JP2004123927A - Copolyamide resin composition - Google Patents
Copolyamide resin composition Download PDFInfo
- Publication number
- JP2004123927A JP2004123927A JP2002290738A JP2002290738A JP2004123927A JP 2004123927 A JP2004123927 A JP 2004123927A JP 2002290738 A JP2002290738 A JP 2002290738A JP 2002290738 A JP2002290738 A JP 2002290738A JP 2004123927 A JP2004123927 A JP 2004123927A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyamide
- raw material
- acid
- copolymerized polyamide
- 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.)
- Pending
Links
- 239000011342 resin composition Substances 0.000 title claims abstract description 21
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 20
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims abstract description 10
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical group NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920002647 polyamide Polymers 0.000 claims description 51
- 239000004952 Polyamide Substances 0.000 claims description 49
- 229920006122 polyamide resin Polymers 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 40
- 239000002667 nucleating agent Substances 0.000 claims description 18
- ALBYIUDWACNRRB-UHFFFAOYSA-N hexanamide Chemical group CCCCCC(N)=O ALBYIUDWACNRRB-UHFFFAOYSA-N 0.000 claims description 3
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 claims 1
- 238000000465 moulding Methods 0.000 abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 45
- 238000004519 manufacturing process Methods 0.000 description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 21
- 239000002981 blocking agent Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 14
- 239000008188 pellet Substances 0.000 description 14
- 238000004898 kneading Methods 0.000 description 12
- 238000001746 injection moulding Methods 0.000 description 11
- 238000011109 contamination Methods 0.000 description 10
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- -1 Aliphatic monocarboxylic acids Chemical class 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 229910052582 BN Inorganic materials 0.000 description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000005749 Copper compound Substances 0.000 description 6
- 150000001880 copper compounds Chemical class 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002366 halogen compounds Chemical class 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 3
- 239000004594 Masterbatch (MB) Substances 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000012760 heat stabilizer Substances 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012770 industrial material Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 150000002763 monocarboxylic acids Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- RUFPHBVGCFYCNW-UHFFFAOYSA-N 1-naphthylamine Chemical compound C1=CC=C2C(N)=CC=CC2=C1 RUFPHBVGCFYCNW-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005639 Lauric acid Substances 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical class OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 229920003188 Nylon 3 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000010485 coping Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- FPIQZBQZKBKLEI-UHFFFAOYSA-N ethyl 1-[[2-chloroethyl(nitroso)carbamoyl]amino]cyclohexane-1-carboxylate Chemical compound ClCCN(N=O)C(=O)NC1(C(=O)OCC)CCCCC1 FPIQZBQZKBKLEI-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000010137 moulding (plastic) Methods 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003873 salicylate salts Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、様々な機械工業部品、電気電子部品などの産業用材料として好適な離型性などの成形性及び成形時の溶融粘度の安定性に優れ、熱分解成分による金型の汚染が低減され、かつ得られる成形品の強度、剛性、靱性、外観に優れ、かつ耐候性、吸水時剛性、真円性に優れる共重合ポリアミド樹脂組成物に関するものである。
【0002】
【従来の技術】
ポリアミドは機械特性、耐熱性、耐薬品性などに優れることからエンジニアリングプラスチックとして自動車部品、電気部品、工業部品などさまざまな用途に用いられている。近年では、ポリアミド樹脂成形品の形状の複雑化、薄肉化、特殊化が進み、これに対応可能なポリアミド樹脂が強く求められるようになっている。その上、産業の高度化に伴い、ポリアミド樹脂成形体に求められる機械特性レベルは一層向上している。更には、経済性の観点から成形時間の短縮が可能であり、生産性が向上できるポリアミド樹脂材料が、経済性の観点や環境問題の観点からハイサイクル化やリサイクルペレットの使用にも対応可能なポリアミド樹脂材料が強く要求されている。更には、過度の外力や熱が加えられるような厳しい環境下で使用可能な高耐久性のポリアミド樹脂材料が要求されている。
【0003】
しかしながらポリアミド樹脂を用いて前記のような特殊な成形品、例えばネジ構造を有する成形品や円筒状の成形品を作る際には、可塑化性や離型性が不十分となったり、成形時の熱分解によるガス成分に基づく金型汚染が起こることがわかった。このような不具合は継続した安定成形を阻害することとなる。また、真円性が不十分であったり、屋外で特に降雨に曝される使用条件下では耐侯性が不十分であったり、更にはガス成分に基づく成形品の外観不良になど成形品の品質低下を招く結果となることもわかった。これらの不具合を改善するために、共重合ポリアミドを用いる方法(例えば、特許文献1及び2参照。)、成形性改良剤を添加する方法(例えば、特許文献3参照。)が開示されているが要求されている特性を満足するには至っていない。
【0004】
【特許文献1】
特開平10−278065号公報
【特許文献2】
特開平10−182850号公報
【特許文献3】
特開平11−42666号公報
【0005】
【発明が解決しようとする課題】
本発明は、様々な機械工業部品、電気電子部品などの産業用材料として好適な離型性などの成形性及び成形時の溶融粘度の安定性に優れ、熱分解成分による金型の汚染が低減され、かつ得られる成形品の強度、剛性、靱性、外観に優れ、かつ耐候性、吸水時剛性、真円性に優れる共重合ポリアミド樹脂組成物を提供することである。
【0006】
【課題を解決するための手段】
本発明者らは、上記本発明課題を解決すべく鋭意検討した結果、特定量の高分子末端が封鎖されているポリアミド66と6からなる特定の共重合ポリアミドに、特定の無機核剤を含有させた共重合ポリアミド樹脂組成物により、上記課題を解決できることを見いだし、本発明を完成させるに至った。
すなわち本発明は、
(1)ポリアミド66(ヘキサメチレンアジパミド)単位90〜99.9重量%とポリアミド6(カプロアミド)単位0.1〜10重量%とからなり、かつ末端がモノカルボン酸あるいはモノアミンで1〜70(ミリ当量/Kg)封鎖されている共重合ポリアミド(A)100重量部に対して、無機核剤(B)0.001〜1重量部を含有することを特徴とする共重合ポリアミド樹脂組成物、
【0007】
(2)ポリアミド66原料90〜99.9重量%、ポリアミド6原料0.1〜10重量%からなるポリアミド原料と、該ポリアミド原料100重量部に対して0.007〜0.4重量%のモノカルボン酸あるいはモノアミンからなる共重合ポリアミド原料を重合して共重合ポリアミド(A)を得、該共重合ポリアミド100重量部に対して溶融混練法にて無機核剤(B)0.001〜1重量部を含有させ得られることを特徴とする請求項1に記載の共重合ポリアミド樹脂組成物。
(3)上記(1)か上記(2)のいずれかに記載の共重合ポリアミド樹脂組成物から得られることを特徴とする射出成形品、
である。以下、本発明について詳細に説明する。
【0008】
本発明における共重合ポリアミドは、ポリアミド66(ヘキサメチレンアジパミド)、ポリアミド6(カプロアミド)ならびに末端封鎖剤としてモノカルボン酸あるいはモノアミンを含有している。
本発明における共重合ポリアミド中のポリアミド66単位の含有量は90〜99.9重量%であり、より好ましくは95〜99.5重量%であり、更に好ましくは97〜99.5重量%である。
【0009】
本発明における共重合ポリアミドのポリアミド6単位の含有量は0.1〜10重量%であり、好ましくは0.5〜5重量%であり、更に好ましくは0.5〜3重量%である。ポリアミド66単位とポリアミド6単位との含有量は、1Hあるいは13C−核磁気共鳴法(NMR)や熱分解ガスクロマトグラフィー(Py−GC)/MS法を用いて測定することができる。共重合ポリアミド中のポリアミド66単位が90重量%未満の場合には、得られる成形品の強度、吸水剛性などが低下する傾向にあり好ましくなく、また99.9重量%を超えた場合には、外観の低下やガス発生による金型汚染の改善効果が低くなる傾向にある。
【0010】
本発明の共重合ポリアミドの末端カルボキシル基濃度[COOH](ミリ当量/Kg)と末端アミノ基濃度(ミリ当量/Kg)は、その和[COOH]+[NH2]が約50〜200(ミリ当量/Kg)であり、かつその比[COOH]/[NH2]が0.1〜10程度の範囲にあることが好ましい。
本発明の共重合ポリアミドは、末端基封鎖剤としてモノカルボン酸あるいはモノアミンを含有している。該末端封鎖剤の含有量([末端封鎖剤](ミリ当量/Kg))は1〜70(ミリ当量/Kg)であり、好ましくは5〜50(ミリ当量/Kg)であり、更に好ましくは10〜30(ミリ当量/Kg)である。末端基封鎖剤であるモノカルボン酸あるいはモノアミンの含有量は、本発明者らの経験から、下記式により求まることがわかっている。すなわちASTM D789に準じて測定して求まる分子量(RV)、測定した末端カルボキシル基濃度[COOH]及び末端アミノ基濃度[NH2]を用いて、下記式から算出できる。
【0011】
重合度(DP)=((RV)/10−0 . 725)1/1 . 285
総末端基数(ミリ当量/Kg)=(2/DP)×106/226=([COOH]+[NH2]+[末端封鎖剤]
従って、
[末端封鎖剤]=(2/DP)×106/226−([COOH]+[NH2])
モノカルボン酸あるいはモノアミンの量が1(ミリ当量/Kg)未満の場合や70(ミリ当量/Kg)を超えた場合には、成形時の溶融粘度の安定性や熱分解成分による金型の汚染の改善効果が十分でない傾向にある。
【0012】
前記モノカルボン酸は、アミノ基との反応性を有するものであれば特に制限はないが、例えば酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、カプリル酸、ラウリン酸、トリデシル酸、ミリスチル酸、パルミチン酸、ステアリン酸、ピバリン酸、イソブチル酸などの脂肪族モノカルボン酸、シクロヘキサンカルボン酸などの脂環式モノカルボン酸、安息香酸、トルイル酸、α−ナフタレンカルボン酸、β−ナフタレンカルボン酸、メチルナフタレンカルボン酸、フェニル酢酸などの芳香族モノカルボン酸などを挙げることができる。本発明では、これらのモノカルボン酸を1種で用いても良いし、2種類以上組み合わせて用いても良い。本発明においては、これらモノカルボン酸の中でも、酢酸、安息香酸が好ましく用いられる。
【0013】
前記モノアミンとは、カルボキシル基との反応性を有するものであれば特に制限はないが、例えばメチルアミン、エチルアミン、プロピルアミン、ブチルアミン、ヘキシルアミン、オクチルアミン、デシルアミン、ステアリルアミン、ジメチルアミン、ジエチルアミン、ジプロピルアミン、ジブチルアミンなどの脂肪族モノアミン、シクロヘキシルアミン、ジシクロヘキシルアミンなどの脂環式モノアミン、アニリン、トルイジン、ジフェニルアミン、ナフチルアミンなどの芳香族モノアミンなどを挙げることができる。本発明では、これらのモノアミンを1種で用いても良いし、2種類以上組み合わせて用いても良い。
【0014】
本発明の共重合ポリアミド原料は、ポリアミド66原料、ポリアミド6原料ならびに末端封止剤として前記モノカルボン酸あるいはモノアミンを含有しているものである。
本発明におけるポリアミド66原料はアジピン酸とヘキサメチレンジアミンとの塩あるいは混合物あるいはそれらのオリゴマーであり、ポリアミド66原料は共重合ポリアミド原料中、90〜99.9重量%であり、好ましくは95〜99.5重量%、更に好ましくは97〜99.5重量%である。
【0015】
本発明におけるポリアミド6原料はε−カプロラクタムあるいはそのオリゴマーである。ポリアミド6原料は共重合ポリアミド原料中0.1〜10重量%であり、好ましくは0.5〜5重量%、更に好ましくは0.5〜3重量%でである。本発明における末端封鎖剤は前記ポリアミド66原料とポリアミド6原料とをからなる共重合ポリアミド原料中0.007〜0.4重量%であり、好ましくは0.01〜0.35重量%であり、更に好ましくは0.05〜0.2重量%である。ポリアミド66原料、ポリアミド6原料、末端封鎖剤が前記範囲を外れた場合には、成形時の溶融粘度の安定性や熱分解成分による金型の汚染の低減効果が不十分となったり、強度、靱性等の機械物性の低下が見られたりするため注意が必要である。
【0016】
なお、本発明の共重合ポリアミドには、本発明の目的を損なわない程度で、ポリアミド66、ポリアミド6以外、例えばポリアミド610、ポリアミド612、ポリアミド6T(T:テレフタル酸)、ポリアミド6I(I:イソフタル酸)などの他のポリアミド成分を混合あるいは共重合させてもかまわない。
本発明の共重合ポリアミド樹脂には、本発明の目的を損なわない範囲で、熱安定剤として銅化合物およびハロゲン銅以外のハロゲン化合物の混合物を加えることができる。かかる銅化合物としては、銅元素の金属化合物を挙げることができ、例えば、銅のハロゲン化物、硫酸塩、酢酸塩、プロピオオン酸塩、安息香酸塩、アジピン酸塩、テレフタル酸塩、サルチル酸塩、ニコチン酸塩、ステアリン酸塩や、エチレンジアミン(en)、エチレンジアミン四酢酸等のキレート化合物など、あるいはこれらの混合物を挙げることができる。この中でも、好ましいものとしては、ヨウ化銅、臭化第一銅、臭化第二銅、塩化第一銅、酢酸銅を挙げることができる。
【0017】
かかるハロゲン銅以外のハロゲン化合物は、臭素あるいはヨウ素と元素周期律表の1あるいは2族の金属元素との塩であり、好ましいものとしては、臭化カリウム、臭化ナトリウム、ヨウ化カリウム、ヨウ化ナトリウムなど、あるいはこれらの混合物を挙げることができ、中でも最も好ましいものとしては、ヨウ化カリウムを挙げることができる。
本発明の銅化合物とハロゲン銅以外のハロゲン化合物との配合量は、共重合ポリアミド100重量部に対して0.01〜1重量部であることが好ましく、0.05〜0.75重量部がより好ましく、0.05〜0.5重量部が最も好ましい。配合量が0.01未満の場合には、金型汚染の低減が顕著でなくなる傾向にあり、また1重量部を越えた場合には、靱性の低下を引き起こす懸念がある。
【0018】
本発明においては、銅化合物とハロゲン銅以外のハロゲン化合物とは、組み合わせて用いるが、金型汚染性がより改善されるという観点から、ハロゲン元素と銅元素とのモル比が1〜50の範囲が好ましく、10〜30の範囲がより好ましい。
共重合ポリアミドに銅化合物とハロゲン銅以外のハロゲン化合物を配合する方法は、例えば、該化合物を共重合ポリアミド原料に配合する方法、共重合ポリアミド重合過程で配合する方法、共重合ポリアミドペレット表面に付着させる方法、共重合ポリアミドに溶融混練法により配合する方法、マスターバッチとして共重合ポリアミドに配合する方法など、あるいはこれらの方法を組み合わせて配合する方法など、いずれの方法を用いてもかまわない。本発明においては、中でも共重合ポリアミド原料に配合する方法が好ましい方法として挙げることができる。
【0019】
本発明の共重合ポリアミドの好ましい重合方法は、より具体的には、ヘキサメチレンアジパミド、カプロラクタム、末端封止剤の共重合ポリアミド原料水溶液に、必要に応じて例えば、銅化合物とハロゲン銅以外のハロゲン化合物、消泡剤等を配合し、混合物を用いて、40〜300℃の温度下、加熱濃縮し、発生する水蒸気圧を常圧〜20気圧の間の圧力に保ち、最終的には圧力を抜き常圧あるいは減圧し重縮合を行う熱溶融重縮合法である。さらには、共重合ポリアミド重縮合物や共重合ポリアミド固体塩の融点以下の温度で行う固相重合法、ジカルボン酸ハライド、ラクタムのハライド、モノカルボン酸ハライド成分等を用いて溶液中で重縮合させる溶液法なども用いることができる。これらの方法は必要に応じて組み合わせてもかまわない。また、重合形態としては、バッチ式でも連続式でもかまわない。また、重合装置も特に制限されるものではなく、公知の装置、例えば、オートクレーブ型の反応器、タンブラー型反応器、ニーダーなどの押出機型反応器などを用いることができる。
【0020】
本発明の共重合ポリアミドの分子量は、ASTM D789に準じて測定して求まる分子量(RV)にして、20〜500が好ましく、25〜350がより好ましく、30〜300が最も好ましい。分子量(RV)は、溶媒として90重量%蟻酸水溶液を用いて、3gサンプル/30ml溶媒の濃度で、25℃の温度条件下で行う。分子量(RV)が20未満の場合には、靱性が低下する傾向にあり、また500以上は成形性が低下する傾向にある。
本発明における無機核剤は、共重合ポリアミドの核剤として作用する無機充填剤であれば特に限定されない。核剤とは、添加により熱示差走査分析(DSC)で測定される結晶化温度を向上させたり、得られる成形品の球晶を微細化あるいはサイズの均一化を行う核剤のことを言う。具体的にはウォラストナイト、タルク、マイカ、カオリン、硫酸バリウム、窒化珪素、層状ケイ酸塩、チタン酸カリウム、二硫化モリブデンなどを挙げることができる。
【0021】
本発明における無機核剤の添加量は、共重合ポリアミド樹脂100重量部に対し離型性の改良効果、剛性、強度、寸法安定性の観点から0.001重量部以上であり、靱性、ウエルド部強度あるいは熱分解成分の観点から1.0重量部以下である。好ましくは0.001〜0.5重量部であり、より好ましくは0.003〜0.45重量部であり、最も好ましくは0.005〜0.4重量部である。
本発明の共重合ポリアミド樹脂組成物の製造方法は、共重合ポリアミド樹脂に無機核剤を配合する方法であれば特に限定されるものではなく、例えば、共重合ポリアミド樹脂ペレット表面に無機核剤を付着させる方法、共重合ポリアミド樹脂に溶融混練法により無機核剤を配合する方法、無機核剤のマスターバッチを共重合ポリアミド樹脂に配合する方法など、あるいはこれらの方法を組み合わせて配合する方法など、いずれの方法を用いてもかまわない。本発明においては、中でも溶融混連法を用いて配合する方法が好ましい。
【0022】
前記溶融混練法を用いる場合には、溶融混練を行う装置としては、一般に実用されている混練機が適用できる。例えば、一軸または多軸混練押出機、ロール、バンバリーミキサーなどを用いれば良い。中でも、減圧装置、およびサイドフィーダー設備を装備した2軸押出機が最も好ましい。溶融混練の方法は、全成分を同時に混練を行ってもよく、あらかじめ予備混練したブレンド物を用いて混練する方法、更に押出機の途中から逐次、各成分をフィードし、混練を行ってもよい。溶融混練の条件は、特に制限されるものではないが、減圧度に関しては、0〜0.07MPa程度が好ましい。混練の温度は、JISK7121に準じた示差走査熱量(DSC)測定で求まる融点より1〜100℃程度高い温度が好ましい。混練機での剪断速度は100(SEC−1)以上程度であることが好ましく、混練時の平均滞留時間は、1〜15分程度が好ましい。樹脂組成物中の溶媒は1重量%程度以下であることが好ましい。上記範囲を外れた場合には、生産性が低下したり、成形加工性が低下したり、得られた成形品の外観が十分でなかったり、また物性の改良効果が十分でなかったりする場合がある。
【0023】
本発明の共重合ポリアミド樹脂組成物には、本発明の目的を損なわない程度で、ポリアミド樹脂に慣用的に用いられる添加剤、例えば顔料および染料、難燃剤、潤滑剤、蛍光漂白剤、可塑化剤、有機酸化防止剤、熱安定剤、紫外線吸収剤、核剤、ゴム、他のポリアミド、ポリアミド以外の樹脂並びに強化剤を含有することもできる。
本発明の共重合ポリアミド樹脂組成物は、公知の成形方法、例えばプレス成形、射出成形、ガスアシスト射出成形、溶着成形、押出成形、吹込成形、フィルム成形、中空成形、多層成形、溶融紡糸など、一般に知られているプラスチック成形方法を用いても、良好に成形加工ができる。中でも、射出成形性に優れる。
本発明における射出成形品は、射出成形により得られた成形品であれば特に限定はされないが、特に、結束バンド、タグピン等のハイサイクルが要求される薄肉成形品、形状が円筒状でかつネジ構造を有する嵌合部品用の成形品、更にはそり、寸法特性が要求される薄肉の平板状の成形品等に好適に利用される。
【0024】
【発明の実施の形態】
以下、本発明を実施例により更に詳細に説明するが、本発明はその要旨を越えない限り、以下の実施例に制限されるものではない。なお、以下の実施例、比較例において記載した物性評価は、以下のように行った。
1.共重合ポリアミド樹脂の特性
(1−1)分子量(RV)
溶媒として90%蟻酸を用いて、3gサンプル/30ml蟻酸の濃度で、25℃の温度条件下で行う。
【0025】
(1−2)末端基濃度
(a)カルボキシル基濃度[COOH](ミリ当量/Kg)
試料4.0gをベンジルアルコール50mlに170℃で溶解し、フェノールフタレインを指示薬として、1/10規定の水酸化ナトリウム溶液(エチレングリコール溶液)で中和滴定して求めた。
(b)アミノ基濃度[NH2](ミリ当量/Kg)
試料4.0gを90重量%フェノール50mlに50℃で溶解し、PHメーターを用い、1/20規定の塩酸で中和滴定して求めた。
(c)末端封鎖剤の含有量[末端封鎖剤](ミリ当量/Kg)
前記(1−1)の方法で求まる分子量(RV)、(1−2)の(a)及び(b)で求まる[COOH]及び[NH2]を用いて、下記式から算出できる。
重合度(DP)=((RV)/10−0 . 725)1/1 . 285
総末端基数(ミリ当量/Kg)=(2/DP)×106/226=([COOH]+[NH2]+[末端封鎖剤]
従って、
[末端封鎖剤]=(2/DP)×106/226−([COOH]+[NH2])
【0026】
2.共重合ポリアミド樹脂組成物の物性
(2−1)ペレットの熱分解によるガス成分の量(重量%)
12mgのペレットをTG−DTA装置(理学電機、Thermo Plus2 TG8120)にセットし、炉内に空気を30ml/minで流通させる空気雰囲気で測定した。温度条件は、100℃/分で室温から300℃まで昇温し、300℃で30分間保持した。300℃になった時の重量(W2)と300℃で30分間保持した後の重量(W3)を測定し、下記式からガス成分の量(重量%)を求めた。
ガス成分の量(重量%)=(W2−W3)×100/W2
【0027】
3.成形性
(3−1)離型性
図1に示すように、成形品の突き出しピン(エジェクターピン)にロードセルを設置した離型力測定装置を取り付けた金型を用いて、下記の成形条件で成形を行い、50ショットの離型力の測定を行い、平均値を算出した。
射出成形機:日精樹脂(株)製FN3000
金型:カップ状成形品
シリンダー温度:280℃
金型温度:80℃
射出圧力:40Mpa
射出時間:7秒
冷却時間:20秒
(3−2)可塑化性
離型性能の評価と同様に成形を行い、可塑化時にスクリューが後退するのに要する時間を測定し、50ショットの可塑化時間の平均値を求めた。
【0028】
4.機械物性
射出成形機(日精樹脂(株)製FN3000)を用いて、シリンダー温度300℃、金型温度80℃に設定し、射出14秒、冷却15秒の射出成形条件で評価用試験片を得た。
(4−1)曲げ弾性率および曲げ強度(MPa)
ASTM D790に準じて行った。
(4−2)引張り強度(MPa)および引張伸度(%)
ASTM D638に準じて行った。
(4−3)ウエルド強度
図2に示すようなウェルド部が形成される金型を用いて、射出成形し評価した。
(4−4)成形収縮率(%)
流動方向、直角方向、厚み方向がそれぞれ90mm、60mm、3mmの平板を成形し、流動方向と直角方向の成形収縮率を求めた。収縮率が小さいものほど、寸法安定性が高いと評価した。
【0029】
5.円筒状でネジ構造を有する嵌合部品の物性
射出成形機(東芝機械(株)製IS150)を用いて、シリンダー温度300℃、金型温度100℃に設定し、射出14秒、冷却30秒の射出成形条件で評価用試験片を得た。円筒状構造を有する筒状部材とネジ構造を有するボルト部品と両端ナット部品を射出成形し評価した。
(5−1)金型汚染性
ナット部の射出成形を30ショット行い、金型の汚れの状態を目視にて評価した。
○:金型がほとんど汚れていない。
△:金型の一部が汚れている。
×:金型が全面汚れている。
【0030】
(5−2)成形品の色調
ボルト部とナット部の成形品の色調を目視にて評価した。
○:成形品はほとんど着色せず白い。
△:成形品はやや着色しており、やや黄色い。
×:成形品の着色がひどく、褐色である。
(5−3)回動操作性
ボルトとナットを互いに嵌合させ、その回動操作時の円滑性の感触の良否、及びきしみ音の発生の有無で評価した。
○:円滑良好かつきしみ音無し
△:ある程度良好かつきしみ音無し
×:不良かつきしみ音有り
(5−4)圧縮試験
23℃×50%RHの雰囲気下で平衡吸水化させたナット部とボルト部を嵌合させ、東洋ボールドウイン(株)製圧縮試験機UTM−5Tを用い、製品高さL=580mm、歪み速度50mm/分で圧縮したときの圧縮強度を測定した。
【0031】
(製造例1)
共重合ポリアミド(1)の製造
共重合ポリアミド原料として、ポリアミド66原料(ヘキサメチレンジアミンとアジピン酸との等モル塩)1600Kgとポリアミド6原料(カプロラクタム)16Kgを含有する50重量%水溶液、末端封鎖剤として酢酸1.38Kgを用いた。この共重合ポリアミド原料水溶液にシリコーン系消泡剤55gを配合し、下部に抜出しノズルを有する約4000リットルのオートクレーブ中に仕込み、50℃の温度条件下で混合し窒素で置換した。次に温度を50℃から約150℃まで約1時間かけて昇温した。この際オートクレーブ内の圧力を、ゲージ圧にして約0.15MPaに保つため水を系外に除去しながら加熱を続けた。更にオートクレーブを密閉状態にし、温度を150℃から約220℃まで約1時間をかけて昇温して圧力をゲージ圧にして約1.77MPaまで上昇させた。
【0032】
その後、温度を約220℃から約280℃まで約1時間をかけて昇温するが、圧力は約1.77MPaで保つように水を系外に除去しながら加熱を行った。最後に、約1時間をかけて圧力を大気圧まで降圧し、大気圧になった後、下部ノズルからストランド状にポリマーを排出し、水冷、カッティングを行い共重合ポリアミド樹脂(1)ペレットを得た。得られたペレットを窒素気流中、90℃の条件下で4時間乾燥した。該共重合ポリアミド(1)ペレットの相対粘度(RV)は46.5であった。また、カールフィッシャー法で測定した水分率は0.20重量%であった。
【0033】
(製造例2)
共重合ポリアミド(2)の製造
共重合ポリアミド原料を、ポリアミド66原料(ヘキサメチレンジアミンとアジピン酸との等モル塩)1600Kgとポリアミド6原料(カプロラクタム)16Kgを含有する50重量%水溶液、末端封鎖剤として酢酸1.38Kgを用いた。この共重合ポリアミド原料水溶液に、ヨウ化銅0.265Kgとヨウ化カリウム4.38Kgの混合物、シリコーン系消泡剤55gを配合し、下部に抜出しノズルを有する約4000リットルのオートクレーブ中に仕込み、50℃の温度条件下で混合し窒素で置換した。次に温度を50℃から約150℃まで約1時間かけて昇温した。この際オートクレーブ内の圧力を、ゲージ圧にして約0.15MPaに保つため水を系外に除去しながら加熱を続けた。更にオートクレーブを密閉状態にし、温度を150℃から約220℃まで約1時間をかけて昇温して圧力をゲージ圧にして約1.77MPaまで上昇させた。その後、温度を約220℃から約280℃まで約1時間をかけて昇温するが、圧力は約1.77MPaで保つように水を系外に除去しながら加熱を行った。最後に、約1時間をかけて圧力を大気圧まで降圧し、大気圧になった後、下部ノズルからストランド状にポリマーを排出し、水冷、カッティングを行い共重合ポリアミド(2)ペレットを得た。得られたペレットを窒素気流中、90℃の条件下で10時間乾燥した。該共重合ポリアミド(2)ペレットの相対粘度(RV)は46.5であった。また、カールフィッシャー法で測定した水分率は0.08重量%であった。
【0034】
(製造例3)
共重合ポリアミド樹脂(3)の製造
末端封鎖剤として酢酸2.76Kgを用いる以外は、実施例1と同様にして実施した。
(製造例4)
共重合ポリアミド樹脂(4)の製造
共重合ポリアミド原料として、ポリアミド66原料(ヘキサメチレンジアミンとアジピン酸との等モル塩)1600Kgとポリアミド6原料(カプロラクタム)40Kgを含有する50重量%水溶液、末端封鎖剤として酢酸1.38Kgを用いる以外は、実施例1と同様にして実施した。
【0035】
(製造例5)
ポリアミド(5)の製造
ポリアミド原料として、ポリアミド66原料1600Kgのみを用いる以外は、製造例1と同様にして実施した。
(製造例6)
共重合ポリアミド(6)の製造
共重合ポリアミド原料に末端封鎖剤を添加せず、製造例1と同様にして実施した。
(製造例7)
共重合ポリアミド(7)の製造
末端封鎖剤として、酢酸7Kgを用いる以外は、製造例1と同様にして実施した。
【0036】
【実施例1】
共重合ポリアミド樹脂(1)に、無機核剤として窒化ホウ素0.005重量部、成形性改良剤として高級脂肪酸金属塩であるモンタン酸カルシウム0.1重量部、更には熱安定性改良剤としてIrganox1098(チバ・スペシャルティ・ケミカルズ(株)社製N,N‘−ヘキサン−1,6−ジイルビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオアミド])0.2重量部を混合し、二軸押出機(東芝機械(株)製TEM35)を用いて290℃の条件下で溶融混練してペレットを得た。更に該ペレットに対して、成形性改良剤としてモンタン酸カルシウム0.05重量部、及びポリエチレングルコール(日本油脂(株)PEG400)0.03重量部とをコーン型タンブラーを用いてブレンドして共重合ポリアミド樹脂組成物を得た。評価結果を表1に示す。
【0037】
【実施例2】
窒化ホウ素の代わりに、層状ケイ酸塩(コープケミカル(株)ソマシフMTE)0.5重量部を用いる以外は、実施例1と同様にして実施した。評価結果を表1に示す。
【0038】
【実施例3】
窒化ホウ素の代わりに、タルク0.01重量部を用いる以外は、実施例1と同様にして実施した。評価結果を表1に示す。
【0039】
【実施例4】
窒化ホウ素の代わりに、二硫化モリブデン0.01重量部を用いる以外は、実施例1と同様にして実施した。評価結果を表1に示す。
【0040】
【実施例5】
共重合ポリアミド樹脂(1)の代わりに、製造例3の共重合ポリアミド(2)を用いる以外は実施例1と同様にして実施した。評価結果を表2に示す。
【0041】
【実施例6】
共重合ポリアミド樹脂(1)の代わりに、製造例4の共重合ポリアミド(3)を用いる以外は実施例1と同様にして実施した。評価結果を表2に示す。
【0042】
【実施例7】
製造例2の共重合ポリアミド(2)100重量部に、無機核剤として窒化ホウ素0.005重量部、成形性改良剤として高級脂肪酸金属塩であるモンタン酸カルシウム0.1重量部、更には熱安定性改良剤としてIrganox1098(チバ・スペシャルティ・ケミカルズ(株)社製N,N‘−ヘキサン−1,6−ジイルビス[3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオアミド])0.2重量部を混合し、黒着色用のマスターバッチを混合し、二軸押出機(東芝機械(株)製TEM35)を用いて290℃の条件下で溶融混練してペレットを得た。更に該ペレット100重量部に対して、成形性改良剤としてモンタン酸カルシウム0.1重量部、及びポリエチレングルコール(日本油脂(株)PEG400)0.05重量部とをコーン型タンブラーを用いてブレンドして共重合ポリアミド樹脂組成物を得た。評価結果を表2に示す。
【0043】
【比較例1】
共重合ポリアミド樹脂(1)の代わりに、製造例5のポリアミド樹脂(5)を用いる以外は実施例1と同様にして実施した。評価結果を表3に示す。
【0044】
【比較例2】
共重合ポリアミド樹脂(1)の代わりに、製造例6の共重合ポリアミド樹脂(6)を用いる以外は実施例1と同様にして実施した。評価結果を3に示す。
【0045】
【比較例3】
共重合ポリアミド樹脂(1)の代わりに、製造例7の共重合ポリアミド樹脂(7)を用いる以外は実施例1と同様にして実施した。評価結果を表3に示す。
【0046】
【比較例4】
実施例1において、無機核剤である窒化ホウ素を添加しない以外は実施例1と同様にして実施した。評価結果を表3に示す。
【0047】
【比較例5】
実施例2において、層状ケイ酸塩の配合量を2.0重量部にする以外は実施例2と同様にして実施した。評価結果を表3に示す。
なお、前記実施例1〜7及び比較例1〜5に記載の無機核剤、成形性改良剤、熱安定剤などの各種添加剤の配合量は、共重合ポリアミドを100重量部として記載している。
【0048】
【表1】
【0049】
【表2】
【0050】
【表3】
【0051】
【発明の効果】
本発明における共重合ポリアミド樹脂組成物は、離型性などの成形性に優れ、成形時の溶融粘度の安定性に優れ、熱分解成分による金型の汚染が低減されるという優れた成形性を有し、かつ得られる成形品の強度、剛性、靱性、外観に優れ、かつ耐候性、吸水時剛性、真円性に優れる。特に射出成形においてその改良効果が顕著であるため、結束バンド、タグピン等のハイサイクルが要求される薄肉成形品、形状が円筒状でかつネジ構造を有する嵌合部品用の成形品、更にはそり、寸法特性が要求される薄肉の平板状の成形品等に好適に利用されることが期待される。
【図面の簡単な説明】
【図1】本発明の実施例、比較例の離型性能を評価するために用いた金型の断面図である。
【図2】本発明の実施例、比較例で用いたウエルド部を有する成形品を得るための金型の平面図である。
【符号の説明】
1;スプルランナー
2;カップ状成形品
3;エジェクターピン
4;エジェクタープレート
5;ロードセル
6;エジェクターロット゛
7;ウエルド部
8;スプル
9;ランナー
10;成形品[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention is excellent in moldability such as mold releasability and stability of melt viscosity at the time of molding suitable for industrial materials such as various mechanical industrial parts and electric and electronic parts, and reduces mold contamination due to thermal decomposition components. The present invention relates to a copolymerized polyamide resin composition having excellent strength, rigidity, toughness, and appearance, and excellent weatherability, rigidity upon water absorption, and roundness.
[0002]
[Prior art]
Polyamide is used as an engineering plastic in various applications such as automobile parts, electric parts, and industrial parts because of its excellent mechanical properties, heat resistance, chemical resistance, and the like. In recent years, the shape, thickness, and specialization of a polyamide resin molded product have become more complicated, and a polyamide resin capable of coping with this has been strongly demanded. Moreover, with the advancement of industry, the level of mechanical properties required for polyamide resin molded articles has been further improved. Furthermore, the molding time can be shortened from the viewpoint of economy, and the polyamide resin material that can improve the productivity can respond to the use of high cycle and recycled pellets from the viewpoint of economy and environmental problems. There is a strong demand for polyamide resin materials. Further, there is a demand for a highly durable polyamide resin material that can be used under severe environments where excessive external force or heat is applied.
[0003]
However, when a special molded product such as described above, for example, a molded product having a screw structure or a cylindrical molded product is made using a polyamide resin, the plasticization property and the releasability become insufficient, It was found that mold contamination based on gas components occurred due to the thermal decomposition of. Such a problem hinders continuous stable molding. In addition, the quality of the molded product is insufficient, such as insufficient roundness, poor weather resistance under the conditions of use especially when exposed to rain outdoors, and poor appearance of the molded product based on gas components. It has also been found that this results in a decrease. In order to improve these problems, a method using a copolyamide (for example, see
[0004]
[Patent Document 1]
JP-A-10-278065 [Patent Document 2]
JP 10-182850 A [Patent Document 3]
JP-A-11-42666
[Problems to be solved by the invention]
INDUSTRIAL APPLICABILITY The present invention is excellent in moldability such as mold releasability and stability of melt viscosity at the time of molding suitable for industrial materials such as various mechanical industrial parts and electric and electronic parts, and reduces mold contamination due to thermal decomposition components. An object of the present invention is to provide a copolymerized polyamide resin composition which is excellent in the strength, rigidity, toughness and appearance of a molded article obtained and is excellent in weather resistance, rigidity upon water absorption and roundness.
[0006]
[Means for Solving the Problems]
The present inventors have conducted intensive studies in order to solve the above-described problems of the present invention, and found that a specific amount of a specific inorganic nucleating agent was contained in a specific copolymer polyamide composed of
That is, the present invention
(1) It is composed of 90 to 99.9% by weight of polyamide 66 (hexamethylene adipamide) unit and 0.1 to 10% by weight of polyamide 6 (caproamide) unit, and has a terminal of monocarboxylic acid or monoamine of 1 to 70%. (Milliequivalent / Kg) Copolymerized polyamide resin composition characterized by containing 0.001 to 1 part by weight of inorganic nucleating agent (B) based on 100 parts by weight of blocked copolymerized polyamide (A). ,
[0007]
(2) A polyamide raw material composed of 90 to 99.9% by weight of a polyamide 66 raw material and 0.1 to 10% by weight of a
(3) An injection molded article obtained from the copolymerized polyamide resin composition according to any of (1) or (2) above,
It is. Hereinafter, the present invention will be described in detail.
[0008]
The copolymerized polyamide in the present invention contains polyamide 66 (hexamethylene adipamide), polyamide 6 (caproamide) and a monocarboxylic acid or monoamine as a terminal blocking agent.
The content of the polyamide 66 units in the copolymerized polyamide in the present invention is 90 to 99.9% by weight, more preferably 95 to 99.5% by weight, and still more preferably 97 to 99.5% by weight. .
[0009]
The content of 6 units of the polyamide in the copolymerized polyamide in the present invention is 0.1 to 10% by weight, preferably 0.5 to 5% by weight, and more preferably 0.5 to 3% by weight. The content of the polyamide 66 units and the
[0010]
The sum of [COOH] + [NH 2 ] of the terminal carboxyl group concentration [COOH] (milli-equivalent / Kg) and terminal amino group concentration (milli-equivalent / Kg) of the copolymerized polyamide of the present invention is about 50 to 200 (milli-equivalent). Equivalent / Kg), and the ratio [COOH] / [NH 2 ] is preferably in the range of about 0.1 to 10.
The copolymerized polyamide of the present invention contains a monocarboxylic acid or a monoamine as a terminal group blocking agent. The content of the terminal blocking agent ([terminal blocking agent] (meq / Kg)) is 1 to 70 (meq / Kg), preferably 5 to 50 (meq / Kg), and more preferably. 10 to 30 (meq / Kg). From the experience of the present inventors, it has been found that the content of the monocarboxylic acid or the monoamine as the terminal group blocking agent can be determined by the following formula. That is, it can be calculated from the following formula using the molecular weight (RV) determined according to ASTM D789, the measured terminal carboxyl group concentration [COOH] and the measured amino group concentration [NH 2 ].
[0011]
Degree of polymerization (DP) = ((RV) / 10 -0. 725) 1/1. 285
Total number of end groups (meq / Kg) = (2 / DP ) × 10 6/226 = ([COOH] + [NH 2] + [ endblocker]
Therefore,
[Endblocker] = (2 / DP) × 10 6/226 - ([COOH] + [NH 2])
If the amount of the monocarboxylic acid or the monoamine is less than 1 (meq / Kg) or exceeds 70 (meq / Kg), the stability of the melt viscosity at the time of molding and the contamination of the mold by the thermal decomposition component. Tend to have an insufficient improvement effect.
[0012]
The monocarboxylic acid is not particularly limited as long as it has reactivity with an amino group.For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristyl acid, Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, pivalic acid and isobutyric acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methyl Examples thereof include aromatic monocarboxylic acids such as naphthalene carboxylic acid and phenylacetic acid. In the present invention, these monocarboxylic acids may be used alone or in combination of two or more. In the present invention, among these monocarboxylic acids, acetic acid and benzoic acid are preferably used.
[0013]
The monoamine is not particularly limited as long as it has reactivity with a carboxyl group.For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, Examples thereof include aliphatic monoamines such as dipropylamine and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, and aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine. In the present invention, these monoamines may be used alone or in combination of two or more.
[0014]
The copolymerized polyamide raw material of the present invention contains the raw material of polyamide 66, the raw material of
The raw material of the polyamide 66 in the present invention is a salt or a mixture of adipic acid and hexamethylenediamine or an oligomer thereof, and the raw material of the polyamide 66 is 90 to 99.9% by weight, preferably 95 to 99% by weight in the raw material of the copolymerized polyamide. 0.5% by weight, more preferably 97 to 99.5% by weight.
[0015]
The raw material of
[0016]
The copolymerized polyamide of the present invention includes polyamide 66 and
To the copolymerized polyamide resin of the present invention, a mixture of a copper compound and a halogen compound other than halogenated copper can be added as a heat stabilizer as long as the object of the present invention is not impaired. Examples of such copper compounds include metal compounds of copper elements, such as copper halides, sulfates, acetates, propionates, benzoates, adipates, terephthalates, salicylates, Examples thereof include nicotinic acid salts, stearic acid salts, chelating compounds such as ethylenediamine (en) and ethylenediaminetetraacetic acid, and the like, and mixtures thereof. Among them, preferred are copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate.
[0017]
Such a halogen compound other than copper halide is a salt of bromine or iodine with a metal element belonging to
The compounding amount of the copper compound of the present invention and the halogen compound other than halogen copper is preferably 0.01 to 1 part by weight, and more preferably 0.05 to 0.75 part by weight based on 100 parts by weight of the copolymerized polyamide. More preferably, 0.05 to 0.5 part by weight is most preferable. If the amount is less than 0.01, the reduction in mold contamination tends to be insignificant, and if it exceeds 1 part by weight, there is a concern that the toughness may be reduced.
[0018]
In the present invention, a copper compound and a halogen compound other than halogen copper are used in combination, but from the viewpoint that mold contamination is further improved, the molar ratio between the halogen element and the copper element is in the range of 1 to 50. Is preferable, and the range of 10 to 30 is more preferable.
The method of blending a copper compound and a halogen compound other than halogen copper in the copolymerized polyamide is, for example, a method of blending the compound into the raw material of the copolymerized polyamide, a method of blending it in the copolymerization polyamide polymerization process, and a method of adhering to the surface of the copolymerized polyamide pellet. Any of these methods may be used, such as a method of mixing, a method of compounding with a copolymerized polyamide by a melt-kneading method, a method of compounding as a masterbatch with a copolymerized polyamide, or a method of combining these methods. In the present invention, among them, a method of blending with the raw material of the copolymerized polyamide can be mentioned as a preferable method.
[0019]
Preferred polymerization method of the copolymerized polyamide of the present invention, more specifically, hexamethylene adipamide, caprolactam, an aqueous solution of the copolymerized polyamide raw material of the terminal blocking agent, if necessary, for example, except copper compound and halogen copper The mixture is heated and concentrated at a temperature of 40 to 300 ° C., and the generated steam pressure is maintained at a pressure between normal pressure and 20 atm. This is a hot-melt polycondensation method in which pressure is released and normal pressure or reduced pressure is applied to perform polycondensation. Further, a solid-phase polymerization method carried out at a temperature equal to or lower than the melting point of the copolyamide polycondensate or copolyamide solid salt, polycondensation in solution using a dicarboxylic acid halide, a lactam halide, a monocarboxylic acid halide component, or the like. A solution method or the like can also be used. These methods may be combined as needed. Further, the polymerization form may be a batch type or a continuous type. The polymerization apparatus is not particularly limited, and a known apparatus, for example, an extruder-type reactor such as an autoclave-type reactor, a tumbler-type reactor, or a kneader can be used.
[0020]
The molecular weight of the copolymerized polyamide of the present invention is preferably 20 to 500, more preferably 25 to 350, and most preferably 30 to 300, as a molecular weight (RV) determined by measuring according to ASTM D789. The molecular weight (RV) is measured at a temperature of 25 ° C. using a 90% by weight formic acid aqueous solution as a solvent at a concentration of 3 g sample / 30 ml solvent. When the molecular weight (RV) is less than 20, the toughness tends to decrease, and when it is 500 or more, the moldability tends to decrease.
The inorganic nucleating agent in the present invention is not particularly limited as long as it is an inorganic filler acting as a nucleating agent for the copolymerized polyamide. The nucleating agent refers to a nucleating agent that increases the crystallization temperature measured by thermal differential scanning analysis (DSC) by adding, or refines the spherulites or uniforms the size of the obtained molded article. Specific examples include wollastonite, talc, mica, kaolin, barium sulfate, silicon nitride, layered silicate, potassium titanate, molybdenum disulfide, and the like.
[0021]
The addition amount of the inorganic nucleating agent in the present invention is 0.001 part by weight or more from the viewpoint of the effect of improving releasability, rigidity, strength, and dimensional stability with respect to 100 parts by weight of the copolymerized polyamide resin, It is 1.0 part by weight or less from the viewpoint of strength or thermal decomposition component. Preferably it is 0.001-0.5 weight part, More preferably, it is 0.003-0.45 weight part, Most preferably, it is 0.005-0.4 weight part.
The method for producing the copolymerized polyamide resin composition of the present invention is not particularly limited as long as it is a method of blending an inorganic nucleating agent into the copolymerized polyamide resin. A method of adhering, a method of blending an inorganic nucleating agent into a copolymerized polyamide resin by a melt-kneading method, a method of blending a master batch of an inorganic nucleating agent into a copolymerized polyamide resin, or a method of combining these methods, Either method may be used. In the present invention, a method of blending using the melt mixing method is particularly preferable.
[0022]
In the case of using the above-mentioned melt-kneading method, a kneader generally used can be applied as an apparatus for performing the melt-kneading. For example, a single-screw or multi-screw kneading extruder, a roll, a Banbury mixer, or the like may be used. Among them, a twin-screw extruder equipped with a decompression device and a side feeder is most preferable. The method of melt kneading may be kneading all the components at the same time, a method of kneading using a preliminarily kneaded blend, further feeding the components sequentially from the middle of the extruder, and kneading. . The conditions for melt-kneading are not particularly limited, but the degree of reduced pressure is preferably about 0 to 0.07 MPa. The kneading temperature is preferably about 1 to 100 ° C. higher than the melting point determined by differential scanning calorimetry (DSC) measurement according to JIS K7121. The shear rate in the kneader is preferably about 100 (SEC -1 ) or more, and the average residence time during kneading is preferably about 1 to 15 minutes. The solvent in the resin composition is preferably about 1% by weight or less. If it is out of the above range, the productivity may be reduced, the molding processability may be reduced, the appearance of the obtained molded product may not be sufficient, or the effect of improving the physical properties may not be sufficient. is there.
[0023]
The copolymerized polyamide resin composition of the present invention contains, to the extent that the purpose of the present invention is not impaired, additives commonly used in polyamide resins, such as pigments and dyes, flame retardants, lubricants, fluorescent bleaching agents, plasticizing agents. Agents, organic antioxidants, heat stabilizers, ultraviolet absorbers, nucleating agents, rubbers, other polyamides, resins other than polyamides, and reinforcing agents.
The copolymerized polyamide resin composition of the present invention is a known molding method, for example, press molding, injection molding, gas assist injection molding, welding molding, extrusion molding, blow molding, film molding, hollow molding, multilayer molding, melt spinning, and the like. Even if a generally known plastic molding method is used, molding can be performed well. Among them, it is excellent in injection moldability.
The injection-molded article of the present invention is not particularly limited as long as it is a molded article obtained by injection molding, but in particular, a thin-walled molded article requiring a high cycle such as a binding band, a tag pin, and a cylindrical and screw-shaped article. It is suitably used for molded products for fitting parts having a structure, and also for warp, thin flat molded products requiring dimensional characteristics, and the like.
[0024]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In addition, the physical property evaluation described in the following Examples and Comparative Examples was performed as follows.
1. Properties of copolymerized polyamide resin (1-1) Molecular weight (RV)
The reaction is performed at a temperature of 25 ° C. at a concentration of 3 g sample / 30 ml formic acid using 90% formic acid as a solvent.
[0025]
(1-2) Terminal group concentration (a) Carboxyl group concentration [COOH] (milliequivalent / Kg)
A sample (4.0 g) was dissolved in benzyl alcohol (50 ml) at 170 ° C., and neutralized and titrated with a 1/10 N sodium hydroxide solution (ethylene glycol solution) using phenolphthalein as an indicator.
(B) Amino group concentration [NH 2 ] (milliequivalent / Kg)
4.0 g of a sample was dissolved in 50 ml of 90% by weight phenol at 50 ° C., and neutralized and titrated with 1/20 N hydrochloric acid using a PH meter.
(C) Content of terminal blocking agent [terminal blocking agent] (milliequivalent / Kg)
The molecular weight (RV) determined by the method (1-1) and [COOH] and [NH 2 ] determined by (a) and (b) of (1-2) can be calculated from the following equation.
Degree of polymerization (DP) = ((RV) / 10 -0. 725) 1/1. 285
Total number of end groups (meq / Kg) = (2 / DP ) × 10 6/226 = ([COOH] + [NH 2] + [ endblocker]
Therefore,
[Endblocker] = (2 / DP) × 10 6/226 - ([COOH] + [NH 2])
[0026]
2. Physical Properties of Copolyamide Resin Composition (2-1) Amount (% by weight) of gas component due to thermal decomposition of pellet
A 12 mg pellet was set in a TG-DTA device (Rigaku Corporation, Thermo Plus2 TG8120), and the measurement was performed in an air atmosphere in which air was flown at 30 ml / min in the furnace. The temperature was raised from room temperature to 300 ° C. at a rate of 100 ° C./min, and kept at 300 ° C. for 30 minutes. The weight (W 2 ) at 300 ° C. and the weight (W 3 ) after holding at 300 ° C. for 30 minutes were measured, and the amount (% by weight) of the gas component was determined from the following equation.
Amount of gas component (% by weight) = (W 2 −W 3 ) × 100 / W 2
[0027]
3. Moldability (3-1) Release Property As shown in FIG. 1, using a mold equipped with a release force measuring device in which a load cell is installed on an ejector pin (ejector pin) of a molded product under the following molding conditions: Molding was performed, the release force of 50 shots was measured, and the average was calculated.
Injection molding machine: FN3000 manufactured by Nissei Plastics Co., Ltd.
Mold: Cup-shaped molded product Cylinder temperature: 280 ° C
Mold temperature: 80 ° C
Injection pressure: 40Mpa
Injection time: 7 seconds Cooling time: 20 seconds (3-2) Plasticization Molding was performed in the same manner as in the evaluation of mold release performance, the time required for the screw to retract during plasticization was measured, and 50 shots were plasticized. The average value of time was determined.
[0028]
4. Using an injection molding machine (FN3000 manufactured by Nissei Plastics Co., Ltd.), a test piece for evaluation was obtained under the conditions of cylinder temperature 300 ° C. and mold temperature 80 ° C., and injection molding conditions of injection 14 seconds and cooling 15 seconds. Was.
(4-1) Flexural modulus and flexural strength (MPa)
Performed according to ASTM D790.
(4-2) Tensile strength (MPa) and tensile elongation (%)
Performed according to ASTM D638.
(4-3) Weld strength Injection molding was performed using a mold having a weld portion as shown in FIG. 2 and evaluated.
(4-4) Mold shrinkage (%)
Flat plates having a flow direction, a right angle direction and a thickness direction of 90 mm, 60 mm and 3 mm, respectively, were formed, and the molding shrinkage in the direction perpendicular to the flow direction was determined. The smaller the shrinkage, the higher the dimensional stability.
[0029]
5. Using a physical property injection molding machine (IS150 manufactured by Toshiba Machine Co., Ltd.) of a fitting part having a cylindrical screw structure, the cylinder temperature was set at 300 ° C. and the mold temperature was set at 100 ° C., and injection was performed for 14 seconds and cooling was performed for 30 seconds. Test pieces for evaluation were obtained under injection molding conditions. A cylindrical member having a cylindrical structure, a bolt part having a screw structure, and a nut part at both ends were injection molded and evaluated.
(5-1) Injection molding of the mold contamination nut portion was performed by 30 shots, and the stain condition of the mold was visually evaluated.
:: The mold is hardly stained.
Δ: Part of the mold is dirty.
×: The mold is entirely dirty.
[0030]
(5-2) Color tone of molded product The color tone of the molded product at the bolt portion and the nut portion was visually evaluated.
:: The molded product is white with almost no coloring.
Δ: The molded product is slightly colored and slightly yellow.
X: The molded article is severely colored and brown.
(5-3) Rotational operability The bolt and the nut were fitted with each other, and the quality of smoothness during the rotation operation was evaluated as to whether or not squeak noise was generated.
:: Good smoothness and no squealing sound △: Somewhat good and no squealing sound ×: Poor and squealing sound Were fitted to each other, and the compression strength when the product was compressed at a product height L of 580 mm and a strain rate of 50 mm / min was measured using a compression tester UTM-5T manufactured by Toyo Baldwin Co., Ltd.
[0031]
(Production Example 1)
Production of Copolyamide (1) A 50% by weight aqueous solution containing 1600 kg of polyamide 66 raw material (equimolar salt of hexamethylenediamine and adipic acid) and 16 kg of
[0032]
Thereafter, the temperature was raised from about 220 ° C. to about 280 ° C. over about 1 hour, and heating was performed while removing water from the system so as to maintain the pressure at about 1.77 MPa. Finally, the pressure is reduced to the atmospheric pressure in about one hour, and after the pressure is reduced to the atmospheric pressure, the polymer is discharged in a strand form from the lower nozzle, water-cooled and cut to obtain a copolymerized polyamide resin (1) pellet. Was. The obtained pellets were dried in a nitrogen stream at 90 ° C. for 4 hours. The relative viscosity (RV) of the copolymer polyamide (1) pellet was 46.5. Further, the water content measured by the Karl Fischer method was 0.20% by weight.
[0033]
(Production Example 2)
Production of Copolyamide (2) A 50% by weight aqueous solution containing 1600 kg of a raw material of polyamide 66 (equimolar salt of hexamethylenediamine and adipic acid) and 16 kg of a raw material of polyamide 6 (caprolactam), and a terminal blocking agent Of acetic acid was used. A mixture of 0.265 Kg of copper iodide and 4.38 Kg of potassium iodide and 55 g of a silicone-based antifoaming agent were blended with this aqueous solution of the raw material of the copolymerized polyamide, and charged in an autoclave of about 4000 liters having a discharge nozzle at the bottom, and The mixture was mixed under a temperature condition of ° C. and replaced with nitrogen. Next, the temperature was raised from 50 ° C. to about 150 ° C. over about 1 hour. At this time, heating was continued while removing water from the system in order to keep the pressure in the autoclave at a gauge pressure of about 0.15 MPa. Further, the autoclave was closed, and the temperature was raised from 150 ° C. to about 220 ° C. over about 1 hour, and the pressure was increased to a gauge pressure of about 1.77 MPa. Thereafter, the temperature was raised from about 220 ° C. to about 280 ° C. over about 1 hour, and heating was performed while removing water from the system so as to maintain the pressure at about 1.77 MPa. Finally, the pressure was reduced to the atmospheric pressure over about one hour, and after the pressure was reduced to the atmospheric pressure, the polymer was discharged in a strand form from the lower nozzle, water-cooled and cut to obtain a copolymerized polyamide (2) pellet. . The obtained pellets were dried in a nitrogen stream at 90 ° C. for 10 hours. The relative viscosity (RV) of the copolymer polyamide (2) pellet was 46.5. The water content measured by the Karl Fischer method was 0.08% by weight.
[0034]
(Production Example 3)
Production of copolymerized polyamide resin (3) The production was carried out in the same manner as in Example 1 except that 2.76 kg of acetic acid was used as a terminal blocking agent.
(Production Example 4)
Production of Copolyamide Resin (4) As a copolyamide raw material, a 50% by weight aqueous solution containing 1600 kg of a raw material of polyamide 66 (equimolar salt of hexamethylenediamine and adipic acid) and 40 kg of a raw material of polyamide 6 (caprolactam); The procedure was performed in the same manner as in Example 1 except that 1.38 kg of acetic acid was used as an agent.
[0035]
(Production Example 5)
Production of Polyamide (5) The same procedure as in Production Example 1 was carried out except that only 1600 kg of a polyamide 66 raw material was used as a polyamide raw material.
(Production Example 6)
Production of Copolyamide (6) The production was carried out in the same manner as in Production Example 1 without adding a terminal blocking agent to the raw material of the copolyamide.
(Production Example 7)
Production of copolymerized polyamide (7) The production was carried out in the same manner as in Production Example 1, except that 7 kg of acetic acid was used as a terminal blocking agent.
[0036]
0.005 parts by weight of boron nitride as an inorganic nucleating agent, 0.1 part by weight of calcium montanate which is a higher fatty acid metal salt as a moldability improving agent, and Irganox 1098 as a thermal stability improving agent were added to the copolymerized polyamide resin (1). (0.2 parts by weight of N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide] manufactured by Ciba Specialty Chemicals Co., Ltd.) Were mixed and melt-kneaded at 290 ° C. using a twin-screw extruder (TEM35, manufactured by Toshiba Machine Co., Ltd.) to obtain pellets. Further, 0.05 parts by weight of calcium montanate as a moldability improver and 0.03 parts by weight of polyethylene glycol (PEG400, Nippon Oil & Fats Co., Ltd.) were blended with the pellets by using a cone type tumbler. A polymerized polyamide resin composition was obtained. Table 1 shows the evaluation results.
[0037]
The procedure was carried out in the same manner as in Example 1, except that 0.5 parts by weight of a layered silicate (COP-Chemical Co., Ltd. Somasif MTE) was used instead of boron nitride. Table 1 shows the evaluation results.
[0038]
Embodiment 3
The procedure was performed in the same manner as in Example 1 except that 0.01 part by weight of talc was used instead of boron nitride. Table 1 shows the evaluation results.
[0039]
Embodiment 4
The procedure was performed in the same manner as in Example 1 except that 0.01 part by weight of molybdenum disulfide was used instead of boron nitride. Table 1 shows the evaluation results.
[0040]
Embodiment 5
The procedure was performed in the same manner as in Example 1 except that the copolymerized polyamide (2) of Production Example 3 was used instead of the copolymerized polyamide resin (1). Table 2 shows the evaluation results.
[0041]
The procedure was performed in the same manner as in Example 1 except that the copolymerized polyamide (3) of Production Example 4 was used instead of the copolymerized polyamide resin (1). Table 2 shows the evaluation results.
[0042]
To 100 parts by weight of the copolymerized polyamide (2) of Production Example 2, 0.005 parts by weight of boron nitride as an inorganic nucleating agent, 0.1 part by weight of calcium montanate, which is a higher fatty acid metal salt, as a moldability improver, and further, heat Irganox 1098 (N, N'-hexane-1,6-diylbis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propioamide manufactured by Ciba Specialty Chemicals Co., Ltd.) as a stability improver ) 0.2 parts by weight, a masterbatch for black coloring was mixed, and melt-kneaded at 290 ° C using a twin-screw extruder (TEM35 manufactured by Toshiba Machine Co., Ltd.) to obtain pellets. . Further, 0.1 part by weight of calcium montanate as a moldability improver and 0.05 part by weight of polyethylene glycol (PEG400, a Japan Oil & Fats Co., Ltd.) are blended with 100 parts by weight of the pellets using a cone type tumbler. As a result, a copolymerized polyamide resin composition was obtained. Table 2 shows the evaluation results.
[0043]
[Comparative Example 1]
The procedure was performed in the same manner as in Example 1 except that the polyamide resin (5) of Production Example 5 was used instead of the copolymerized polyamide resin (1). Table 3 shows the evaluation results.
[0044]
[Comparative Example 2]
The procedure was performed in the same manner as in Example 1 except that the copolymerized polyamide resin (6) of Production Example 6 was used instead of the copolymerized polyamide resin (1). The evaluation results are shown in 3.
[0045]
[Comparative Example 3]
The procedure was performed in the same manner as in Example 1 except that the copolymerized polyamide resin (7) of Production Example 7 was used instead of the copolymerized polyamide resin (1). Table 3 shows the evaluation results.
[0046]
[Comparative Example 4]
Example 1 was carried out in the same manner as in Example 1 except that boron nitride as an inorganic nucleating agent was not added. Table 3 shows the evaluation results.
[0047]
[Comparative Example 5]
Example 2 was carried out in the same manner as in Example 2 except that the amount of the layered silicate was changed to 2.0 parts by weight. Table 3 shows the evaluation results.
In addition, the compounding amount of various additives such as the inorganic nucleating agent, the moldability improver, and the heat stabilizer described in the above Examples 1 to 7 and Comparative Examples 1 to 5 is described assuming that the copolymer polyamide is 100 parts by weight. I have.
[0048]
[Table 1]
[0049]
[Table 2]
[0050]
[Table 3]
[0051]
【The invention's effect】
The copolymerized polyamide resin composition of the present invention has excellent moldability such as excellent moldability such as mold releasability, excellent stability of melt viscosity at the time of molding, and reduced contamination of a mold by a thermal decomposition component. It has excellent strength, stiffness, toughness, and appearance, and excellent weatherability, rigidity when absorbing water, and roundness. In particular, since the improvement effect is remarkable in injection molding, a thin-walled molded product such as a binding band or a tag pin requiring a high cycle, a molded product for a fitting part having a cylindrical shape and a screw structure, and further, a warp It is expected to be suitably used for a thin-walled flat molded product requiring dimensional characteristics.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view of a mold used for evaluating the release performance of an example of the present invention and a comparative example.
FIG. 2 is a plan view of a mold for obtaining a molded product having a weld portion used in Examples and Comparative Examples of the present invention.
[Explanation of symbols]
1;
Claims (3)
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2006273945A (en) * | 2005-03-28 | 2006-10-12 | Asahi Kasei Chemicals Corp | Production method for polyamide resin composition |
JP2007246561A (en) * | 2006-03-13 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin molded article |
WO2017110918A1 (en) * | 2015-12-25 | 2017-06-29 | 東レ株式会社 | End-modified polyamide resin and method for producing same |
JP2017210544A (en) * | 2016-05-25 | 2017-11-30 | 株式会社豊田中央研究所 | Low-linear-expansion polyamide resin composition and polyamide resin molding composed of the same |
WO2018101054A1 (en) * | 2016-11-29 | 2018-06-07 | 東レ株式会社 | Terminally modified polyamide resin |
WO2022048663A1 (en) * | 2020-09-07 | 2022-03-10 | 军事科学院系统工程研究院军需工程技术研究所 | Method for preparing functionalized polyamide 56 short fibers |
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Cited By (12)
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JP2006273945A (en) * | 2005-03-28 | 2006-10-12 | Asahi Kasei Chemicals Corp | Production method for polyamide resin composition |
JP2007246561A (en) * | 2006-03-13 | 2007-09-27 | Asahi Kasei Chemicals Corp | Polyamide resin molded article |
WO2017110918A1 (en) * | 2015-12-25 | 2017-06-29 | 東レ株式会社 | End-modified polyamide resin and method for producing same |
JP6172409B1 (en) * | 2015-12-25 | 2017-08-02 | 東レ株式会社 | Terminal-modified polyamide resin and method for producing the same |
CN108137799A (en) * | 2015-12-25 | 2018-06-08 | 东丽株式会社 | Terminal-modified polyamide and its manufacturing method |
KR20180098223A (en) * | 2015-12-25 | 2018-09-03 | 도레이 카부시키가이샤 | -Termodified polyamide resin and method for producing the same |
KR102000896B1 (en) | 2015-12-25 | 2019-07-16 | 도레이 카부시키가이샤 | -Termodified polyamide resin and method for producing the same |
CN108137799B (en) * | 2015-12-25 | 2020-01-07 | 东丽株式会社 | Terminal-modified polyamide resin and method for producing same |
US10556989B2 (en) | 2015-12-25 | 2020-02-11 | Toray Industries, Inc. | End-modified polyamide resin and method for producing same |
JP2017210544A (en) * | 2016-05-25 | 2017-11-30 | 株式会社豊田中央研究所 | Low-linear-expansion polyamide resin composition and polyamide resin molding composed of the same |
WO2018101054A1 (en) * | 2016-11-29 | 2018-06-07 | 東レ株式会社 | Terminally modified polyamide resin |
WO2022048663A1 (en) * | 2020-09-07 | 2022-03-10 | 军事科学院系统工程研究院军需工程技术研究所 | Method for preparing functionalized polyamide 56 short fibers |
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