JP2005263927A - Polyacetal resin composition - Google Patents
Polyacetal resin composition Download PDFInfo
- Publication number
- JP2005263927A JP2005263927A JP2004076928A JP2004076928A JP2005263927A JP 2005263927 A JP2005263927 A JP 2005263927A JP 2004076928 A JP2004076928 A JP 2004076928A JP 2004076928 A JP2004076928 A JP 2004076928A JP 2005263927 A JP2005263927 A JP 2005263927A
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- JP
- Japan
- Prior art keywords
- polyacetal resin
- weight
- parts
- component
- resin composition
- 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
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- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 66
- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 60
- 239000011342 resin composition Substances 0.000 title claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 43
- 239000011347 resin Substances 0.000 claims abstract description 43
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 30
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 21
- 239000000194 fatty acid Substances 0.000 claims abstract description 21
- 229930195729 fatty acid Natural products 0.000 claims abstract description 21
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 13
- 229920001515 polyalkylene glycol Polymers 0.000 claims abstract description 6
- 150000001408 amides Chemical class 0.000 claims abstract description 5
- 230000007246 mechanism Effects 0.000 claims description 15
- 238000001746 injection moulding Methods 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000000465 moulding Methods 0.000 abstract description 10
- 230000002542 deteriorative effect Effects 0.000 abstract description 2
- 238000012545 processing Methods 0.000 abstract description 2
- -1 fatty acid ester Chemical class 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002156 mixing Methods 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 239000008188 pellet Substances 0.000 description 6
- 229940000635 beta-alanine Drugs 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000012760 heat stabilizer Substances 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 150000005846 sugar alcohols Polymers 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 4
- 239000011354 acetal resin Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002828 fuel tank Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229920006122 polyamide resin Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FCKXGFANXSHGAW-DTXPUJKBSA-N (2s)-n,n'-bis[(2s)-1-(2-chloro-4-nitroanilino)-1-oxo-3-phenylpropan-2-yl]-2-hydroxybutanediamide Chemical compound C([C@H](NC(=O)C[C@H](O)C(=O)N[C@@H](CC=1C=CC=CC=1)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C(=O)NC=1C(=CC(=CC=1)[N+]([O-])=O)Cl)C1=CC=CC=C1 FCKXGFANXSHGAW-DTXPUJKBSA-N 0.000 description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-Tetramethylpiperidine Substances CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 3
- PQJZHMCWDKOPQG-UHFFFAOYSA-N 2-anilino-2-oxoacetic acid Chemical compound OC(=O)C(=O)NC1=CC=CC=C1 PQJZHMCWDKOPQG-UHFFFAOYSA-N 0.000 description 3
- 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
- 229920000877 Melamine resin Polymers 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 3
- 239000012964 benzotriazole Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- LHPPDQUVECZQSW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-ditert-butylphenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1O LHPPDQUVECZQSW-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 159000000007 calcium salts Chemical class 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- LSFBQOPXRBJSSI-UHFFFAOYSA-L calcium;tetradecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O LSFBQOPXRBJSSI-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- OKRSVCKJPLEHEY-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) acetate Chemical compound CC(=O)OC1CC(C)(C)NC(C)(C)C1 OKRSVCKJPLEHEY-UHFFFAOYSA-N 0.000 description 1
- KPQYTXOCFDUOQL-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) n-cyclohexylcarbamate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)NC1CCCCC1 KPQYTXOCFDUOQL-UHFFFAOYSA-N 0.000 description 1
- GSTKDOVQEARANU-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) n-phenylcarbamate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)NC1=CC=CC=C1 GSTKDOVQEARANU-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- QLAFGHVZDNLIDW-UHFFFAOYSA-N 1-[3-(benzotriazol-2-yl)-5-(3-methylbutyl)phenyl]-3-methylbutan-2-ol Chemical compound CC(C)CCC1=CC(CC(O)C(C)C)=CC(N2N=C3C=CC=CC3=N2)=C1 QLAFGHVZDNLIDW-UHFFFAOYSA-N 0.000 description 1
- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- BWJKLDGAAPQXGO-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-octadecoxypiperidine Chemical compound CCCCCCCCCCCCCCCCCCOC1CC(C)(C)NC(C)(C)C1 BWJKLDGAAPQXGO-UHFFFAOYSA-N 0.000 description 1
- IUKIOUVQRQCBOX-UHFFFAOYSA-N 2,2,6,6-tetramethyl-4-phenoxypiperidine Chemical compound C1C(C)(C)NC(C)(C)CC1OC1=CC=CC=C1 IUKIOUVQRQCBOX-UHFFFAOYSA-N 0.000 description 1
- MKTJWUMCSNLAOX-UHFFFAOYSA-N 2,2-bis(2,2,6,6-tetramethylpiperidin-4-yl)propanedioic acid Chemical compound C1C(C)(C)NC(C)(C)CC1C(C(O)=O)(C(O)=O)C1CC(C)(C)NC(C)(C)C1 MKTJWUMCSNLAOX-UHFFFAOYSA-N 0.000 description 1
- IXNXCCLDPLCSJK-UHFFFAOYSA-N 2,4,6-tris(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,3,5-tricarboxylic acid Chemical compound C1C(C)(C)NC(C)(C)CC1C1=C(C(O)=O)C(C2CC(C)(C)NC(C)(C)C2)=C(C(O)=O)C(C2CC(C)(C)NC(C)(C)C2)=C1C(O)=O IXNXCCLDPLCSJK-UHFFFAOYSA-N 0.000 description 1
- ITLDHFORLZTRJI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-5-octoxyphenol Chemical compound OC1=CC(OCCCCCCCC)=CC=C1N1N=C2C=CC=CC2=N1 ITLDHFORLZTRJI-UHFFFAOYSA-N 0.000 description 1
- OMCYEZUIYGPHDJ-UHFFFAOYSA-N 2-hydroxy-N-[(2-hydroxyphenyl)methylideneamino]benzamide Chemical compound OC1=CC=CC=C1C=NNC(=O)C1=CC=CC=C1O OMCYEZUIYGPHDJ-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
- MWANTFVULLQTHU-UHFFFAOYSA-N 3,5,6-tris(2,2,6,6-tetramethylpiperidin-4-yl)benzene-1,2,4-tricarboxylic acid Chemical compound C1C(C)(C)NC(C)(C)CC1C(C(=C(C1CC(C)(C)NC(C)(C)C1)C(C(O)=O)=C1C(O)=O)C(O)=O)=C1C1CC(C)(C)NC(C)(C)C1 MWANTFVULLQTHU-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- ACQVGHUCSAVFRL-UHFFFAOYSA-N 4-[1,4-dimethyl-6-(2,2,6,6-tetramethylpiperidin-4-yl)oxycyclohexa-2,4-dien-1-yl]oxy-2,2,6,6-tetramethylpiperidine Chemical group CC1(NC(CC(C1)OC1(C(C=C(C=C1)C)OC1CC(NC(C1)(C)C)(C)C)C)(C)C)C ACQVGHUCSAVFRL-UHFFFAOYSA-N 0.000 description 1
- HWQKEDNHWREBQJ-UHFFFAOYSA-N 4-methyl-2-(triazol-2-yl)phenol Chemical compound CC1=CC=C(O)C(N2N=CC=N2)=C1 HWQKEDNHWREBQJ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- IUPCCEURIZKZNX-UHFFFAOYSA-N C(C1=CC=CC=C1)OC1CC(NC(C1)(C)C)(C)C.C1(CCCCC1)OC1CC(NC(C1)(C)C)(C)C Chemical compound C(C1=CC=CC=C1)OC1CC(NC(C1)(C)C)(C)C.C1(CCCCC1)OC1CC(NC(C1)(C)C)(C)C IUPCCEURIZKZNX-UHFFFAOYSA-N 0.000 description 1
- OBCGQZURKAMABT-UHFFFAOYSA-N C(N)(OC(C(CCCCOC(N)=O)C1CC(NC(C1)(C)C)(C)C)(C1CC(NC(C1)(C)C)(C)C)C1CC(NC(C1)(C)C)(C)C)=O Chemical compound C(N)(OC(C(CCCCOC(N)=O)C1CC(NC(C1)(C)C)(C)C)(C1CC(NC(C1)(C)C)(C)C)C1CC(NC(C1)(C)C)(C)C)=O OBCGQZURKAMABT-UHFFFAOYSA-N 0.000 description 1
- AGGDCJKITASIEK-UHFFFAOYSA-N COC1CC(NC(C1)(C)C)(C)C.C(C1=CC=CC=C1)(=O)OC1CC(NC(C1)(C)C)(C)C.C1(=CC=CC=C1)CC(=O)OC1CC(NC(C1)(C)C)(C)C Chemical compound COC1CC(NC(C1)(C)C)(C)C.C(C1=CC=CC=C1)(=O)OC1CC(NC(C1)(C)C)(C)C.C1(=CC=CC=C1)CC(=O)OC1CC(NC(C1)(C)C)(C)C AGGDCJKITASIEK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920003189 Nylon 4,6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- GHJBIWHWRNKOFW-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,4-dicarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=C(C(=O)OC2CC(C)(C)NC(C)(C)C2)C=C1 GHJBIWHWRNKOFW-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- UROGBLCMTWAODF-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) hexanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 UROGBLCMTWAODF-UHFFFAOYSA-N 0.000 description 1
- GMHDUYXGKJNFHH-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) oxalate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C(=O)OC1CC(C)(C)NC(C)(C)C1 GMHDUYXGKJNFHH-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000447 dimerizing effect Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- PFBWBEXCUGKYKO-UHFFFAOYSA-N ethene;n-octadecyloctadecan-1-amine Chemical compound C=C.CCCCCCCCCCCCCCCCCCNCCCCCCCCCCCCCCCCCC PFBWBEXCUGKYKO-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000020778 linoleic acid Nutrition 0.000 description 1
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- CQDGTJPVBWZJAZ-UHFFFAOYSA-N monoethyl carbonate Chemical compound CCOC(O)=O CQDGTJPVBWZJAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-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
- RDDGGSBCDBLPDO-UHFFFAOYSA-N octadecyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C)=C(O)C(C(C)(C)C)=C1 RDDGGSBCDBLPDO-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000005702 oxyalkylene group Chemical group 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- VLCLHFYFMCKBRP-UHFFFAOYSA-N tricalcium;diborate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]B([O-])[O-].[O-]B([O-])[O-] VLCLHFYFMCKBRP-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Description
本発明は、ポリアセタール樹脂の本来有する優れた機械的特性を実質上全く損なうことなく、成形加工時の離型性を極めて高度に改善すると同時に、あわせて耐熱エージング性、耐熱水性といった長期熱安定性にも優れたポリアセタール樹脂組成物及びそれを用いて得られた精密機構部品に関する。 The present invention improves the releasability at the time of molding processing to a very high degree without substantially damaging the excellent mechanical properties inherent in the polyacetal resin, and at the same time, provides long-term thermal stability such as heat aging resistance and water resistance. The present invention also relates to an excellent polyacetal resin composition and a precision mechanism component obtained using the same.
ポリアセタール樹脂は、バランスのとれた機械的性質、優れた耐摩擦磨耗性を有しており、自動車、電気・電子機器、建材等の諸分野で広範囲の用途に使用されている。
また、殆どの場合、その成形は射出成形によっており、機械部品、精密機構部品としての用途が多いポリアセタール樹脂の場合、それら成形品の構造は複雑な場合が多い。複雑な構造の一例として例えば、単一成形品において厚肉部と薄肉部、更には超薄肉部が互いに入り組んだ上、更に中空円筒状突起物等が備わっている等の形状等があるが、それらはまた、数グラムから高々数十グラム程度の重量の小物部品の場合が多い。このような複雑な形状の成形品の場合、溶融樹脂がシリンダーから射出され金型内で冷却された後の、成形品の突き出し離型はできるだけスムーズでなければならない。何故なら、成形された複雑形状の製品を過度に強い力で突き出し離型した場合、製品は破損した状態で得られたり、また、破損を生じないまでも、過度の力で離型された場合、製品において過度の力を受けた箇所は成形歪みを製品内部に保存することになり、製品が長期にわたって使用される場合、それらの影響がやがて悪く露呈し、いずれの場合も極めて好ましくない。
Polyacetal resins have well-balanced mechanical properties and excellent frictional wear resistance, and are used in a wide range of applications in various fields such as automobiles, electrical / electronic devices, and building materials.
In most cases, the molding is performed by injection molding. In the case of polyacetal resin, which is often used as mechanical parts and precision mechanism parts, the structures of these molded products are often complicated. As an example of a complicated structure, for example, there is a shape in which a thick part and a thin part, and furthermore, an ultra-thin part are intertwined in a single molded product, and further provided with a hollow cylindrical projection etc. They are also often small parts weighing from a few grams to a few tens of grams at most. In the case of such a molded product having a complicated shape, the molded product should be ejected and released as smoothly as possible after the molten resin is injected from the cylinder and cooled in the mold. This is because when a molded product with a complicated shape is ejected with an excessively strong force and released, the product is obtained in a damaged state, or when it is released with an excessive force until it does not break. When the product is subjected to excessive force, the molding distortion is stored inside the product, and when the product is used for a long period of time, the influence of the product will eventually be worsened, which is extremely undesirable in either case.
ポリアセタール樹脂は、エンジニアリングプラスチックとして求められる性質の殆どを備えた極めて有用な材料であるがゆえに、前述の如き用途において使用されているものであるが、それらの性質に加えて更に極めて優れた流動性を有しているため、必然的に複雑な形状の製品に用いられる場合が多くなり、前述の理由によりできうる限り小さな離型力で製品が得られることが説に望まれるのである。 Polyacetal resin is an extremely useful material that has most of the properties required for engineering plastics, so it is used in applications such as those described above. In addition to these properties, it has extremely superior fluidity. Therefore, it is inevitably used in products with complicated shapes, and it is theoretically desired that the product be obtained with as little release force as possible for the above-mentioned reasons.
離型性を改良する方法として、これまで次に示す種々の方法が提案されている。
例えば、リノール酸を二量化することによって得られるダイマー酸の金属塩をアセタール樹脂に添加する方法(例えば、特許文献1参照)、アセタール樹脂に炭素数22〜32の高級脂肪酸の1種以上を添加する方法(例えば、特許文献2参照)、アセタール樹脂100重量部に対し炭素数2〜10を有する多価アルコールと炭素数22〜32を有する高級脂肪酸とから誘導される多価アルコール脂肪酸エステルの1種以上を0.01〜2.0重量部又は該多価アルコール脂肪酸エステルの1種以上0.01〜2.0重量部と炭素数10以上の直鎖を有する高級脂肪酸アミドの1種以上0.01〜2.0重量部とを配合する方法(例えば、特許文献3参照)、アセタール樹脂100重量部に対して、末端エーテル化ポリアルキレングリコールの1種以上を0.01〜5重量部と炭素数2〜10の多価アルコールと炭素数22〜32の高級脂肪酸とから誘導される多価アルコール脂肪酸エステルの1種以上を0.01〜2重量部配合する方法(例えば、特許文献4参照)、ポリアセタール樹脂100重量部に対し、炭素数4以上のアルキレン基を持つアルキレンビスステアリルアミドを0.1〜5重量部配合する方法(例えば、特許文献5参照)、ポリオキシメチレン樹脂100重量部に、例えばアルコールへのアルキレンオキシド付加物のような特定のエーテル化合物を0.01〜20重量部、及び特定のPHと粒径を有するタルク1〜30重量部を添加混合する方法(例えば、特許文献6参照)、ポリアセタール樹脂100重量部に対し、特定のアルキル置換ジフェニルエーテルを0.1〜5重量部配合する方法(例えば、特許文献7参照)、ポリアセタール樹脂100重量部に対し、液状変性エチレン・α−オレフィン系重合体0.2〜25重量部を配合する方法(例えば、特許文献8参照)などが例示できる。
The following various methods have been proposed as methods for improving the releasability.
For example, a method of adding a metal salt of dimer acid obtained by dimerizing linoleic acid to an acetal resin (see, for example, Patent Document 1), adding one or more higher fatty acids having 22 to 32 carbon atoms to the acetal resin 1 of polyhydric alcohol fatty acid ester derived from polyhydric alcohol having 2 to 10 carbon atoms and higher fatty acid having 22 to 32 carbon atoms with respect to 100 parts by weight of acetal resin 0.01 to 2.0 parts by weight of one or more species or one or more of 0.01 to 2.0 parts by weight of the polyhydric alcohol fatty acid ester and one or more higher fatty acid amides having a straight chain having 10 or more carbon atoms .01-2.0 parts by weight (for example, see Patent Document 3), terminal etherified polyalkylene glycol with respect to 100 parts by weight of acetal resin One or more kinds of polyhydric alcohol fatty acid esters derived from 0.01 to 5 parts by weight, a polyhydric alcohol having 2 to 10 carbon atoms and a higher fatty acid having 22 to 32 carbon atoms are added to 0.01 to 2 A method of blending parts by weight (for example, see Patent Document 4), a method of blending 0.1 to 5 parts by weight of alkylenebisstearylamide having an alkylene group having 4 or more carbon atoms with respect to 100 parts by weight of a polyacetal resin (for example, patents) Reference 5), to 100 parts by weight of polyoxymethylene resin, 0.01 to 20 parts by weight of a specific ether compound such as an alkylene oxide adduct to alcohol, and talc having a specific pH and particle size of 1 to 20 A method of adding and mixing 30 parts by weight (for example, see Patent Document 6), a specific alkyl-substituted diphenyl ether with respect to 100 parts by weight of a polyacetal resin A method of blending 0.1 to 5 parts by weight (for example, see Patent Document 7), a method of blending 0.2 to 25 parts by weight of a liquid modified ethylene / α-olefin polymer with respect to 100 parts by weight of a polyacetal resin (for example, , See Patent Document 8).
これらの方法により離型力はかなり低下するものの、ポリアセタール樹脂の長所である機械的特性が低下する場合が多い。また、近年従来より複雑な部品形状がより要求されるようになり、このような超複雑部品では依然として高い離型力が必要で、部品破損が発生する場合がある。更に、これらの超複雑部品に用いられるポリアセタール樹脂にも従来より高い機械的特性が要求されるようになり、より高分子量のポリアセタール樹脂や、より結晶化度の高い高融点のコポリマーやホモポリマーが用いられる場合が増加している。分子量が高くなるとポリアセタール樹脂の流動性が低下し、目標寸法の成形品が得られにくい。また、結晶化度が高くなると成形収縮率が大きくなり、同じく目標寸法の成形品が得られにくくなる。そして、目標寸法の成形品が得られないと、それに付随して離型力が極端に高くなる場合が多い。 Although the release force is considerably reduced by these methods, the mechanical properties which are the advantages of the polyacetal resin are often lowered. In recent years, more complex part shapes have been required than ever before, and such super-complex parts still require a high release force and may cause damage to the parts. In addition, polyacetal resins used in these ultra-complex parts are required to have higher mechanical properties than before, and higher molecular weight polyacetal resins, higher crystallinity, high melting point copolymers and homopolymers are available. Increasing use. When the molecular weight increases, the fluidity of the polyacetal resin decreases, and it is difficult to obtain a molded product having a target dimension. Further, when the degree of crystallinity increases, the molding shrinkage rate increases, and it becomes difficult to obtain a molded product having the same target size. If a molded product having a target dimension is not obtained, the release force is often extremely increased.
また、連続射出成形する場合に、金型形状によっては、離型力が安定せず、当初低かった離型力が成形ショット数に比例して徐々に上昇する現象が発生する場合もある。これに対する一般的な対策としては、離型力が許容限界を超える前に金型に市販の離型剤を塗布する方法があるが、操作が煩雑であるばかりでなく、市販の離型剤が成形品表面に付着し精密な電子・電気機器等では汚染源となって嫌われる場合があるためできるだけ離型剤を塗布せずに長期連続安定的に射出成形できるのが好ましい。
更に、超複雑部品においては、その形状の複雑さゆえ、成形品に歪みが残りやすく、これらを高温雰囲気や、熱水雰囲気といった過酷な条件下で用いた場合に歪み残留箇所に早期にクラックが発生し、部品が破壊してしまうといった問題が発生する場合がある。
Further, in the case of continuous injection molding, depending on the mold shape, the release force may not be stable, and a phenomenon may occur in which the release force initially low gradually increases in proportion to the number of molding shots. As a general countermeasure against this, there is a method of applying a commercially available release agent to the mold before the release force exceeds the allowable limit, but not only is the operation complicated, but a commercially available release agent is Since it may be disliked as a contamination source when it adheres to the surface of a molded product and is a precise electronic / electrical device, it is preferable that injection molding can be stably performed over a long period of time without applying a release agent as much as possible.
Furthermore, because of the complexity of the shape of ultra-complex parts, distortion tends to remain in the molded product, and when these are used under harsh conditions such as high-temperature atmospheres or hot water atmospheres, cracks are left early in the strain-remaining parts. There is a case where a problem occurs that the parts are destroyed.
本発明は、機械的特性を低下させることなく、射出成形時の離型力を低下させると共に、その低い離型力を長期連続射出成形時にも安定性に発現させ、同時に、得られた成形部品の耐熱エージング性及び耐熱水性をも改良するポリアセタール樹脂組成物並びにその樹脂組成物を成形して得られる精密機構部品を提供することを目的とする。 The present invention reduces the mold release force at the time of injection molding without deteriorating the mechanical characteristics, and also exhibits the low mold release force in the stability at the time of long-term continuous injection molding, and at the same time, the obtained molded part It is an object of the present invention to provide a polyacetal resin composition that also improves the heat aging resistance and water resistance of water and a precision mechanism component obtained by molding the resin composition.
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、ポリアセタール樹脂に、少なくとも1種の炭素数12〜22を有する高級脂肪酸由来のN,N‘−エチレンビス脂肪酸アミドと少なくとも1種の数平均分子量3000〜20000のポリアルキレングリコールを各々特定量添加することによりその目的を達成できることを見出し、この知見に基づいて本発明をなすに至った。
すなわち、本発明は、
(1)(A)ポリアセタール樹脂100重量部に対して、(B)炭素数12〜22を有する高級脂肪酸由来のN,N‘−エチレンビス脂肪酸アミドの少なくとも1種を0.25〜0.35重量部および(C)数平均分子量3000〜20000のポリアルキレングリコールの少なくとも1種を前記(B)成分の1/4〜1/2倍重量部添加してなるポリアセタール樹脂組成物、
As a result of intensive studies to solve the above problems, the present inventors have found that polyacetal resin contains at least one N, N′-ethylenebisfatty acid amide derived from a higher fatty acid having 12 to 22 carbon atoms and at least one. The inventors have found that the purpose can be achieved by adding specific amounts of polyalkylene glycols having a number average molecular weight of 3000 to 20000, respectively, and based on this finding, the present invention has been made.
That is, the present invention
(1) (B) At least one kind of N, N′-ethylenebisfatty acid amide derived from a higher fatty acid having 12 to 22 carbon atoms is added to 0.25 to 0.35 with respect to 100 parts by weight of (A) polyacetal resin. A polyacetal resin composition comprising at least one part by weight of (C) a polyalkylene glycol having a number average molecular weight of 3000 to 20000 and 1/4 to 1/2 times by weight of the component (B),
(2)(B)成分がN,N‘−エチレンビスステアリルアミドであり、かつ(C)成分がポリエチレングリコールである前記1記載のポリアセタール樹脂組成物、
(3)(C)成分が、数平均分子量5000〜10000のポリエチレングリコールである前記1又は2記載のポリアセタール樹脂組成物、
(4)(A)成分に安定剤が添加されたポリアセタール樹脂である前記1〜3のいずれかに記載のポリアセタール樹脂、
(5)(1)〜(4)のいずれかに記載のポリアセタール樹脂組成物を射出成形して得られる精密機構部品、
(6)自動車部品に用いられる前記5に記載の精密機構部品、
に関する。
(2) The polyacetal resin composition according to 1 above, wherein the component (B) is N, N′-ethylenebisstearylamide and the component (C) is polyethylene glycol.
(3) The polyacetal resin composition according to 1 or 2, wherein the component (C) is a polyethylene glycol having a number average molecular weight of 5000 to 10,000,
(4) The polyacetal resin according to any one of 1 to 3, which is a polyacetal resin obtained by adding a stabilizer to the component (A),
(5) Precision mechanism parts obtained by injection molding the polyacetal resin composition according to any one of (1) to (4),
(6) The precision mechanism part as described in 5 above, which is used for automobile parts,
About.
本発明のポリアセタール樹脂組成物は、ポリアセタール樹脂の本来有する優れた機械的特性を実質上全く損なうことなく、成形加工時の離型性が極めて高度に改善されている。したがって、複雑形状を有するような精密機構部品の射出成形用ポリアセタール樹脂として好適である。また、本発明のポリアセタール樹脂は耐熱エージング性、耐熱水性といった長期熱安定性にも優れているため、これらの性能が特に要求される自動車関係部品、特に燃料タンクフランジなどの燃料回り部品や、シートベルト巻き取り機構などのシートベルト回り部品用として特に好適である。 In the polyacetal resin composition of the present invention, the releasability at the time of molding is extremely improved without substantially impairing the excellent mechanical properties inherent in the polyacetal resin. Therefore, it is suitable as a polyacetal resin for injection molding of precision mechanism parts having complicated shapes. In addition, since the polyacetal resin of the present invention is excellent in long-term thermal stability such as heat aging resistance and hot water resistance, parts related to automobiles such as fuel tank flanges, seats such as fuel tank flanges, and seats particularly required for these performances. It is particularly suitable for parts around a seat belt such as a belt winding mechanism.
以下、本願発明について具体的に説明する。
本発明で用いられる(A)成分のポリアセタール樹脂とは、ホルムアルデヒド単量体又は、その3量体(トリオキサン)若しくは4量体(テトラオキサン)等の環状オリゴマーを原料として製造された実質的にオキシメチレン単位の繰り返しよりなるポリオキシメチレンホモポリマーまたは、上記原料とエチレンオキサイド、プロピレンオキサイド、エピクロルヒドリン、1,3−ジオキソラン、グリコールのホルマール、ジグリコールのホルマール等の環状エーテルとから製造された、炭素数2〜8のオキシアルキレン単位を0.1〜20重量%、好ましくは0.2〜10重量%含有するオキシメチレンコポリマー、更に架橋や分岐状分子鎖を有するものや、オキシメチレン単位とオキシエチレン単位やオキシプロピレン単位、メチレン単位、プロピレン単位などのオキシメチレン単位と異なる繰り返し単位を有するポリオキシメチレンブロックコポリマーなどを包含する。また、上記した種々のポリアセタール樹脂の混合物であってもよい。
Hereinafter, the present invention will be specifically described.
The polyacetal resin of component (A) used in the present invention is a substantially oxymethylene produced using a formaldehyde monomer or a cyclic oligomer such as a trimer (trioxane) or tetramer (tetraoxane) as a raw material. A polyoxymethylene homopolymer consisting of repeating units, or the above raw material and a cyclic ether such as ethylene oxide, propylene oxide, epichlorohydrin, 1,3-dioxolane, glycol formal, diglycol formal, etc. An oxymethylene copolymer containing 0.1 to 20% by weight, preferably 0.2 to 10% by weight of -8 oxyalkylene units, further having a crosslinked or branched molecular chain, oxymethylene units and oxyethylene units, Oxypropylene unit, methylene unit And polyoxymethylene block copolymers having repeating units different from oxymethylene units such as propylene units. Moreover, the mixture of various polyacetal resin mentioned above may be sufficient.
本発明のポリアセタール樹脂組成物のメルトインデックス(MI:g/10分)に特に制限はないが、本発明の組成物は、射出成形が難しいポリアセタール樹脂に特に有効で、具体的には、高分子量で流動性の低い、例えばMIが5g/10min以下のポリアセタール樹脂が上げられる。また、ポリオキシメチレンホモポリマーは結晶化速度が非常に早く、また、結晶化度が高いゆえに成形後の収縮率が大きく、そのため成形品の寸法不良が発生しやすく、その結果として、成形品の離型不良が発生する場合が多いが、本願発明の組成物はこれらホモポリマーの離型改良に非常に有効である。 The melt index (MI: g / 10 min) of the polyacetal resin composition of the present invention is not particularly limited, but the composition of the present invention is particularly effective for polyacetal resins that are difficult to be injection-molded. And a polyacetal resin having low fluidity, for example, MI of 5 g / 10 min or less. In addition, polyoxymethylene homopolymer has a very high crystallization rate and a high degree of crystallinity, resulting in a large shrinkage ratio after molding, which tends to cause dimensional defects in the molded product. In many cases, defective release occurs, but the composition of the present invention is very effective for improving the release of these homopolymers.
本発明の(B)成分である炭素数12〜22を有する高級脂肪酸由来のN,N‘−エチレンビス脂肪酸アミドの高級脂肪酸としては、直鎖構造を持つものが好ましく、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸などの飽和脂肪酸及びオレイン酸、エルカ酸などの不飽和脂肪酸を代表例としてあげることができる。本発明の効果を発現させるために最も好ましいのは、N,N‘−エチレンビスステアリルアミドであり、これら(B)成分は2種類以上を組み合わせて用いることも可能である。また、(B)成分は(A)ポリアセタール樹脂100重量部に対して0.25〜0.35重量部添加される。0.25重量部より少ないと離型性の改良が十分でない。0.35重量部より多いと機械的特性が低下し、また、耐熱エージング性、耐熱水性も悪化するため好ましくない。本願発明の効果を発揮させるためには、0.25〜0.35重量部という非常に限定された範囲内での添加のみが有効である。 As the higher fatty acid of N, N′-ethylenebisfatty acid amide derived from higher fatty acid having 12 to 22 carbon atoms which is component (B) of the present invention, those having a linear structure are preferred, lauric acid, myristic acid, Representative examples include saturated fatty acids such as palmitic acid, stearic acid, and behenic acid, and unsaturated fatty acids such as oleic acid and erucic acid. In order to express the effect of the present invention, N, N′-ethylenebisstearylamide is most preferable, and these (B) components can be used in combination of two or more. Moreover, (B) component is added 0.25-0.35 weight part with respect to 100 weight part of (A) polyacetal resin. If the amount is less than 0.25 parts by weight, the releasability is not sufficiently improved. When the amount is more than 0.35 parts by weight, the mechanical properties are deteriorated, and the heat aging resistance and the hot water resistance are also deteriorated. In order to exhibit the effects of the present invention, only addition within a very limited range of 0.25 to 0.35 parts by weight is effective.
本願発明の(C)成分であるポリアルキレングリコールとしては、ポリエチレングリコール、ポリプロピレングリコールを代表例としてあげることができる。本願発明においては、特にポリエチレングリコールが好ましく、中でも数平均分子量3000〜20000、特に5000〜10000のものが好ましい。数平均分子量が小さすぎても、大きすぎても離型性の改良効果が十分でない。これら(C)成分は2種類以上を組み合わせて用いることも可能である。また、(C)成分の添加量は(B)成分の1/4〜1/2倍重量部添加することが必要である。1/4倍重量部より少ないと、離型性改良効果、特に低い離型力を長期安定的に発現させることができない。また、1/2倍重量部より多いと、機械的特性が低下し好ましくない。 Typical examples of the polyalkylene glycol which is the component (C) of the present invention include polyethylene glycol and polypropylene glycol. In the present invention, polyethylene glycol is particularly preferable, and among these, a number average molecular weight of 3000 to 20000, particularly 5000 to 10,000 is preferable. If the number average molecular weight is too small or too large, the effect of improving the releasability is not sufficient. These (C) components can be used in combination of two or more. Moreover, it is necessary that the addition amount of the component (C) is 1/4 to 1/2 times by weight of the component (B). When the amount is less than 1/4 times by weight, the effect of improving the releasability, particularly the low releasability, cannot be expressed stably for a long time. On the other hand, when the amount is more than 1/2 times by weight, the mechanical properties are lowered, which is not preferable.
本願発明においては、非常に限定された範囲量の(B)成分と(C)成分が同時にポリアセタール樹脂に添加されていることが必須であり、このことによって、初期の離型力を大幅に低減できると同時にその低い離型力を長期安定的に発現することができる。さらに、機械的特性を実質的に低下させることなく、あわせて耐熱エージング性、耐熱水性も向上する。極めて限定された範囲の(B)成分と(C)成分との相乗効果により、これら効果が発現されることはこれまで全く知られておらず新規なものである。
本願発明の組成物に用いられる安定剤としては、例えば熱安定剤、耐候(光)安定剤等を単独またはこれらを組み合わせて用いることができる。熱安定剤としては、酸化防止剤、ホルムアルデヒドや蟻酸の補足剤およびこれらの併用が効果を発揮する。
In the present invention, it is essential that the components (B) and (C) in a very limited range are simultaneously added to the polyacetal resin, thereby greatly reducing the initial release force. At the same time, the low release force can be stably expressed for a long time. Furthermore, heat aging resistance and hot water resistance are also improved without substantially reducing the mechanical properties. It has not been known so far and is novel because of the synergistic effect of component (B) and component (C) in a very limited range.
As the stabilizer used in the composition of the present invention, for example, a heat stabilizer, a weather resistance (light) stabilizer, or the like can be used alone or in combination. As heat stabilizers, antioxidants, formaldehyde and formic acid supplements and combinations thereof are effective.
酸化防止剤としては、ヒンダードフェノール系酸化防止剤が好ましい。例えば、n−オクタデシル−3−(3´5´−ジ−t−ブチル−4´−ヒドロキシフェニル)−プロピオネート、n−オクタデシル−3−(3´−メチルー5´−t−ブチル−4´−ヒドロキシフェニル)−プロピオネート、n−テトラデシル−3−(3´5´−ジ−t−ヒドロキシフェニル)−プロピオネート、1、6−ヘキサンジオール−ビス−(3−(3、5−ジ−t−ブチル−4−ヒドロキシフェニル)−プロピオネート、1、4−ブタンジオール−ビス−(3−(3、5−ジ−t−ブチル−4−ヒドロキシフェニル)−プロピオネート、トリエチレングリコール−ビス−(3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)−プロピオネート)である。 As the antioxidant, a hindered phenol antioxidant is preferable. For example, n-octadecyl-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl-5′-t-butyl-4′- Hydroxyphenyl) -propionate, n-tetradecyl-3- (3'5'-di-t-hydroxyphenyl) -propionate, 1,6-hexanediol-bis- (3- (3,5-di-t-butyl) -4-hydroxyphenyl) -propionate, 1,4-butanediol-bis- (3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, triethylene glycol-bis- (3- ( 3-t-butyl-5-methyl-4-hydroxyphenyl) -propionate).
また、テトラキス−(メチレン−3−(3´5´−ジ−t−ブチル−4´−ヒドロキシフェニル)−プロピオネートメタン、3、9−ビス(2−(3−(3−t−ブチル−4−ヒドロキシ−5−メチルフェニル)プロピオニルオキシ)1、1−ジメチルエチル)2、4、8、10−テトラオキサスピロ(5、5´)ウンデカン、N、N´−ビス−3−(3´、5´−ジ−t−ブチル−4−ヒドロキシフェノール)プリピオニルヘキサメチレンジアミン、N、N´−テトラメチレンビス−3−(3´−メチル−5´−t−ブチル−4−ヒドロキシフェノール)プリピオニルジアミン、N、N´−ビス−3−(3´、5´−ジ−t−ブチル−4−ヒドロキシフェノール)プリピオニル)ヒドラジン、N−サリチロイル−N´−サリチリデンヒドラジン、3−(N−サリチロイル)アミン−1、2、4−トリアゾール、N、N´−ビス−(2−(3−(3、5−ジ−ブチル−4−ヒドロキシフェニル)プロピオニルオキシ)エチル)オキシアミド等がある。 Tetrakis- (methylene-3- (3′5′-di-t-butyl-4′-hydroxyphenyl) -propionate methane, 3,9-bis (2- (3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propionyloxy) 1,1-dimethylethyl) 2,4,8,10-tetraoxaspiro (5,5 ') undecane, N, N'-bis-3- (3 '5'-di-t-butyl-4-hydroxyphenol) priionyl hexamethylenediamine, N, N'-tetramethylenebis-3- (3'-methyl-5'-t-butyl-4-hydroxy Phenol) pripionyldiamine, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenol) prepionyl) hydrazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amine-1,2,4-triazole, N, N′-bis- (2- (3- (3,5-di-butyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide and the like is there.
これらヒンダードフェノール系酸化防止剤のなかでも、トリエチレングリコール−ビス−(3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)−プロピオネート)、テトラキス−(メチレン−3−(3´5´−ジ−t−ブチル−4´−ヒドロキシフェニル)−プロピオネートメタンが好ましい。これらの酸化防止剤はポリアセタール樹脂100重量部に対して、0.01〜3重量部、好ましくは0.05〜2重量部、さらに好ましくは0.1〜1重量部ぼ範囲で用いられる。
ホルムアルデヒドや蟻酸の補足剤としては、(イ)ホルムアルデヒド反応性窒素を含む化合物および重合体、(ロ)アルカリ金属またはアルカリ土類金属の水酸化物、無機酸塩およびカルボン酸塩が挙げられる。
Among these hindered phenolic antioxidants, triethylene glycol-bis- (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate), tetrakis- (methylene-3- (3 '5'-di-t-butyl-4'-hydroxyphenyl) -propionate methane. These antioxidants are 0.01 to 3 parts by weight, preferably 0, based on 100 parts by weight of the polyacetal resin. 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight.
Examples of formaldehyde and formic acid scavengers include (a) compounds and polymers containing formaldehyde-reactive nitrogen, and (b) alkali metal or alkaline earth metal hydroxides, inorganic acid salts, and carboxylate salts.
(イ)ホルムアルデヒド反応性窒素を含む化合物および重合体としては、ジシアンアミド、メラミン、メラミンとホルムアルデヒドとの化合物、ポリアミド樹脂(例えば、ナイロン46、6、66、610、612、12、66−6、66−66−10、66−12等)、ポリ−β−アラニン、ポリアクリルアミド等が挙げられる。これらのなかでは、メラミンとホルムアルデヒドとの共縮合物、ポリアミド樹脂、ポリ−β−アラニン、ポリアクリルアミドが好ましく、ポリアミド樹脂、ポリ−β−アラニンがさらに好ましい。これらはポリアセタール樹脂100重量部に対して、0.001〜5重量部、好ましくは0.005〜3重量部、さらに好ましくは0.01〜2重量部である。 (I) Formaldehyde-reactive nitrogen-containing compounds and polymers include dicyanamide, melamine, melamine and formaldehyde compounds, polyamide resins (for example, nylon 46, 6, 66, 610, 612, 12, 66-6, 66 -66-10, 66-12, etc.), poly-β-alanine, polyacrylamide and the like. Among these, a cocondensate of melamine and formaldehyde, a polyamide resin, poly-β-alanine, and polyacrylamide are preferable, and a polyamide resin and poly-β-alanine are more preferable. These are 0.001-5 weight part with respect to 100 weight part of polyacetal resin, Preferably it is 0.005-3 weight part, More preferably, it is 0.01-2 weight part.
(ロ)アルカリ金属またはアルカリ土類金属の水酸化物、無機酸塩およびカルボン酸塩としては、例えば、ナトリウム、カリウム、マグネシウム、カルシウムもしくはバリウムなどの水酸化物、上記金属の炭酸塩、リン酸塩、珪酸塩、ほう酸塩が挙げられる。具体的にはカルシウム塩が最も好ましく、水酸化カルシウム、炭酸カルシウム、リン酸カルシウム、珪酸カルシウム、ほう酸カルシウム、および脂肪酸カルシウム(ステアリン酸カルシウム、ミリスチン酸カルシウム等)であり、これらの脂肪酸は、ヒドロキシル基で置換されていてもよい。これらのなかでは、脂肪酸カルシウム塩(ステアリン酸カルシウム、ミリスチン酸カルシウム)が好ましい。これらアルカリ金属またはアルカリ土類金属の水酸化物、無機酸塩およびカルボン酸塩はポリアセタール樹脂100重量部に対して、0.01〜3重量部、好ましくは0.03〜1重量部、さらに好ましくは0.03〜0.5重量部である。 (B) Examples of alkali metal or alkaline earth metal hydroxides, inorganic acid salts and carboxylate salts include hydroxides such as sodium, potassium, magnesium, calcium or barium, carbonates of the above metals, and phosphoric acid. Examples include salts, silicates, and borates. Specifically, calcium salts are most preferred, and are calcium hydroxide, calcium carbonate, calcium phosphate, calcium silicate, calcium borate, and fatty acid calcium (calcium stearate, calcium myristate, etc.), and these fatty acids are substituted with hydroxyl groups. It may be. Of these, fatty acid calcium salts (calcium stearate, calcium myristate) are preferred. These alkali metal or alkaline earth metal hydroxides, inorganic acid salts and carboxylates are used in an amount of 0.01 to 3 parts by weight, preferably 0.03 to 1 part by weight, more preferably 100 parts by weight of the polyacetal resin. Is 0.03 to 0.5 parts by weight.
耐候(光)安定剤としては、(イ)ベンゾトリアゾール系物質、(ロ)シュウ酸アニリド系物質および(ハ)ヒンダードアミン系物質が好ましい。
(イ)ベンゾトリアゾール系物質としては、例えば2−(2´−ヒドロキシ−5´−メチルフェニル)トリアゾール、2−(2´−ヒドロキシ−3、5´−ジ−t−ブチルフェニル)ベンゾトリアゾール、2−(2´−ヒドロキシ−3、5´−ジ−イソアミルフェニル)ベンゾトリアゾール、2−[2´−ヒドロキシ−3、5−ビス−(α、α´−ジメチルベンジル)フェニル]−2H−ベンゾトリアゾール、2−(2´−ヒドロキシ−4´−オクトキシフェニル)ベンゾトリアゾール等が挙げられる。好ましくは2−[2´−ヒドロキシ−3、5−ビス−(α、α´−ジメチルベンジル)フェニル]−2H−ベンゾトリアゾール、2−(2´−ヒドロキシ−3、5´−ジ−t−ブチルフェニル)ベンゾトリアゾールである。
As the weathering (light) stabilizer, (i) a benzotriazole-based material, (b) an oxalic acid anilide-based material, and (c) a hindered amine-based material are preferable.
(I) Examples of the benzotriazole-based substance include 2- (2′-hydroxy-5′-methylphenyl) triazole, 2- (2′-hydroxy-3,5′-di-t-butylphenyl) benzotriazole, 2- (2′-hydroxy-3,5′-di-isoamylphenyl) benzotriazole, 2- [2′-hydroxy-3,5-bis- (α, α′-dimethylbenzyl) phenyl] -2H-benzo Examples include triazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole. Preferably 2- [2′-hydroxy-3,5-bis- (α, α′-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (2′-hydroxy-3,5′-di-t- Butylphenyl) benzotriazole.
(ロ)シュウ酸アニリド系物質としては、例えば2−エトキシ−2´−エチルオキザリックアシッドビスアニリド、2−エトキシ−5−ブチル−2´−エチル−エチルオキザリックアシッドビスアニリド、2−エトキシ−3´−ドデシルエチルオキザリックアシッドビスアニリド等が挙げられる。これらの物質は単独また組み合わせて用いられる。
(ハ)ヒンダードアミン系物質としては、4−アセトキシ−2、2、6、6−テトラメチルピペレジン、4−ステロイルオキシ−2、2、6、6−テトラメチルピペレジン、4−アクロ−ステロイルオキシ−2、2、6、6−テトラメチルピペレジン、4−(フェニルアセトキシ)−2、2、6、6−テトラメチルピペリジン4−ベンゾイルオキシ−2、2、6、6−テトラメチルピペリジン、4−メトキシ−2、2、6、6−テトラメチルピペリジン、4−ステアリルオキシ−2、2、6、6−テトラメチルピペリジン、4−シクロヘキシルオキシ−2、2、6、6−テトラメチルピペリジン、4−ベンジルオキシ−2、2、6、6−テトラメチルピペリジン、4−フェノキシ−2、2、6、6−テトラメチルピペリジン、4−(エチルカルバモイルオキシ)−2、2、6、6−テトラメチルピペリジン、4−(シクロヘキシルカルバモイルオキシ)−2、2、6、6−テトラメチルピペリジン、4−(フェニルカルバモイルオキシ)−2、2、6、6−テトラメチルピペリジンが挙げられる。
(B) Examples of the oxalic acid anilide-based substance include 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxy-5-butyl-2′-ethyl-ethyloxalic acid bisanilide, 2- Examples include ethoxy-3'-dodecylethyl oxalic acid bisanilide. These substances are used alone or in combination.
(C) Examples of hindered amine substances include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-steroyloxy-2,2,6,6-tetramethylpiperidine, and 4-acro-steroloid. Luoxy-2,2,6,6-tetramethylpiperidine, 4- (phenylacetoxy) -2,2,6,6-tetramethylpiperidine 4-benzoyloxy-2,2,6,6-tetramethylpiperidine 4-methoxy-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexyloxy-2,2,6,6-tetramethylpiperidine 4-benzyloxy-2,2,6,6-tetramethylpiperidine, 4-phenoxy-2,2,6,6-tetramethylpiperidine, 4- (ethyl carbonate) (Vamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (cyclohexylcarbamoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenylcarbamoyloxy) -2,2,6,6 -Tetramethylpiperidine.
また、ビス(2、2、6、6−テトラメチル−4−ピペリジン)−カーボネート、ビス(2、2、6、6−テトラメチル−4−ピペリジル)−オキサレート、ビス(2、2、6、6−テトラメチル−4−ピペリジル)−マロネート、ビス(2、2、6、6−テトラメチル−4−ピペリジル)−セバケート、ビス(2、2、6、6−テトラメチル−4−ピペリジル)−アジペート、ビス(2、2、6、6−テトラメチル−4−ピペリジル)−テレフタレート、1、2−ビス(2、2、6、6−テトラメチル−4−ピペリジルオキシ)−p−キシレンが挙げられる。 Also, bis (2,2,6,6-tetramethyl-4-piperidine) -carbonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -oxalate, bis (2,2,6, 6-tetramethyl-4-piperidyl) -malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl)- Adipate, bis (2,2,6,6-tetramethyl-4-piperidyl) -terephthalate, 1,2-bis (2,2,6,6-tetramethyl-4-piperidyloxy) -p-xylene It is done.
また、ビス(2、2、6、6−テトラメチル−4−ピペリジル)トリレン−2、4−ジカルボメート、トリス(2、2、6、6−テトラメチル−4−ピペリジル)−ヘキサメチレン1,6−ジカルバメート、トリス(2、2、6、6−テトラメチル−4−ピペリジル)−ベンゼン−1,3、5−トリカルボキシレート、トリス(2、2、6、6−テトラメチル−4−ピペリジル)−ベンゼン−1,3、4−トリカルボキシレート等が挙げられる。上記ヒンダードアミン系物質は単独あるいは併用して用いてよい。また、上記ベンゾトリアゾール系物質、シュウ酸アニリド系物質とヒンダードアミン系物質の組み合わせが最もよい。これらはポリアセタール樹脂100重量部に対して、0.01〜3重量部、好ましくは0.05〜2重量部、さらに好ましくは0.1〜2重量部用いられる。 Also, bis (2,2,6,6-tetramethyl-4-piperidyl) tolylene-2,4-dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylene 1,6 Dicarbamate, tris (2,2,6,6-tetramethyl-4-piperidyl) -benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl ) -Benzene-1,3,4-tricarboxylate and the like. The above hindered amine materials may be used alone or in combination. The combination of the benzotriazole-based material, oxalic acid anilide-based material and hindered amine-based material is the best. These are used in an amount of 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyacetal resin.
本願の樹脂組成物における安定剤の好ましい組み合わせとしては、ヒンダードフェノール(特にトリエチレングリコール−ビス−(3−(3−t−ブチル−5−メチル−4−ヒドロキシフェニル)−プロピオネート)、テトラキス−(メチレン−3−(3´、5´−ジ−t−ブチル−4´−ヒドロキシフェニル)プロピオネートメタン))、ホルムアルデヒド反応性窒素を含む重合体(特にポリアミド樹脂、ポリ−β−アラニン)およびアルカリ土類金属の脂肪酸塩(特に脂肪酸カルシウム塩)の併用である。その添加量は、ポリアセタール樹脂に対して、0.1〜0.5重量%、ホルムアルデヒド反応性窒素を含む重合体0.01〜1.0重量%、およびアルカリ土類金属の脂肪酸塩(特に脂肪酸カルシウム塩)0.05〜0.5重量%である。
本願発明の組成物には、公知の熱安定剤、酸化防止剤、蟻酸捕捉剤、耐候(光)安定剤、及び本願発明の効果を損なわない限りにおいて、潤滑剤、タルク、窒化硼素などの結晶核剤、顔料、補強材、導電材、熱可塑性樹脂、熱可塑性エラストマーなどを添加することができる。
Preferred combinations of stabilizers in the resin composition of the present application include hindered phenols (particularly triethylene glycol-bis- (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) -propionate), tetrakis- (Methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate methane)), a polymer containing formaldehyde-reactive nitrogen (especially polyamide resin, poly-β-alanine) And alkaline earth metal fatty acid salts (particularly fatty acid calcium salts). The addition amount is 0.1 to 0.5% by weight relative to the polyacetal resin, 0.01 to 1.0% by weight of a polymer containing formaldehyde-reactive nitrogen, and an alkaline earth metal fatty acid salt (particularly a fatty acid). Calcium salt) 0.05 to 0.5% by weight.
The composition of the present invention includes known heat stabilizers, antioxidants, formic acid scavengers, weathering (light) stabilizers, and crystals of lubricants, talc, boron nitride, etc., as long as the effects of the present invention are not impaired. Nucleating agents, pigments, reinforcing materials, conductive materials, thermoplastic resins, thermoplastic elastomers and the like can be added.
本発明のポリアセタール樹脂組成物を製造する方法に特に制限はないが、各成分を混合し、溶融混練する方法が一般的である。(A)成分のポリアセタール樹脂としては、パウダー状やペレット状いずれも使用可能で、(B)成分、(C)成分、及び必要に応じてその他の添加剤とともにヘンシェルミキサーや、タンブラー、V字型ブレンダーなどで混合後1軸や2軸の押出機などで溶融混練される。混合時に、極少量の流動パラフィンや脂肪酸エステルなどの添着剤を用いてもよい。また、予め混合することなく、定量フィーダーなどで各成分を単独であるいは数種類ずつまとめて押出機に連続フィードすることにより本発明のポリアセタール樹脂を製造することも可能である。また、予め(A)、(B)、(C)成分からなる高濃度マスターバッチを作っておいて、押出溶融混練時または射出成形時にポリアセタール樹脂で薄めることにより本発明の組成物を得ることもできる。 Although there is no restriction | limiting in particular in the method of manufacturing the polyacetal resin composition of this invention, The method of mixing each component and melt-kneading is common. As the polyacetal resin of component (A), both powder and pellets can be used, and together with component (B), component (C), and other additives as necessary, Henschel mixer, tumbler, V-shaped After mixing with a blender or the like, it is melt-kneaded with a single screw or twin screw extruder. At the time of mixing, a very small amount of an additive such as liquid paraffin or fatty acid ester may be used. Moreover, it is also possible to produce the polyacetal resin of the present invention by continuously feeding each component alone or several kinds at a time using a quantitative feeder or the like without continuous mixing and feeding them continuously to an extruder. Alternatively, a high-concentration masterbatch comprising the components (A), (B), and (C) is prepared in advance, and the composition of the present invention can be obtained by diluting with a polyacetal resin at the time of extrusion melt kneading or injection molding. it can.
本発明におけるポリアセタール樹脂組成物は、特に射出成形時に低離型力が要求される複雑形状を有する精密機構部品に適しているが、ガスインジェクション成形や押出成形、ブロー成形、圧縮成形などにも使用できる。加えて、本発明のポリアセタール樹脂は機械的特性、長期熱安定性にも優れているため、自動車関係の精密機構部品、特に燃料タンクフランジなどの燃料回り部品や、シートベルト巻き取り機構などのシートベルト回り部品用として特に好適である。 The polyacetal resin composition in the present invention is particularly suitable for precision mechanism parts having complicated shapes that require low mold release force during injection molding, but is also used for gas injection molding, extrusion molding, blow molding, compression molding, etc. it can. In addition, since the polyacetal resin of the present invention is excellent in mechanical properties and long-term thermal stability, automobile-related precision mechanism parts, particularly fuel-related parts such as fuel tank flanges, and seats such as seat belt winding mechanisms. It is particularly suitable for belt-around parts.
本発明を実施例、比較例に基づいて説明する。
まず、実施例、比較例において用いた評価方法を以下に示す。
(1)メルトインデックス(MI:g/10分)
ASTM−D1238により東洋精機製のMELTINDEXERを用いて190℃、2160gの条件下で測定した。
(2)曲げ弾性率(GPa)
住友重機(株)製SH−75射出成形機を用い、シリンダー温度210℃、射出圧力80MPa、射出速度30%、射出時間25秒、冷却時間15秒、金型温度70℃にて試験片を作成し、ASTM−D790に基づき測定した。
The present invention will be described based on examples and comparative examples.
First, the evaluation methods used in Examples and Comparative Examples are shown below.
(1) Melt index (MI: g / 10 min)
The measurement was performed under conditions of 190 ° C. and 2160 g using ASTM-D1238 using a MELTININDEXER manufactured by Toyo Seiki.
(2) Flexural modulus (GPa)
Using a SH-75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., a test piece was prepared at a cylinder temperature of 210 ° C., an injection pressure of 80 MPa, an injection speed of 30%, an injection time of 25 seconds, a cooling time of 15 seconds, and a mold temperature of 70 ° C. And measured based on ASTM-D790.
(3)引張強度(MPa)
上記(2)と同じ条件にて試験片を作成し、ASTM−D638に基づき測定した。
(4)離型力(N)
住友重機(株)製SH−75射出成形機を用い、シリンダー温度220℃、射出圧力30MPa、射出速度30%、射出時間25秒、冷却時間15秒、金型温度95℃にて、高さ50mm、外径50mm、厚さ2mmの有底円筒型の成形体を連続成形し、成形体を金型から突き出しピンを突き出して離型するときの突き出しピンにかかる抵抗力をロードセルにて測定し離型力とした。成形開始後5ショット目の離型力が低いほど初期離型性に優れ、また、5ショット目と50ショット目の離型力の差異が小さいほど、離型力の長期安定性に優れる。
なお、離型力測定方法及び装置については特開平11−12460号公報を参考とした。
(3) Tensile strength (MPa)
Test pieces were prepared under the same conditions as in (2) above and measured based on ASTM-D638.
(4) Release force (N)
Using a SH-75 injection molding machine manufactured by Sumitomo Heavy Industries, Ltd., cylinder temperature 220 ° C., injection pressure 30 MPa, injection speed 30%, injection time 25 seconds, cooling time 15 seconds, mold temperature 95 ° C., height 50 mm The bottomed cylindrical molded body having an outer diameter of 50 mm and a thickness of 2 mm is continuously formed, and the resistance force applied to the protruding pin when the molded body is released from the mold by protruding the protruding pin is measured by a load cell. It was set as a mold force. The lower the release force at the fifth shot after the start of molding, the better the initial release property, and the smaller the difference between the release forces at the fifth and 50th shots, the better the long-term stability of the release force.
For the method and apparatus for measuring the release force, Japanese Patent Application Laid-Open No. 11-12460 was referred to.
(5)耐熱エージング性(引張強度90%保持日数)
上記(2)で作成した試験片を120℃又は140℃のギアオーブン中に放置し、引張強度が初期強度の90%に低下するまでの日数を求めて引張強度90%保持日数とした。引張強度90%保持日数が長いほど耐熱エージング性に優れる。
(6)耐熱水性(引張強度80%保持日数)
上記(2)で作成した試験片を100℃又は120℃の熱水中に浸漬し、引張強度が初期強度の80%に低下するまでの日数を求めて引張強度80%保持日数とした。引張強度80%保持日数が長いほど耐熱水性に優れる。
(5) Heat aging resistance (90% tensile strength retention days)
The test piece prepared in the above (2) was left in a gear oven at 120 ° C. or 140 ° C., and the number of days until the tensile strength was reduced to 90% of the initial strength was determined and used as the retention day of 90% tensile strength. The longer the 90% tensile strength retention days, the better the heat aging resistance.
(6) Hot water resistance (Tensile strength 80% retention days)
The test piece prepared in the above (2) was immersed in hot water at 100 ° C. or 120 ° C., and the number of days until the tensile strength was reduced to 80% of the initial strength was determined and was defined as the retention strength of 80%. The longer the number of days the tensile strength is 80%, the better the hot water resistance.
[実施例1、比較例1〜7]
(A)成分のポリアセタール樹脂として、MI=2g/10分のポリアセタールホモポリマー粉末(特許文献10に記載の公知の方法で製造)100重量部に対して、(B)成分としてN,N‘−エチレンビスステアリルアミド、(C)成分として数平均分子量6000のポリエチレングリコールを表1に記載した量添加し、更に熱安定剤としてポリ−β−アラニン共重合体を0.2重量部、酸化防止剤としてエチレンビス(オキシエチレン)ビス[3−(5−tert−ブチル−4−ヒドロキシ−m−トリル)プロピオネート]0.15重量部を添加し、ヘンシェルミキサーで混合した後、L/D=30のベント付き30mm2軸押出機で設定温度200℃、スクリュー回転数100回転、吐出量4kg/時間の条件で溶融混練しペレットを得た。ペレットを80℃で3時間乾燥した後各評価に用いた。評価結果を表1にまとめて示す。なお、耐熱エージング性評価は120℃、耐熱水性評価は100℃にて行った。
[Example 1, Comparative Examples 1-7]
As polyacetal resin of component (A), polyacetal homopolymer powder of MI = 2 g / 10 min (manufactured by a known method described in Patent Document 10) with respect to 100 parts by weight, N, N′— as component (B) Ethylene bisstearylamide, polyethylene glycol having a number average molecular weight of 6000 as component (C) is added in the amount shown in Table 1, and 0.2 parts by weight of poly-β-alanine copolymer as a heat stabilizer, antioxidant. 0.15 parts by weight of ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate] as a mixture and mixing with a Henschel mixer, L / D = 30 The pellets were melt-kneaded with a vented 30mm twin-screw extruder under the conditions of a set temperature of 200 ° C, a screw speed of 100 revolutions, and a discharge rate of 4 kg / hour. It was. The pellet was dried at 80 ° C. for 3 hours and then used for each evaluation. The evaluation results are summarized in Table 1. The heat aging evaluation was performed at 120 ° C., and the hot water evaluation was performed at 100 ° C.
[実施例2、比較例8]
(A)成分のポリアセタール樹脂として、熱安定剤としてナイロン6−6が0.1重量%、酸化防止剤としてエチレンビス(オキシエチレン)ビス[3−(5−tert−ブチル−4−ヒドロキシ−m−トリル)プロピオネート]が0.3重量%添加された、トリオキサン1モルに対してコモノマーとして1,3−ジオキソランを0.045モル共重合させて得られたMI=3g/10分のポリアセタールコポリマーペレット(特許文献11に記載の公知の方法で製造)100重量部に対して、(B)成分としてN,N‘−エチレンビスステアリルアミド、(C)成分として数平均分子量6000のポリエチレングリコールを表2に記載した量添加し、ヘンシェルミキサーで混合した後、L/D=30のベント付き30mm2軸押出機で設定温度200℃、スクリュー回転数100回転、吐出量4kg/時間の条件で溶融混練しペレットを得た。ペレットを80℃で3時間乾燥した後各評価に用いた。評価結果を表2にまとめて示す。なお、耐熱エージング性評価は140℃、耐熱水性評価は120℃にて行った。
[Example 2, comparative example 8]
As the polyacetal resin of component (A), nylon 6-6 is 0.1% by weight as a heat stabilizer, and ethylene bis (oxyethylene) bis [3- (5-tert-butyl-4-hydroxy-m) as an antioxidant. -Tolyl) propionate] was added to the polyacetal copolymer pellets with MI = 3 g / 10 min obtained by copolymerizing 0.045 mol of 1,3-dioxolane as a comonomer with respect to 1 mol of trioxane. (Manufactured by a known method described in Patent Document 11) 100 parts by weight of N, N′-ethylenebisstearylamide as component (B) and polyethylene glycol having a number average molecular weight of 6000 as component (C) After mixing with the Henschel mixer, the set temperature is set with a 30 mm twin-screw extruder with a vent of L / D = 30. The mixture was melt-kneaded under the conditions of a temperature of 200 ° C., a screw rotation speed of 100 rotations, and a discharge rate of 4 kg / hour to obtain pellets. The pellet was dried at 80 ° C. for 3 hours and then used for each evaluation. The evaluation results are summarized in Table 2. The heat aging evaluation was performed at 140 ° C. and the hot water evaluation was performed at 120 ° C.
本発明のポリアセタール樹脂組成物は、複雑形状を有する精密機構部品の射出成形用ポリアセタール樹脂として好適である。特に、燃料タンクフランジなどの燃料回り部品や、シートベルト巻き取り機構などのシートベルト回り部品等の自動車関係の精密機構部品用として好適である。 The polyacetal resin composition of the present invention is suitable as a polyacetal resin for injection molding of precision mechanism parts having complicated shapes. Particularly, it is suitable for fuel-related parts such as a fuel tank flange and parts for automobile-related precision mechanisms such as seat-belt parts such as a seat belt retracting mechanism.
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JPH11246737A (en) * | 1998-03-05 | 1999-09-14 | Polyplastics Co | Colored polyoxymethylene resin composition and molded article |
JP2005263929A (en) * | 2004-03-17 | 2005-09-29 | Asahi Kasei Chemicals Corp | Polyacetal resin composition having excellent mold releasability |
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