin composition of the present invention satisfies both the releasability and the reduction of gas generation in a well-balanced manner, can provide a molded article having a good appearance property, and is an electrical / electronic device component in which appearance property is important In addition, it is possible to provide a molded article suitable for home appliances, automobile interior / exterior parts, housing equipment members, and the like with high productivity, and therefore, industrial applicability is extremely high.
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