JP2020041133A - Polyacetal resin composition and metal resin composition - Google Patents
Polyacetal resin composition and metal resin composition Download PDFInfo
- Publication number
- JP2020041133A JP2020041133A JP2019143122A JP2019143122A JP2020041133A JP 2020041133 A JP2020041133 A JP 2020041133A JP 2019143122 A JP2019143122 A JP 2019143122A JP 2019143122 A JP2019143122 A JP 2019143122A JP 2020041133 A JP2020041133 A JP 2020041133A
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- Prior art keywords
- resin composition
- polyacetal resin
- mass
- metal
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229930182556 Polyacetal Natural products 0.000 title claims abstract description 109
- 229920006324 polyoxymethylene Polymers 0.000 title claims abstract description 109
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 97
- 239000002184 metal Substances 0.000 title claims abstract description 97
- 239000011342 resin composition Substances 0.000 title claims abstract description 78
- 229920005989 resin Polymers 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 47
- -1 nitrogen-containing compound Chemical class 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 38
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 31
- 239000000194 fatty acid Substances 0.000 claims abstract description 31
- 229930195729 fatty acid Natural products 0.000 claims abstract description 31
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 29
- 239000000155 melt Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 5
- 230000001629 suppression Effects 0.000 abstract description 8
- 238000001125 extrusion Methods 0.000 abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002685 polymerization catalyst Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 5
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 5
- 229920001519 homopolymer Polymers 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920002292 Nylon 6 Polymers 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- WQEPLUUGTLDZJY-UHFFFAOYSA-N pentadecanoic acid Chemical compound CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920002302 Nylon 6,6 Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- GWEHVDNNLFDJLR-UHFFFAOYSA-N 1,3-diphenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1=CC=CC=C1 GWEHVDNNLFDJLR-UHFFFAOYSA-N 0.000 description 2
- QUFMVAWAOYDYFV-UHFFFAOYSA-N 10-hydroxyhexadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCC(O)=O QUFMVAWAOYDYFV-UHFFFAOYSA-N 0.000 description 2
- ZDHCZVWCTKTBRY-UHFFFAOYSA-N 12-hydroxylauric acid Chemical compound OCCCCCCCCCCCC(O)=O ZDHCZVWCTKTBRY-UHFFFAOYSA-N 0.000 description 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- UGAGPNKCDRTDHP-UHFFFAOYSA-N 16-hydroxyhexadecanoic acid Chemical compound OCCCCCCCCCCCCCCCC(O)=O UGAGPNKCDRTDHP-UHFFFAOYSA-N 0.000 description 2
- FYSSBMZUBSBFJL-UHFFFAOYSA-N 3-hydroxydecanoic acid Chemical compound CCCCCCCC(O)CC(O)=O FYSSBMZUBSBFJL-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-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
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- VXZBFBRLRNDJCS-UHFFFAOYSA-N heptacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O VXZBFBRLRNDJCS-UHFFFAOYSA-N 0.000 description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- ISYWECDDZWTKFF-UHFFFAOYSA-N nonadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCCC(O)=O ISYWECDDZWTKFF-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- RGTIBVZDHOMOKC-UHFFFAOYSA-N stearolic acid Chemical compound CCCCCCCCC#CCCCCCCCC(O)=O RGTIBVZDHOMOKC-UHFFFAOYSA-N 0.000 description 2
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- ZDPHROOEEOARMN-UHFFFAOYSA-N undecanoic acid Chemical compound CCCCCCCCCCC(O)=O ZDPHROOEEOARMN-UHFFFAOYSA-N 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- FUSNPOOETKRESL-ZPHPHTNESA-N (z)-n-octadecyldocos-13-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCC\C=C/CCCCCCCC FUSNPOOETKRESL-ZPHPHTNESA-N 0.000 description 1
- VZGOTNLOZGRSJA-ZZEZOPTASA-N (z)-n-octadecyloctadec-9-enamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCC\C=C/CCCCCCCC VZGOTNLOZGRSJA-ZZEZOPTASA-N 0.000 description 1
- AUAGGMPIKOZAJZ-UHFFFAOYSA-N 1,3,6-trioxocane Chemical compound C1COCOCCO1 AUAGGMPIKOZAJZ-UHFFFAOYSA-N 0.000 description 1
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 1
- FYGFTTWEWBXNMP-UHFFFAOYSA-N 10-amino-10-oxodecanoic acid Chemical compound NC(=O)CCCCCCCCC(O)=O FYGFTTWEWBXNMP-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- JFGVTUJBHHZRAB-UHFFFAOYSA-N 2,6-Di-tert-butyl-1,4-benzenediol Chemical compound CC(C)(C)C1=CC(O)=CC(C(C)(C)C)=C1O JFGVTUJBHHZRAB-UHFFFAOYSA-N 0.000 description 1
- MZZYGYNZAOVRTG-UHFFFAOYSA-N 2-hydroxy-n-(1h-1,2,4-triazol-5-yl)benzamide Chemical compound OC1=CC=CC=C1C(=O)NC1=NC=NN1 MZZYGYNZAOVRTG-UHFFFAOYSA-N 0.000 description 1
- AHLVXBLYNKLIGD-UHFFFAOYSA-N 2-n,4-n-diphenyl-1,3,5-triazine-2,4,6-triamine Chemical compound N=1C(NC=2C=CC=CC=2)=NC(N)=NC=1NC1=CC=CC=C1 AHLVXBLYNKLIGD-UHFFFAOYSA-N 0.000 description 1
- YZEZMSPGIPTEBA-UHFFFAOYSA-N 2-n-(4,6-diamino-1,3,5-triazin-2-yl)-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2N=C(N)N=C(N)N=2)=N1 YZEZMSPGIPTEBA-UHFFFAOYSA-N 0.000 description 1
- JIHOVGXINXMLLR-UHFFFAOYSA-N 2-n-phenyl-1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(NC=2C=CC=CC=2)=N1 JIHOVGXINXMLLR-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
- 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 1
- RNIOOCGWPGSASJ-UHFFFAOYSA-N 4-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]butyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 RNIOOCGWPGSASJ-UHFFFAOYSA-N 0.000 description 1
- ZLJVXNHINYJKPM-UHFFFAOYSA-N 4-cyclohexyltriazine Chemical compound C1CCCCC1C1=CC=NN=N1 ZLJVXNHINYJKPM-UHFFFAOYSA-N 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 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
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-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
- 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
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-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
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- LDKDGDIWEUUXSH-UHFFFAOYSA-N Thymophthalein Chemical compound C1=C(O)C(C(C)C)=CC(C2(C3=CC=CC=C3C(=O)O2)C=2C(=CC(O)=C(C(C)C)C=2)C)=C1C LDKDGDIWEUUXSH-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical compound NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910002065 alloy metal Inorganic materials 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 235000021342 arachidonic acid Nutrition 0.000 description 1
- 229940114079 arachidonic acid Drugs 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- FIASKJZPIYCESA-UHFFFAOYSA-L calcium;octacosanoate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O FIASKJZPIYCESA-UHFFFAOYSA-L 0.000 description 1
- LSFBQOPXRBJSSI-UHFFFAOYSA-L calcium;tetradecanoate Chemical compound [Ca+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O LSFBQOPXRBJSSI-UHFFFAOYSA-L 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 1
- DPUOLQHDNGRHBS-KTKRTIGZSA-N erucic acid Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-KTKRTIGZSA-N 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229960004488 linolenic acid Drugs 0.000 description 1
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- YSRVJVDFHZYRPA-UHFFFAOYSA-N melem Chemical compound NC1=NC(N23)=NC(N)=NC2=NC(N)=NC3=N1 YSRVJVDFHZYRPA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DJWFNQUDPJTSAD-UHFFFAOYSA-N n-octadecyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)CCCCCCCCCCCCCCCCC DJWFNQUDPJTSAD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- MQOCIYICOGDBSG-UHFFFAOYSA-M potassium;hexadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCC([O-])=O MQOCIYICOGDBSG-UHFFFAOYSA-M 0.000 description 1
- QLNJFJADRCOGBJ-UHFFFAOYSA-N propionamide Chemical compound CCC(N)=O QLNJFJADRCOGBJ-UHFFFAOYSA-N 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- UORVCLMRJXCDCP-UHFFFAOYSA-N propynoic acid Chemical compound OC(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 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
- 238000007613 slurry method Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical class [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- MVJKXJPDBTXECY-UHFFFAOYSA-N trifluoroborane;hydrate Chemical compound O.FB(F)F MVJKXJPDBTXECY-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 150000004901 trioxanes Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229960002703 undecylenic acid Drugs 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/04—Copolyoxymethylenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ポリアセタール樹脂組成物及び金属樹脂組成物に関する。 The present invention relates to a polyacetal resin composition and a metal resin composition.
ポリアセタール樹脂組成物は、バランスのとれた機械物性と優れた疲労特性を有していることから、広く自動車、電子機器、電気機器等の部品に利用されている。
ところで、近年では、ポリアセタール樹脂組成物は金属粉末射出成形のためのバインダーとしての利用も増えてきており、ポリアセタール樹脂をバインダーに用いた技術としては、例えばバインダー成分がポリアセタール樹脂とポリオレフィン樹脂と別のポリマーからなる技術（先行文献１）が紹介されている。
BACKGROUND ART Polyacetal resin compositions have been widely used for parts of automobiles, electronic devices, electric devices, and the like because of having balanced mechanical properties and excellent fatigue characteristics.
By the way, in recent years, the use of a polyacetal resin composition as a binder for metal powder injection molding has been increasing, and as a technique using a polyacetal resin as a binder, for example, a binder component is different from a polyacetal resin and a polyolefin resin. A technique comprising a polymer (Prior Art 1) is introduced.
ここで、金属粉末射出成形のためのバインダーとして用いられるポリアセタール樹脂組成物に求められる特性としては、金属粉末をポリアセタール樹脂組成物中に均一に分散させるために流動性が高いこと（メルトフローインデックス（ＭＩ）が高い）であること、作業環境の観点から熱安定性が優れること、及び、最終の金属製品への影響を抑制するため、熱安定性や押出性の不良等に起因して製造中に発生するホルムアルデヒドや添加物の炭化物等の異物の含有が低いこと、が挙げられる。熱安定性を向上させる技術としては、例えば、ポリアセタール樹脂に２種類の酸化防止剤、脂肪酸カルシウム塩、ホルムアルデヒド反応性窒素含有化合物、及び滑剤を配合して、耐熱性、耐溶剤性、耐酸性を向上させる技術（特許文献２）が紹介されている。 Here, the properties required for the polyacetal resin composition used as a binder for metal powder injection molding include high fluidity in order to uniformly disperse the metal powder in the polyacetal resin composition (melt flow index (melt flow index ( MI) is high, the thermal stability is excellent from the viewpoint of the working environment, and in order to suppress the influence on the final metal product, the product is being manufactured due to poor thermal stability or extrudability. Low content of foreign substances such as formaldehyde and carbides of additives which are generated in water. As a technique for improving thermal stability, for example, two kinds of antioxidants, fatty acid calcium salts, formaldehyde-reactive nitrogen-containing compounds, and lubricants are blended with polyacetal resin to improve heat resistance, solvent resistance, and acid resistance. A technique for improving the performance (Patent Document 2) is introduced.
しかし、特許文献１、２に記載の技術では、上記のポリアセタール樹脂組成物に求められる特性が十分とは言えず、特に、特許文献２では、比較的高ＭＩのポリアセタール樹脂組成物の物性において改善の余地があった。 However, according to the techniques described in Patent Documents 1 and 2, the properties required for the above-mentioned polyacetal resin composition cannot be said to be sufficient. In particular, in Patent Document 2, the properties of the polyacetal resin composition having a relatively high MI are improved. There was room for
本発明では、押出し性、熱安定性、異物の抑制に優れ、更には金属粉末との分散性に優れたポリアセタール樹脂組成物、並びに、押出し性及び熱安定性に優れ、異物含有が少なく、更には金属粉末が効果的に分散した、金属粉末とポリアセタール樹脂組成物との金属樹脂組成物を提供することを目的とする。 In the present invention, extrudability, heat stability, excellent suppression of foreign matter, furthermore a polyacetal resin composition excellent in dispersibility with metal powder, and extrudability and heat stability are excellent, the foreign matter content is small, furthermore An object of the present invention is to provide a metal resin composition of a metal powder and a polyacetal resin composition in which the metal powder is effectively dispersed.
本発明者らは、上述した課題を解決するべく鋭意検討した結果、ポリアセタール樹脂に対して、窒素含有化合物、脂肪酸金属塩を所定の含有量で含有させるとともに、窒素含有化合物と脂肪酸金属塩の含有量を所定の比率とし、所定のメルトフローインデックスを有するポリアセタール樹脂組成物とすることで上記課題を解決できることを見出し、本発明に到達した。 The present inventors have conducted intensive studies to solve the above-described problems, and found that the polyacetal resin contains a nitrogen-containing compound and a fatty acid metal salt at a predetermined content, and contains the nitrogen-containing compound and the fatty acid metal salt. The inventors have found that the above problems can be solved by setting the amount to a predetermined ratio and forming a polyacetal resin composition having a predetermined melt flow index, and arrived at the present invention.
すなわち、本発明は、以下の通りである。
［１］
（Ａ）ポリアセタール樹脂１００質量部と、（Ｂ）窒素含有化合物０．００５〜０．２質量部と、（Ｃ）脂肪酸金属塩０．０１〜０．８質量部とを含み、
１９０℃、２．１６ｋｇの条件で測定したメルトフローインデックスが６０ｇ／１０分以上２００ｇ／１０分未満であり、
前記（Ｂ）窒素含有化合物の含有量に対する前記（Ｃ）脂肪酸金属塩の含有量の比（（Ｃ）／（Ｂ））が１〜１５であることを特徴とする、ポリアセタール樹脂組成物。
［２］
前記（Ｂ）窒素含有化合物の含有量に対する（Ｃ）脂肪酸金属塩の含有量の比（（Ｃ）／（Ｂ））が１〜１０である、［１］に記載のポリアセタール樹脂組成物。
［３］
前記（Ａ）ポリアセタール樹脂１００質量部に対して、
前記（Ｂ）窒素含有化合物の含有量が、０．００５〜０．１質量部であり、前記（Ｃ）脂肪酸金属塩の含有量が０．０１〜０．６質量部である、［１］又は［２］に記載のポリアセタール樹脂組成物。
［４］
更に、（Ｄ）酸化防止剤を前記（Ａ）ポリアセタール樹脂１００質量部に対して０．０１〜１．０質量部の含有量で含む、［１］〜［３］のいずれかに記載のポリアセタール樹脂組成物。
［５］
金属粉末と、［１］〜［４］のいずれかに記載の前記ポリアセタール樹脂組成物とを含む金属樹脂組成物であって、当該金属粉末の含有量が金属樹脂組成物１００質量％中に７０〜９５質量％である金属樹脂組成物。
That is, the present invention is as follows.
[1]
(A) 100 parts by mass of a polyacetal resin, (B) 0.005 to 0.2 parts by mass of a nitrogen-containing compound, and (C) 0.01 to 0.8 parts by mass of a fatty acid metal salt,
A melt flow index measured at 190 ° C. and 2.16 kg is 60 g / 10 min or more and less than 200 g / 10 min;
A polyacetal resin composition, wherein the ratio ((C) / (B)) of the content of the (C) fatty acid metal salt to the content of the (B) nitrogen-containing compound is 1 to 15.
[2]
The polyacetal resin composition according to [1], wherein a ratio ((C) / (B)) of the content of the (C) fatty acid metal salt to the content of the (B) nitrogen-containing compound is 1 to 10.
[3]
(A) 100 parts by mass of the polyacetal resin,
[1] The content of the (B) nitrogen-containing compound is 0.005 to 0.1 parts by mass, and the content of the (C) fatty acid metal salt is 0.01 to 0.6 parts by mass. Or the polyacetal resin composition according to [2].
[4]
Furthermore, the polyacetal according to any one of [1] to [3], further comprising (D) an antioxidant in a content of 0.01 to 1.0 part by mass based on 100 parts by mass of the polyacetal resin (A). Resin composition.
[5]
A metal resin composition comprising a metal powder and the polyacetal resin composition according to any one of [1] to [4], wherein the content of the metal powder is 70% by mass in 100% by mass of the metal resin composition. A metal resin composition of about 95% by mass.
本発明によれば、押出し性、熱安定性、異物の抑制に優れ、更には金属粉末との分散性に優れたポリアセタール樹脂組成物、及び、金属粉末とポリアセタール樹脂組成物との金属樹脂組成物を提供することができる。 According to the present invention, a polyacetal resin composition having excellent extrudability, heat stability, and suppression of foreign matter, and further having excellent dispersibility with metal powder, and a metal resin composition of metal powder and polyacetal resin composition Can be provided.
以下、本発明を実施するための形態について詳細に説明する。なお、本発明は、以下の記載に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following description, and can be implemented with various modifications within the scope of the gist.
（ポリアセタール樹脂組成物）
本実施形態に係るポリアセタール樹脂組成物は、（Ａ）ポリアセタール樹脂１００質量部と、（Ｂ）窒素含有化合物０．００５〜０．２質量部と、（Ｃ）脂肪酸金属塩０．０１〜０．８質量部とを含む。また、当該樹脂組成物は、１９０℃、２．１６ｋｇの条件で測定したメルトフローインデックスが６０ｇ／１０分以上２００ｇ／１０分未満であり、（Ｂ）窒素含有化合物の含有量に対する（Ｃ）脂肪酸金属塩の含有量の比（（Ｃ）／（Ｂ））が１〜１５であることを特徴とする。これにより、ポリアセタール樹脂組成物を製造する際の押出し性、熱安定性、異物の抑制を優れたものにするとともに、金属粉末との分散性にも優れたものにすることができる。
(Polyacetal resin composition)
The polyacetal resin composition according to the present embodiment comprises (A) 100 parts by mass of a polyacetal resin, (B) 0.005 to 0.2 parts by mass of a nitrogen-containing compound, and (C) 0.01 to 0. 8 parts by mass. The resin composition has a melt flow index measured at 190 ° C. and 2.16 kg of not less than 60 g / 10 min and less than 200 g / 10 min, and (B) the fatty acid (C) relative to the content of the nitrogen-containing compound. The metal salt content ratio ((C) / (B)) is 1 to 15. Thereby, extrudability, heat stability, and suppression of foreign matter when producing the polyacetal resin composition can be improved, and the dispersibility with the metal powder can be improved.
〔（Ａ）ポリアセタール樹脂〕
本実施形態における（Ａ）ポリアセタール樹脂は、ポリアセタールホモポリマー、ポリアセタールコポリマー、又はその混合物である。本実施形態における（Ａ）ポリアセタール樹脂は、熱安定性の観点からポリアセタールコポリマーが好ましい。
ポリアセタールホモポリマーは、オキシメチレン基を主鎖に有するポリマーであり、重合体の両末端をエステル基又はエーテル基により封鎖することができる。ポリアセタールホモポリマーは、ホルムアルデヒド及び公知の分子量調節剤を原料として得ることができ、それら原料から、公知のオニウム塩系重合触媒を用いて炭化水素等を溶媒として公知のスラリー法、例えば特公昭４７―６４２０号公報や特公昭４７−１００５９号公報に記載の重合方法で得ることができる。
なお、ポリアセタールホモポリマーは、両末端を除く主鎖の９９．８ｍｏｌ％以上がオキシメチレン基で構成されることが好ましく、両末端を除く主鎖がオキシメチレン基のみで構成されるポリアセタールホモポリマーであることがより好ましい。
[(A) polyacetal resin]
The (A) polyacetal resin in the present embodiment is a polyacetal homopolymer, a polyacetal copolymer, or a mixture thereof. The polyacetal resin (A) in the present embodiment is preferably a polyacetal copolymer from the viewpoint of thermal stability.
The polyacetal homopolymer is a polymer having an oxymethylene group in the main chain, and both ends of the polymer can be blocked with an ester group or an ether group. The polyacetal homopolymer can be obtained by using formaldehyde and a known molecular weight regulator as raw materials. From these raw materials, a known slurry method using a hydrocarbon or the like as a solvent by using a known onium salt-based polymerization catalyst, for example, It can be obtained by a polymerization method described in JP-A-6420 or JP-B-47-10059.
The polyacetal homopolymer is preferably a polyacetal homopolymer in which 99.8 mol% or more of the main chain excluding both ends is composed of oxymethylene groups, and the main chain excluding both ends is composed of only oxymethylene groups. More preferably, there is.
ポリアセタールコポリマーは、トリオキサンと、環状エーテル及び／又は環状ホルマールを重合触媒の存在下で共重合して得られるポリアセタール樹脂である。
トリオキサンとは、ホルムアルデヒドの環状３量体であり、一般的には酸性触媒の存在下でホルマリン水溶液を反応させることにより得られる。
このトリオキサンは、水、メタノール、蟻酸、蟻酸メチル等の連鎖移動させる不純物を含有している場合があるので、例えば蒸留等の方法でこれら不純物を除去精製することが好ましい。その場合、連鎖移動させる不純物の合計量をトリオキサン１ｍｏｌに対して、１×１０−３ｍｏｌ以下とすることが好ましく、より好ましくは０．５×１０−３ｍｏｌ以下とする。不純物の量を上記数値のように低減化することにより、重合反応速度を実用上十分に高めることができ、生成したポリマーにおいて優れた熱安定性が得られる。
The polyacetal copolymer is a polyacetal resin obtained by copolymerizing trioxane and a cyclic ether and / or cyclic formal in the presence of a polymerization catalyst.
Trioxane is a cyclic trimer of formaldehyde, and is generally obtained by reacting an aqueous formalin solution in the presence of an acidic catalyst.
Since this trioxane may contain impurities that cause chain transfer, such as water, methanol, formic acid, and methyl formate, it is preferable to remove and purify these impurities by a method such as distillation. In that case, the total amount of impurities to be chain-transferred is preferably 1 × 10 −3 mol or less, more preferably 0.5 × 10 −3 mol or less, per 1 mol of trioxane. By reducing the amount of impurities as described above, the polymerization reaction rate can be sufficiently increased for practical use, and excellent thermal stability can be obtained in the produced polymer.
環状エーテル及び／又は環状ホルマールは、前記トリオキサンと共重合可能な成分であり、例えば、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド、エピクルロルヒドリン、エピブロモヒドリン、スチレンオキサイド、オキサタン、１，３−ジオキソラン、エチレングリコールホルマール、プロピレングリコールホルマール、ジエチレングリコールホルマール、トリエチレングリコールホルマール、１，４−ブタンジオールホルマール、１，５−ペンタンジオールホルマール、１，６−ヘキサンジオールホルマール等が挙げられる。特に、１，３−ジオキソラン、１，４−ブタンジオールホルマールが好ましい。これらは、１種のみを単独で使用してもよく、２種以上を併用してもよい。 The cyclic ether and / or cyclic formal is a component copolymerizable with the trioxane. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, epichlorohydrin, epibromohydrin, styrene oxide, oxatan, and 1,3. -Dioxolan, ethylene glycol formal, propylene glycol formal, diethylene glycol formal, triethylene glycol formal, 1,4-butanediol formal, 1,5-pentanediol formal, 1,6-hexanediol formal and the like. In particular, 1,3-dioxolan and 1,4-butanediol formal are preferred. These may be used alone or in combination of two or more.
環状エーテル及び環状ホルマールの添加量は、前記トリオキサン１ｍｏｌに対して１．０ｍｏｌ％以上が好ましく、より好ましくは３．０ｍｏｌ％以上、更に好ましくは３．５ｍｏｌ％以上である。また、前記トリオキサン１ｍｏｌに対して８．０ｍｏｌ％以下が好ましく、より好ましくは７．０ｍｏｌ％以下、更に好ましくは５．０ｍｏｌ％以下である。 The addition amount of the cyclic ether and the cyclic formal is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, and still more preferably 3.5 mol% or more based on 1 mol of the trioxane. Further, the amount is preferably 8.0 mol% or less, more preferably 7.0 mol% or less, and still more preferably 5.0 mol% or less based on 1 mol of the trioxane.
重合触媒としては、ルイス酸に代表されるホウ酸、スズ、チタン、リン、ヒ素及びアンチモン化物が挙げられ、特に、三フッ化ホウ素、三フッ化ホウ素系水和物、及び酸素原子又は硫黄原子を含む有機化合物と三フッ化ホウ素との配位錯化合物が好ましい。例えば、三フッ化ホウ素、三フッ化ホウ素ジエチルエーテラート、三フッ化ホウ素−ジ−ｎ−ブチルエーテラートを好適例として挙げられる。これらは、１種のみを単独で使用してもよく、２種以上を併用してもよい。 Examples of the polymerization catalyst include boric acid represented by a Lewis acid, tin, titanium, phosphorus, arsenic, and antimonide. Particularly, boron trifluoride, boron trifluoride hydrate, and oxygen atom or sulfur atom And a coordination complex compound of boron trifluoride and an organic compound containing For example, preferable examples include boron trifluoride, boron trifluoride diethyl etherate, and boron trifluoride-di-n-butyl etherate. These may be used alone or in combination of two or more.
重合触媒の添加量は、前記トリオキサン１ｍｏｌに対して０．１×１０−５〜０．１×１０−３ｍｏｌの範囲が好ましく、より好ましくは０．３×１０−５〜０．５×１０−４ｍｏｌの範囲であり、さらに好ましくは０．５×１０−５〜０．４×１０−４ｍｏｌの範囲である。重合触媒の添加量が前記範囲内であるとき、安定して長時間の重合反応を実施することができる。 The amount of the polymerization catalyst to be added is preferably in a range of 0.1 × 10 −5 to 0.1 × 10 −3 mol, more preferably 0.3 × 10 −5 to 0.5 × 10 5 mol per 1 mol of the trioxane. −4 mol, more preferably 0.5 × 10 −5 to 0.4 × 10 −4 mol. When the addition amount of the polymerization catalyst is within the above range, the polymerization reaction can be stably performed for a long time.
ポリアセタールコポリマーの製造において、重合触媒の失活は、重合反応によって得られたポリアセタール樹脂を、アンモニア、トリエチルアミン、トリ−ｎ−ブチルアミン等のアミン類、又はアルカリ金属もしくはアルカリ土類金属の水酸化物、無機酸塩、有機酸塩等の触媒中和失活剤の少なくとも一種を含む水溶液または有機溶剤液中に投入し、スラリー状態で一般的には数分〜数時間攪拌することにより行われる。触媒中和失活後のスラリーは濾過、洗浄により、未反応モノマーや触媒中和失活剤、触媒中和塩が除去された後、乾燥される。 In the production of polyacetal copolymer, deactivation of the polymerization catalyst, the polyacetal resin obtained by the polymerization reaction, ammonia, triethylamine, amines such as tri-n-butylamine, or an alkali metal or alkaline earth metal hydroxide, It is generally carried out by introducing the mixture into an aqueous solution or an organic solvent solution containing at least one catalyst neutralizing deactivator such as an inorganic acid salt or an organic acid salt, and stirring the slurry in a slurry state for several minutes to several hours. The slurry after the catalyst neutralization deactivation is filtered and washed to remove unreacted monomers, catalyst neutralization deactivators, and catalyst neutralization salts, and then dried.
また、重合触媒の失活としては、アンモニア、トリエチルアミン等の蒸気とポリアセタール共重合体とを接触させて重合触媒を失活させる方法や、ヒンダードアミン類、トリフェニルホスフィン及び水酸化カルシウム等のうち少なくとも一種とポリアセタール樹脂とを混合機で接触させて触媒失活させる方法も用いることができる。 Further, as the deactivation of the polymerization catalyst, a method of contacting a vapor of ammonia, triethylamine or the like with a polyacetal copolymer to deactivate the polymerization catalyst, or at least one of hindered amines, triphenylphosphine, calcium hydroxide and the like And a method of bringing the polyacetal resin into contact with a polyacetal resin to deactivate the catalyst.
また、重合触媒の失活を行わずに、ポリアセタールコポリマーの融点以下の温度で、不活性ガス雰囲気下において加熱することによって、重合触媒が揮発低減されたポリアセタールコポリマーを用いて本実施形態の後述の末端安定化処理を行っても良い。以上の重合触媒の失活操作及び重合触媒の揮発低減操作は、必要に応じて、重合反応によって得られたポリアセタール樹脂を粉砕した後で行っても良い。 Further, without deactivating the polymerization catalyst, by heating under an inert gas atmosphere at a temperature equal to or lower than the melting point of the polyacetal copolymer, the polymerization catalyst is volatilized using the reduced polyacetal copolymer to be described later in the present embodiment. A terminal stabilization treatment may be performed. The operation of deactivating the polymerization catalyst and the operation of reducing the volatilization of the polymerization catalyst may be performed, if necessary, after pulverizing the polyacetal resin obtained by the polymerization reaction.
得られた（Ａ）ポリアセタール樹脂の末端安定化処理は、次の方法によって不安定末端部分を分解除去する。不安定末端部の分解除去方法としては、例えば、ベント付き単軸スクリュー式押出機やベント付き２軸スクリュー式押出機を用いて、切欠剤としてアンモニアやトリエチルアミン、トリブチルアミン等の脂肪酸アミン、水酸化カルシウムに代表されるアルカリ金属又はアルカリ土類金属の水酸化物、無機弱酸塩、有機弱酸塩等の公知の不安定末端部を分解するこのできる塩基性物質の存在下に、ポリアセタール樹脂を溶融し、不安定末端部を分解除去することができる。 In the terminal stabilization treatment of the obtained polyacetal resin (A), the unstable terminal portion is decomposed and removed by the following method. As a method of decomposing and removing the unstable terminal portion, for example, using a single screw type extruder with a vent or a twin screw type extruder with a vent, a fatty acid amine such as ammonia, triethylamine, tributylamine, etc. Melting the polyacetal resin in the presence of a basic substance capable of decomposing known unstable terminal parts such as alkali metal or alkaline earth metal hydroxides such as calcium, inorganic weak acid salts and organic weak acid salts. The unstable terminal can be decomposed and removed.
本実施形態の（Ａ）ポリアセタール樹脂のメルトフローインデックス（ＭＩ）は、ＡＳＴＭ−Ｄ−１２３８−５７Ｔに準拠し、１９０℃、２．１６ｋｇの条件で測定して、６０ｇ／１０分以上２００ｇ／１０分未満が好ましく、より好ましくは６０ｇ／１０分以上１６０ｇ／１０分未満であり、さらに好ましくは７０ｇ／１０分以上１４０ｇ／１０分未満である。メルトフローインデックスを６０ｇ／１０分以上とすることにより、金属粉末との分散性が向上し、メルトフローインデックスを２００ｇ／１０分未満とすることにより、金属粉末との分散性が向上するとともに、（Ａ）ポリアセタール樹脂を重合する際の押出し性も向上させることができる。
なお、（Ａ）ポリアセタール樹脂のメルトフローインデックスは、重合時に添加する分子量調節剤の量を多くすることにより、メルトフローインデックスが大きくなるように操作することができる。
The melt flow index (MI) of the polyacetal resin (A) of the present embodiment is measured at 190 ° C. and 2.16 kg in accordance with ASTM-D-1238-57T, and is from 60 g / 10 min to 200 g / 10. Min, more preferably 60 g / 10 min or more and less than 160 g / 10 min, and even more preferably 70 g / 10 min or more and less than 140 g / 10 min. By setting the melt flow index to 60 g / 10 min or more, the dispersibility with the metal powder is improved. By setting the melt flow index to less than 200 g / 10 min, the dispersibility with the metal powder is improved, and ( A) The extrudability at the time of polymerizing a polyacetal resin can also be improved.
In addition, the melt flow index of the polyacetal resin (A) can be controlled so as to increase the melt flow index by increasing the amount of the molecular weight modifier added at the time of polymerization.
〔（Ｂ）窒素含有化合物〕
本実施形態に係るポリアセタール樹脂組成物は、（Ｂ）窒素含有化合物を含有しており、（Ｃ）脂肪酸金属塩と相まって熱安定性を向上することができる。（Ｂ）窒素含有化合物としては、特に限定されないが例えば、ポリアミド樹脂、アミド化合物、尿素誘導体、トリアジン誘導体、等が挙げられる。これらは１種で用いてもよいし、２種以上を組み合わせて用いてもよい。
ポリアミド樹脂としては、特に限定されないが例えば、ジアミンとジカルボン酸との縮合、アミノ酸の縮合、ラクタムの開環重合等によって得られるナイロン６、ナイロン１１、ナイロン１２、ナイロン６６、ナイロン６・１０、ナイロン６／６・１０、ナイロン６／６・６、ナイロン６・６／６・１０、ナイロン６／６・６／６・１０、ポリ−β−アラニン等が挙げられる。
[(B) nitrogen-containing compound]
The polyacetal resin composition according to this embodiment contains (B) a nitrogen-containing compound, and can improve thermal stability in combination with (C) a fatty acid metal salt. (B) The nitrogen-containing compound is not particularly limited, and examples thereof include a polyamide resin, an amide compound, a urea derivative, and a triazine derivative. These may be used alone or in combination of two or more.
Examples of the polyamide resin include, but are not particularly limited to, nylon 6, nylon 11, nylon 12, nylon 66, nylon 6,10, and nylon 6 obtained by condensation of a diamine and a dicarboxylic acid, condensation of an amino acid, ring-opening polymerization of a lactam, and the like. 6/6/10, nylon 6/6/6, nylon 6.6 / 6/10, nylon 6/6/6/6/10, poly-β-alanine and the like.
アミド化合物としては、特に限定されないが例えば、脂肪族モノカルボン酸、脂肪族ジカルボン酸、芳香族モノカルボン酸又は芳香族ジカルボン酸と脂肪族モノアミン、脂肪族ジアミン、芳香族モノアミン、芳香族ジアミンとから生成されるステアリルステアリン酸アミド、ステアリルオレイン酸アミド、ステアリルエルカ酸アミド、エチレンジアミン−ジステアリン酸アミド、エチレンジアミン−ジベヘニン酸アミド、ヘキサメチレンジアミン−ジステアリン酸アミド、エチレンジアミン−ジエルカ酸アミド、キシリレンジアミン−ジエルカ酸アミド、ジ（キシリレンジアミン−ステアリン酸アミド）、セバシン酸アミド等が挙げられる。 Examples of the amide compound include, but are not particularly limited to, aliphatic monocarboxylic acids, aliphatic dicarboxylic acids, aromatic monocarboxylic acids or aromatic dicarboxylic acids and aliphatic monoamines, aliphatic diamines, aromatic monoamines, and aromatic diamines. The resulting stearyl stearamide, stearyl oleamide, stearyl erucamide, ethylenediamine-distearamide, ethylenediamine-dibehenamide, hexamethylenediamine-distearamide, ethylenediamine-dierucaramide, xylylenediamine-dierucaric acid Examples include amide, di (xylylenediamine-stearic acid amide), sebacic amide and the like.
尿素誘導体としては、特に限定されないが例えば、Ｎ−フェニル尿素、Ｎ，Ｎ’−ジフェニル尿素、Ｎ−フェニルチオ尿素、Ｎ，Ｎ’−ジフェニルチオ尿素等が挙げられる。 Examples of the urea derivative include, but are not particularly limited to, N-phenylurea, N, N'-diphenylurea, N-phenylthiourea, N, N'-diphenylthiourea and the like.
トリアジン誘導体としては、特に限定されないが例えば、メラミン、ベンゾグアナミン、Ｎ−フェニルメラミン、メレム、Ｎ，Ｎ’−ジフェニルメラミン、Ｎ−メチロールメラミン、Ｎ，Ｎ’−トリメチロールメラミン、２，４−ジアミノ−６−シクロヘキシルトリアジン、メラム等が挙げられる。 Examples of the triazine derivative include, but are not particularly limited to, melamine, benzoguanamine, N-phenylmelamine, melem, N, N′-diphenylmelamine, N-methylolmelamine, N, N′-trimethylolmelamine, and 2,4-diamino-. 6-cyclohexyltriazine, melam and the like.
（Ｂ）窒素含有化合物の含有量は、ポリアセタール樹脂１００質量部に対して、０．００５〜０．２質量部であり、好ましくは０．００５〜０．１質量部である。
当該含有量を０．００５質量部以上とすることにより、熱安定性を向上させるとともに、異物の含有量を抑制することができる。また、当該含有量を０．２質量部以下とすることにより、異物の含有量を抑制することができる。
(B) The content of the nitrogen-containing compound is 0.005 to 0.2 part by mass, preferably 0.005 to 0.1 part by mass, based on 100 parts by mass of the polyacetal resin.
By setting the content to 0.005 parts by mass or more, the thermal stability can be improved and the content of foreign matter can be suppressed. Further, by setting the content to 0.2 parts by mass or less, the content of foreign matter can be suppressed.
〔（Ｃ）脂肪酸金属塩〕
本実施形態に係るポリアセタール樹脂組成物は、（Ｃ）脂肪酸金属塩を含有しており、（Ｂ）窒素含有化合物と相まって長期の熱安定性を維持することができる。（Ｃ）脂肪酸金属塩としては、特に限定されないが例えば、炭素数１０〜３５の飽和若しくは不飽和の脂肪酸又は水酸基で置換されている脂肪酸と、アルカリ金属若しくはアルカリ土類金属の水酸化物、酸化物又は塩化物と、から得られた脂肪酸金属塩が挙げられる。
[(C) fatty acid metal salt]
The polyacetal resin composition according to this embodiment contains (C) a fatty acid metal salt, and can maintain long-term thermal stability in combination with (B) a nitrogen-containing compound. (C) The fatty acid metal salt is not particularly limited, but may be, for example, a saturated or unsaturated fatty acid having 10 to 35 carbon atoms or a fatty acid substituted with a hydroxyl group, a hydroxide of an alkali metal or an alkaline earth metal, oxidation, or the like. Product or chloride and a fatty acid metal salt obtained from the product.
脂肪酸金属塩の脂肪酸としては、カプリン酸、ウンデシル酸、ラウリン酸、トリデシル酸、ミリスチン酸、ペンタデシル酸、パルミトン酸、ヘプタデシル酸、ステアリン酸、ノナデカン酸、アラキン酸、ベヘン酸、リグリセリン酸、セロチン酸、ヘプタコサン酸、モンタン酸、ウンデシレン酸、オレイン酸、エライジン酸、セトレイン酸、エルカ酸、ブラシジン酸、ソルビン酸、リノール酸、リノレン酸、アラキドン酸、プロピオール酸、ステアロール酸、１２−ヒドロキシドデカン酸、３−ヒドオキシデカン酸、１６−ヒドロキシヘキサデカン酸、１０−ヒドロキシヘキサデカン酸、１２−ヒドロキシオクタデカン酸、１０−ヒドロキシ−８−オクタデカン酸等が挙げられる。また、金属化合物としては、ナトリウム、リチウム、カリウム及びカルシウム、マグネシウム、バリウム、亜鉛、アルミニウム、ストロンチウムのアルカリ金属、アルカリ土類金属の水酸化物若しくは塩化物である。中でも好ましくは、脂肪酸がミリスチン酸、パルミチン酸、ステアリン酸であり、金属化合物がカルシウムの水酸化物、酸化物及び塩化物である。具体的な脂肪酸金属塩の例としては、ミリスチン酸カルシウム、パルミチン酸カリシウム、ステアリン酸カルシウムである。 Fatty acids of fatty acid metal salts include capric acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, heptadecylic acid, stearic acid, nonadecanoic acid, arachiic acid, behenic acid, ligglyceric acid, and serotinic acid , Heptacosanoic acid, montanic acid, undecylenic acid, oleic acid, elaidic acid, setleic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearolic acid, 12-hydroxydodecanoic acid, Examples thereof include 3-hydroxydecanoic acid, 16-hydroxyhexadecanoic acid, 10-hydroxyhexadecanoic acid, 12-hydroxyoctadecanoic acid, and 10-hydroxy-8-octadecanoic acid. Examples of the metal compound include sodium, lithium, potassium and calcium, magnesium, barium, zinc, aluminum and strontium hydroxides and chlorides of alkali metals and alkaline earth metals. Among them, the fatty acids are preferably myristic acid, palmitic acid and stearic acid, and the metal compounds are calcium hydroxides, oxides and chlorides. Specific examples of fatty acid metal salts include calcium myristate, potassium palmitate, and calcium stearate.
（Ｃ）脂肪酸金属塩の含有量は、ポリアセタール樹脂１００質量部に対して、０．０１〜０．８質量部、好ましくは０．０１〜０．６質量部である。
当該含有量を０．０１質量部以上とすることにより、熱安定性を向上させるとともに、異物の含有量を抑制することができる。また、当該含有量を０．８質量部以下とすることにより、熱安定性を向上させるとともに、異物の含有量を抑制することができる。
(C) The content of the fatty acid metal salt is 0.01 to 0.8 parts by mass, preferably 0.01 to 0.6 parts by mass, based on 100 parts by mass of the polyacetal resin.
When the content is 0.01 parts by mass or more, the thermal stability can be improved and the content of foreign substances can be suppressed. Further, by setting the content to 0.8 parts by mass or less, the thermal stability can be improved and the content of foreign matter can be suppressed.
〔（Ｂ）窒素含有化合物の含有量に対する（Ｃ）脂肪酸金属塩の含有量の比〕
本実施形態では、（Ｂ）窒素含有化合物の含有量に対する（Ｃ）脂肪酸金属塩の含有量の比が特定の範囲にあることが重要であり、具体的には当該比が１〜１５であり、好ましくは１〜１０である。当該比を１以上とすることにより、異物の含有量を抑制することができる。また、当該比を１５以下とすることにより、熱安定性を向上させるとともに、異物の含有量を抑制することができる。
[Ratio of content of (C) fatty acid metal salt to content of (B) nitrogen-containing compound]
In the present embodiment, it is important that the ratio of the content of the (C) fatty acid metal salt to the content of the (B) nitrogen-containing compound is in a specific range, and specifically, the ratio is 1 to 15. , Preferably 1 to 10. By setting the ratio to be 1 or more, the content of foreign matter can be suppressed. Further, by setting the ratio to 15 or less, the thermal stability can be improved and the content of foreign matter can be suppressed.
〔その他の添加剤〕
本実施形態において、ポリアセタール樹脂組成物に添加可能なその他添加剤としては、本発明の効果を損なわない限り限定されるものではないが、好ましい添加剤として酸化防止剤を挙げることができる。
酸化防止剤としては、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−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−ブチル−４’−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）、３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオン、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’−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート）メタン、Ｎ，Ｎ’−ビス−（３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェノール）プロピオニル）ヒドラジン、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）プロピオニルジアミン、Ｎ，Ｎ’−ビス−３−（３’，５’−ジ−ｔ−ブチル−４−ヒドロキシフェノール）プロピオニルヘキサメチレンジアミン、３−（Ｎ−サリチロイル）アミノ−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、Ｎ，Ｎ’−ヘキサメチレン−ビス−（３−３，５−ｔ−ブチル−４−ヒドロキシフェニル）プロパンアミド）等が挙げられる。これら酸化防止剤は１種で用いてもよいし、２種以上を組み合わせて用いてもよい。
[Other additives]
In the present embodiment, other additives that can be added to the polyacetal resin composition are not limited as long as the effects of the present invention are not impaired, but preferable additives include antioxidants.
Examples of the antioxidant include n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate and n-octadecyl-3- (3′-methyl-5′-). t-butyl-4'-hydroxyphenyl) propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-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) , 3- (3,5-di-t-butyl-4-hydroxyphenyl) propion, triethylene glycol-bis- (3- (3-t-butyl-5-methyl-4-hydroxyphenyl) Propionate), tetrakis (methylene 3- (3'-t-butyl-4-hydroxyphenyl) propionate) methane, N, N'-bis- (3- (3,5-di-t-butyl-4-hydroxyphenol) ) Propionyl) hydrazine, N, N'-tetramethylene-bis-3- (3'-methyl-5'-t-butyl-4-hydroxyphenol) propionyldiamine, N, N'-bis-3- (3 ' , 5'-Di-t-butyl-4-hydroxyphenol) propionylhexamethylenediamine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N'-bis- (2- (3- (3,5-dibutyl-4-hydroxyphenyl) propionyloxy) ethyl) oxyamide, N, N'-hexamethylene-bis- (3-3,5-t-butyl-4-hydrido) Kishifeniru) propanamide), and the like. These antioxidants may be used alone or in combination of two or more.
酸化防止剤の含有量は、ポリアセタール樹脂１００質量部に対して、０．０１〜１．０質量部、好ましくは０．０５〜０．５質量部である。含有量が前記範囲内にあることで、熱安定性が向上する。 The content of the antioxidant is 0.01 to 1.0 part by mass, preferably 0.05 to 0.5 part by mass, based on 100 parts by mass of the polyacetal resin. When the content is within the above range, thermal stability is improved.
〔ポリアセタール樹脂組成物の特性〕
本実施形態のポリアセタール樹脂組成物のメルトフローインデックス（ＭＩ）は、ＡＳＴＭ−Ｄ−１２３８−５７Ｔに準拠し、１９０℃、２．１６ｋｇの条件で測定して、６０ｇ／１０分以上２００ｇ／１０分未満であり、好ましくは６０ｇ／１０分以上１６０ｇ／１０分未満であり、より好ましくは７０ｇ／１０分以上１４０ｇ／１０分未満である。メルトフローインデックスを６０ｇ／１０分以上とすることにより、金属粉末との分散性が向上し、メルトフローインデックスを２００ｇ／１０分未満とすることにより、押出し性、熱安定性、異物の抑制、及び金属粉末との分散性が向上する。
なお、ポリアセタール樹脂組成物のメルトフローインデックスは、例えば、使用する（Ａ）ポリアセタール樹脂により上記範囲に制御することができ、（Ａ）ポリアセタール樹脂のメルトフローインデックスが大きいほど、ポリアセタール樹脂組成物のメルトフローインデックスも大きくなる傾向がある。
(Characteristics of polyacetal resin composition)
The melt flow index (MI) of the polyacetal resin composition of the present embodiment is measured at 190 ° C. and 2.16 kg in accordance with ASTM-D-1238-57T, and is from 60 g / 10 min to 200 g / 10 min. Less than 60 g / 10 min and less than 160 g / 10 min, and more preferably 70 g / 10 min and less than 140 g / 10 min. By setting the melt flow index to 60 g / 10 min or more, dispersibility with metal powder is improved, and by setting the melt flow index to less than 200 g / 10 min, extrudability, heat stability, suppression of foreign matter, and Dispersibility with metal powder is improved.
The melt flow index of the polyacetal resin composition can be controlled within the above range by, for example, the (A) polyacetal resin used. As the melt flow index of the (A) polyacetal resin increases, the melt flow index of the polyacetal resin composition increases. The flow index also tends to increase.
〔ポリアセタール樹脂組成物の製造方法〕
本実施形態において、ポリアセタール樹脂組成物の製造方法は、特に限定されなく公知の方法により製造することができる。具体的には、上述した（Ａ）〜（Ｃ）成分、任意の添加剤等を、例えば、ヘンシェルミキサー、タンブラー、Ｖ字型ブレンダ―等で混合した後、単軸押出し機、或いは２軸押出し機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて溶融混練することにより製造することができ、ストランド状、ペレット状等、種々の形態の製品として得ることができる。
(Production method of polyacetal resin composition)
In the present embodiment, the method for producing the polyacetal resin composition is not particularly limited, and can be produced by a known method. Specifically, after mixing the above-mentioned components (A) to (C), optional additives, and the like with a Henschel mixer, a tumbler, a V-shaped blender, or the like, a single-screw extruder or a twin-screw extruder is used. It can be manufactured by melt-kneading using a kneader such as a kneader, a heating roll, a kneader, and a Banbury mixer, and can be obtained as products in various forms such as a strand shape and a pellet shape.
（金属樹脂組成物）
本実施形態の金属樹脂組成物は、金属粉末と、上記のポリアセタール樹脂組成物とを含む金属樹脂組成物であって、金属粉末の含有量が金属樹脂組成物１００質量％中に７０〜９５質量％である。これによれば、押出し性、熱安定性、異物の抑制を優れたたものにするとともに、金属粉末との分散性にも優れたものとすることができる。なお、当該金属樹脂組成物は、金属粉末射出成形に用いることができる。
金属粉末としては、機能性を付与するために、金属やセラミックスが好ましい。具体的な金属としては、アルミニウム、マグネシウム、バリウム、カルシウム、コバルト、亜鉛、銅、ニッケル、鉄、ケイ素、チタン、タングステン、並びに、これらをベースとする金属化合物及び金属合金が挙げられる。ここで、既に完成された合金のみならず、個々の合金成分の混合物を使用することもできる。
(Metal resin composition)
The metal resin composition of the present embodiment is a metal resin composition containing a metal powder and the above-mentioned polyacetal resin composition, wherein the content of the metal powder is 70 to 95 mass% in 100 mass% of the metal resin composition. %. According to this, extrudability, thermal stability, and suppression of foreign matter can be excellent, and also excellent in dispersibility with metal powder can be obtained. The metal resin composition can be used for metal powder injection molding.
As the metal powder, metals and ceramics are preferable in order to impart functionality. Specific metals include aluminum, magnesium, barium, calcium, cobalt, zinc, copper, nickel, iron, silicon, titanium, tungsten, and metal compounds and metal alloys based on these. Here, not only an already completed alloy but also a mixture of individual alloy components can be used.
具体的なセラミックスとしては、酸化亜鉛、酸化アルミニウム、ジルコニアなどの酸化物；ハイドロキシアパタイトなどの水酸化物；炭化ケイ素等の炭化物；窒化ケイ素や窒化ホウ素などの窒化物；蛍石などのハロゲン化物；ステアライトなどのケイ酸塩；チタン酸バリウムやチタン酸ジルコン酸鉛などのチタン酸塩；炭酸塩；リン酸塩；フェライト；高温超伝導物質；等も挙げられる。
これら無機物質は、１種単独で用いてもよく、種々の金属や金属合金、又はセラミックス等、幾つかの無機物質を組み合わせて用いることも可能である。
特に好ましい金属や合金金属としては、チタン合金やＳＵＳ３１６Ｌが挙げられ、セラミックとしては、Ａｌ２Ｏ３、ＺｒＯ２が挙げられる。
これら金属の粒子径は３０μｍ以下が好ましく、より好ましくは２０μｍ以下である。
Specific ceramics include oxides such as zinc oxide, aluminum oxide, and zirconia; hydroxides such as hydroxyapatite; carbides such as silicon carbide; nitrides such as silicon nitride and boron nitride; halides such as fluorite; Silicates such as stearite; titanates such as barium titanate and lead zirconate titanate; carbonates; phosphates; ferrites;
These inorganic substances may be used alone or in combination of several inorganic substances such as various metals, metal alloys, and ceramics.
Particularly preferred metals and alloy metals include titanium alloy and SUS316L, and examples of ceramics include Al 2 O 3 and ZrO 2 .
The particle size of these metals is preferably 30 μm or less, more preferably 20 μm or less.
本実施形態において、金属粉末と、上記のポリアセタール樹脂組成物とを含む金属樹脂組成物における金属粉末の含有量は、７０〜９５質量％であり、好ましくは８０〜９０質量％である。当該金属樹脂組成物は、金属粉末と上記のポリアセタール樹脂組成物の他に任意に添加剤を添加可能であるが、添加剤の含有量は、金属樹脂組成物１００質量％中に５質量％以下が好ましく、より好ましくは２質量％以下、さらに好ましくは０質量％である。 In the present embodiment, the content of the metal powder in the metal resin composition including the metal powder and the polyacetal resin composition is 70 to 95% by mass, and preferably 80 to 90% by mass. In the metal resin composition, an additive can be arbitrarily added in addition to the metal powder and the polyacetal resin composition, but the content of the additive is 5% by mass or less in 100% by mass of the metal resin composition. Is more preferred, more preferably 2% by mass or less, and still more preferably 0% by mass.
本実施形態においては、金属樹脂組成物中の金属粉末の分散性は、後述の実施例に記載の評価方法で測定して、１．２０以下が好ましく、より好ましくは１．１５以下であり、さらに好ましくは１．１０以下である。これにより、金属樹脂組成物より良好な成形体が得られる。 In the present embodiment, the dispersibility of the metal powder in the metal resin composition is preferably 1.20 or less, more preferably 1.15 or less, as measured by the evaluation method described in Examples described below, More preferably, it is 1.10. Thereby, a molded article better than the metal resin composition is obtained.
〔金属樹脂組成物の製造方法〕
本実施形態において、金属樹脂組成物の製造方法は、特に限定されなく公知の方法により製造することができる。具体的には、上述した金属粉末とポリアセタール樹脂組成物等を、例えば、ヘンシェルミキサー、タンブラー、Ｖ字型ブレンダ―等で混合した後、単軸押出し機、或いは２軸押出し機、加熱ロール、ニーダー、バンバリーミキサー等の混練機を用いて半溶融状態で溶融混練することにより製造することができ、ストランド状、ペレット状等、種々の形態の製品として得ることができる。
(Production method of metal resin composition)
In the present embodiment, the method for producing the metal resin composition is not particularly limited, and can be produced by a known method. Specifically, after mixing the above metal powder and the polyacetal resin composition with a Henschel mixer, a tumbler, a V-shaped blender, or the like, a single screw extruder or a twin screw extruder, a heating roll, a kneader It can be manufactured by melt-kneading in a semi-molten state using a kneader such as a Banbury mixer, and can be obtained as products in various forms such as a strand shape and a pellet shape.
以下、具体的な実施例及び比較例を挙げて本発明について詳細に説明するが、本発明は以下の実施例に限定されるものではない。
尚、実施例及び比較例中の用語及び特性の測定法は以下の通りとする。
Hereinafter, the present invention will be described in detail with reference to specific examples and comparative examples, but the present invention is not limited to the following examples.
In addition, the measuring method of the term and characteristic in an Example and a comparative example is as follows.
〔（Ａ）ポリアセタール樹脂〕
（Ａ−１）
熱媒を通すことのできるジャケット付き２軸パドル型連続重合反応機（（株）栗本鐵工所製、径２Ｂ、Ｌ／Ｄ＝１４．８）を温度８０℃に調整した。
重合触媒として三フッ化ホウ素−ジ−ｎ−ブチルエーテラートをシクロヘキサンにて０．２６質量％に希釈した触媒調合液６９ｇ／ｈｒと、トリオキサン３５００ｇ／ｈｒ、１，３−ジオキソラン１２１ｇ／ｈｒ、分子量調節剤としてメチラール７．１ｇ／ｈｒを、重合反応機に連続的に供給し重合を行った。
重合反応機から排出されたものは、０．５質量％のトリエチルアミン水溶液中に投入し重合触媒の失活を行った後、濾過、洗浄、乾燥を行った。
次に、２００℃に設定されたベント付の２軸押出し機（Ｌ／Ｄ＝４０）に供給し、末端安定化ゾーンに、０．８質量％トリエチルアミン水溶液を、窒素の量に換算して２０ｐｐｍになるように液添し、９０ｋＰａで減圧脱気しながら安定化させ、ペレタイザーにてペレット化した。その後１００℃で２ｈｒ乾燥を行い、（Ａ−１）ポリアセタール樹脂を得た。
得られた（Ａ−１）ポリアセタール樹脂は、融点１６４℃、メルトフローインデックス７１ｇ／１０分であった。
[(A) polyacetal resin]
(A-1)
The temperature of a jacketed twin-screw paddle type continuous polymerization reactor (made by Kurimoto Iron Works Co., Ltd., diameter 2B, L / D = 14.8) through which a heat medium can pass was adjusted to 80 ° C.
69 g / hr of a catalyst mixture prepared by diluting boron trifluoride-di-n-butyl etherate to 0.26% by mass with cyclohexane as a polymerization catalyst, 3500 g / hr of trioxane, 121 g / hr of 1,3-dioxolane, molecular weight 7.1 g / hr of methylal as a regulator was continuously supplied to the polymerization reactor to perform polymerization.
The product discharged from the polymerization reactor was put into a 0.5% by mass aqueous solution of triethylamine to deactivate the polymerization catalyst, followed by filtration, washing and drying.
Next, the mixture was fed to a vented twin-screw extruder (L / D = 40) set at 200 ° C., and the end stabilization zone was treated with a 0.8% by mass aqueous solution of triethylamine in an amount of 20 ppm in terms of nitrogen. , Stabilized while deaerated under reduced pressure at 90 kPa, and pelletized with a pelletizer. Thereafter, drying was performed at 100 ° C. for 2 hours to obtain (A-1) a polyacetal resin.
The obtained (A-1) polyacetal resin had a melting point of 164 ° C. and a melt flow index of 71 g / 10 minutes.
（Ａ−２）
分子量調節剤としてのメチラールの流量を９．４ｇ／ｈｒとした以外は、（Ａ−１）ポリアセタール樹脂の製造方法と同様に（Ａ−２）ポリアセタール樹脂を製造した。
得られた（Ａ−２）ポリアセタール樹脂は、融点１６４℃、メルトフローインデックス１２１ｇ／１０分であった。
(A-2)
(A-2) A polyacetal resin was produced in the same manner as in the production method of (A-1) polyacetal resin, except that the flow rate of methylal as a molecular weight regulator was 9.4 g / hr.
The obtained (A-2) polyacetal resin had a melting point of 164 ° C. and a melt flow index of 121 g / 10 minutes.
（Ａ−３）
分子量調節剤としてのメチラールの流量を１０．６ｇ／ｈｒとした以外は、（Ａ−１）ポリアセタール樹脂の製造方法と同様に（Ａ−３）ポリアセタール樹脂を製造した。
得られた（Ａ−３）ポリアセタール樹脂は、融点１６４℃、メルトフローインデックス１８０ｇ／１０分であった。
(A-3)
(A-3) A polyacetal resin was produced in the same manner as in the production method of (A-1) polyacetal resin except that the flow rate of methylal as a molecular weight regulator was 10.6 g / hr.
The obtained (A-3) polyacetal resin had a melting point of 164 ° C. and a melt flow index of 180 g / 10 minutes.
（Ａ−４）
分子量調節剤としてのメチラールの流量を４．４ｇ／ｈｒとした以外は、（Ａ−１）ポリアセタール樹脂の製造方法と同様に（Ａ−３）ポリアセタール樹脂を製造した。
得られた（Ａ−３）ポリアセタール樹脂は、融点１６４℃、メルトフローインデックス３１ｇ／１０分であった。
(A-4)
(A-3) A polyacetal resin was produced in the same manner as in the production method of (A-1) polyacetal resin, except that the flow rate of methylal as a molecular weight modifier was 4.4 g / hr.
The obtained (A-3) polyacetal resin had a melting point of 164 ° C. and a melt flow index of 31 g / 10 minutes.
（Ａ−５）
分子量調節剤としてのメチラールの流量を１１．６ｇ／ｈｒとした以外は、（Ａ−１）ポリアセタール樹脂の製造方法と同様に（Ａ−５）ポリアセタール樹脂を製造した。
得られた（Ａ−５）ポリアセタール樹脂は、融点１６４℃、メルトフローインデックス２１３ｇ／１０分であった。
(A-5)
(A-5) A polyacetal resin was produced in the same manner as in the production method of (A-1) polyacetal resin, except that the flow rate of methylal as a molecular weight regulator was 11.6 g / hr.
The obtained (A-5) polyacetal resin had a melting point of 164 ° C. and a melt flow index of 213 g / 10 minutes.
〔（Ｂ）窒素含有化合物〕
（Ｂ−１）ナイロン６６（分子量１００００）
（Ｂ−２）メラミン（日産化学工業（株）社製）
[(B) nitrogen-containing compound]
(B-1) Nylon 66 (molecular weight 10,000)
(B-2) Melamine (manufactured by Nissan Chemical Industries, Ltd.)
〔（Ｃ）脂肪酸金属塩〕
（Ｃ−１）ステアリン酸カルシウム
（Ｃ−２）モンタン酸カルシウム
[(C) fatty acid metal salt]
(C-1) Calcium stearate (C-2) Calcium montanate
〔その他添加剤〕
（Ｄ−１）
酸化防止剤：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］（ＢＡＳＦ（株）社製 Ｉｒｇａｎｏｘ２４５）
(Other additives)
(D-1)
Antioxidant: triethylene glycol-bis- [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (Irganox 245 manufactured by BASF Corporation)
〔メルトフローインデックス（ＭＩ）〕
ＡＳＴＭ−Ｄ−１２３８に準拠し、東洋精機製のＭＥＬＴ ＩＮＤＥＸＥＲを用いて１９０℃、２１６０ｇの条件下でＭＩ（メルトフローインデックス：ｇ／１０分）を測定した。
[Melt flow index (MI)]
Based on ASTM-D-1238, MI (melt flow index: g / 10 minutes) was measured at 190 ° C. and 2160 g using MELT INDEXER manufactured by Toyo Seiki.
〔熱安定性〕
押出しで得られたポリアセタール樹脂組成物（３±０．０１ｇ）を、窒素雰囲気下（５０ｎｌ／ｈｒ）で、２３０℃に加熱、溶融させ、滞留時間２〜３０分間に発生するホルムガスを、１ｍｏｌ／ｌの亜硫酸ナトリウム水溶液に吸収させ、生成する水酸化ナトリウムを、１／１００規定の硫酸で滴定し、ホルムガス量に換算して求めた。
この滴定には、指示薬としてチモールフタレインを用い、青色が無色となった時点を終点とした。
(Thermal stability)
The polyacetal resin composition (3 ± 0.01 g) obtained by extrusion was heated and melted at 230 ° C. under a nitrogen atmosphere (50 nl / hr), and the form gas generated during a residence time of 2 to 30 minutes was reduced to 1 mol / mol. 1 of sodium sulfite aqueous solution, and the resulting sodium hydroxide was titrated with 1 / 100N sulfuric acid and converted to the amount of form gas.
In this titration, thymolphthalein was used as an indicator, and the time when the blue color became colorless was determined as the end point.
〔押出し性〕
押出しで得られたポリアセタール樹脂組成物のペレット２．５ｋｇを、目視で確認し、ペレットが繋がった形の物を連粒と称し、その連流物を取出し重量を測定した。
その割合を計算し点数付けを行った。点数が大きければ大きいほど押し出し性が良い（連粒の割合が多いほど押出し性が良くない）ことを示す。
３：連粒なし
２：連粒の割合が１０％未満
１：連粒の割合が５０％以上
[Extrusion property]
2.5 kg of pellets of the polyacetal resin composition obtained by the extrusion were visually confirmed, and the connected pellets were referred to as continuous grains, and the connected products were taken out and the weight was measured.
The ratio was calculated and scored. The larger the score, the better the extrudability (the larger the ratio of continuous grains, the poorer the extrudability).
3: No consecutive grains 2: The proportion of consecutive grains is less than 10% 1: The proportion of consecutive grains is 50% or more
〔異物〕
ポリアセタール樹脂組成物を、２２０℃に設定したホットプレス（松田製作所製）で、型枠として１８０ｍｍ×１８０ｍｍ×２ｍｍ（厚み）を用いて、平板をプレス成形した。
成形板の両面について、ルーペを用いて０．１ｍｍ以上の異物の数を測定した。
異物は、黒、茶、赤、黄等の色があるが全てを数えた。
(Foreign matter)
Using a hot press (manufactured by Matsuda Seisakusho) set at 220 ° C., the polyacetal resin composition was used to press-mold a flat plate using a 180 mm × 180 mm × 2 mm (thickness) mold.
The number of foreign substances having a size of 0.1 mm or more was measured on both surfaces of the molded plate using a loupe.
The foreign substances were black, brown, red, yellow and other colors, but all were counted.
〔金属粉末の分散性〕
設定１７０℃に加温したラボプラストミルを用いて、２０μｍのＳＵＳ３１６Ｌ粉末７０ｇと、下記の実施例・比較例で得られたポリアセタール樹脂組成物３０ｇとを半溶融状態で３０分混練し、おこし状の固形物（体積３６ｃｍ３）を作製した。得られた固形物から、任意に選択した部分５か所を１０ｇずつ切出した。
次に、設定５５０℃の電気炉中でポリアセタール樹脂組成物を脱脂させ、残った金属の重量を測定した。そして最大重量と最少重量の比を求めた。この比が小さいものほど分散性が良いことを示す。
(Dispersibility of metal powder)
Using a Labo Plastomill heated to a setting of 170 ° C., 70 g of SUS316L powder of 20 μm and 30 g of a polyacetal resin composition obtained in the following Examples and Comparative Examples were kneaded in a semi-molten state for 30 minutes, and the resulting mixture was kneaded. (Solid volume: 36 cm 3 ) was prepared. Five arbitrarily selected portions were cut out at 10 g each from the obtained solid material.
Next, the polyacetal resin composition was degreased in an electric furnace set at 550 ° C., and the weight of the remaining metal was measured. Then, the ratio between the maximum weight and the minimum weight was determined. The smaller the ratio, the better the dispersibility.
〔実施例１〕
（Ａ−１）ポリアセタール樹脂１００質量部に、（Ｂ−１）ナイロン６６を０．０５質量部、（Ｃ−１）ステアリン酸カルシウム０．３質量部、を均一添加混合し、２００℃に設定されたベント付の２軸押出し機（Ｌ／Ｄ＝４０）に供給し、９０ｋＰａで減圧脱気しながらペレット化した。その後１００℃で２ｈｒ乾燥を行った。
得られたペレットについて、評価を実施し、結果を表１に示した。
[Example 1]
(A-1) 100 parts by mass of polyacetal resin, 0.05 parts by mass of (B-1) nylon 66 and 0.3 parts by mass of calcium stearate (C-1) were uniformly added and mixed. The mixture was supplied to a twin-screw extruder (L / D = 40) equipped with a vent, and pelletized while degassing at 90 kPa under reduced pressure. Thereafter, drying was performed at 100 ° C. for 2 hours.
The obtained pellets were evaluated and the results are shown in Table 1.
〔実施例２〜１３〕
表１に記載の組成にて、実施例１と同様の操作を実施した。得られたペレットについて、評価を実施し、結果を表１に示した。
[Examples 2 to 13]
The same operations as in Example 1 were performed with the compositions shown in Table 1. The obtained pellets were evaluated and the results are shown in Table 1.
〔比較例１〜９〕
表２に記載の組成にて、実施例１と同様の操作を実施した。得られたペレットについて、評価を実施し、結果を表２に示した。
[Comparative Examples 1 to 9]
The same operations as in Example 1 were performed with the compositions shown in Table 2. The obtained pellets were evaluated, and the results are shown in Table 2.
前記表１、２の評価結果から明らかなように、（Ａ）ポリアセタール樹脂と、（Ｂ）窒素含有化合物と、（Ｃ）脂肪酸金属塩とを所定の含有量で含み、メルトフローインデックスが所定の範囲であり、（Ｂ）窒素含有化合物の含有量に対する（Ｃ）脂肪酸金属塩の含有量の比が所定の範囲である実施例は、熱安定性、押出し性、異物の抑制に優れ、更に、金属粉末との分散性にも優れていることがわかった。 As is clear from the evaluation results in Tables 1 and 2, (A) a polyacetal resin, (B) a nitrogen-containing compound, and (C) a fatty acid metal salt at a predetermined content, and a melt flow index is a predetermined value. Examples in which the ratio of the content of the (C) fatty acid metal salt to the content of the (B) nitrogen-containing compound is within a predetermined range are excellent in heat stability, extrudability, and suppression of foreign matter, and It was also found that the dispersibility with the metal powder was excellent.
本発明によれば、押出し性、熱安定性、異物の抑制に優れ、更には金属粉末との分散性に優れたポリアセタール樹脂組成物、並びに、押出し性及び熱安定性に優れ、異物含有が少なく、更には金属粉末が効果的に分散した、金属粉末とポリアセタール樹脂組成物との金属樹脂組成物を提供することができる。 According to the present invention, extrudability, heat stability, excellent suppression of foreign matter, furthermore a polyacetal resin composition excellent in dispersibility with metal powder, and extrudability and heat stability are excellent, foreign matter content is small Further, it is possible to provide a metal resin composition of a metal powder and a polyacetal resin composition in which the metal powder is effectively dispersed.
Claims (5)
１９０℃、２．１６ｋｇの条件で測定したメルトフローインデックスが６０ｇ／１０分以上２００ｇ／１０分未満であり、
前記（Ｂ）窒素含有化合物の含有量に対する前記（Ｃ）脂肪酸金属塩の含有量の比（（Ｃ）／（Ｂ））が１〜１５であることを特徴とする、ポリアセタール樹脂組成物。 (A) 100 parts by mass of a polyacetal resin, (B) 0.005 to 0.2 parts by mass of a nitrogen-containing compound, and (C) 0.01 to 0.8 parts by mass of a fatty acid metal salt,
A melt flow index measured at 190 ° C. and 2.16 kg is 60 g / 10 min or more and less than 200 g / 10 min;
A polyacetal resin composition, wherein a ratio ((C) / (B)) of the content of the (C) fatty acid metal salt to the content of the (B) nitrogen-containing compound is 1 to 15.
前記（Ｂ）窒素含有化合物の含有量が、０．００５〜０．１質量部であり、前記（Ｃ）脂肪酸金属塩の含有量が０．０１〜０．６質量部である、請求項１又は２に記載のポリアセタール樹脂組成物。 (A) 100 parts by mass of the polyacetal resin,
The content of the (B) nitrogen-containing compound is 0.005 to 0.1 parts by mass, and the content of the (C) fatty acid metal salt is 0.01 to 0.6 parts by mass. Or the polyacetal resin composition according to 2.
A metal resin composition comprising a metal powder and the polyacetal resin composition according to any one of claims 1 to 4, wherein the content of the metal powder is 70% by mass in 100% by mass of the metal resin composition. A metal resin composition of about 95% by mass.
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| WO2023282135A1 (en) | 2021-07-06 | 2023-01-12 | 三菱瓦斯化学株式会社 | Polyacetal resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2022158105A1 (en) | 2021-01-25 | 2022-07-28 | 三菱瓦斯化学株式会社 | Polyacetal resin composition |
| KR20230138447A (en) | 2021-01-25 | 2023-10-05 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyacetal resin composition |
| WO2023282135A1 (en) | 2021-07-06 | 2023-01-12 | 三菱瓦斯化学株式会社 | Polyacetal resin composition |
| KR20240031215A (en) | 2021-07-06 | 2024-03-07 | 미쯔비시 가스 케미칼 컴파니, 인코포레이티드 | Polyacetal resin composition |
| WO2023243658A1 (en) * | 2022-06-15 | 2023-12-21 | 三菱瓦斯化学株式会社 | Polyacetal resin composition |
Also Published As
| Publication number | Publication date |
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| CN110878167A (en) | 2020-03-13 |
| TWI773922B (en) | 2022-08-11 |
| JP7301664B2 (en) | 2023-07-03 |
| TW202016208A (en) | 2020-05-01 |
| CN110878167B (en) | 2023-02-21 |
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