CN110914353A - 组合物、含有其的热塑性树脂组合物和其成型品 - Google Patents
组合物、含有其的热塑性树脂组合物和其成型品 Download PDFInfo
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- CN110914353A CN110914353A CN201980002959.XA CN201980002959A CN110914353A CN 110914353 A CN110914353 A CN 110914353A CN 201980002959 A CN201980002959 A CN 201980002959A CN 110914353 A CN110914353 A CN 110914353A
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- general formula
- thermoplastic resin
- butyl
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- 239000000203 mixture Substances 0.000 title claims abstract description 75
- 229920005992 thermoplastic resin Polymers 0.000 title claims abstract description 59
- 239000011342 resin composition Substances 0.000 title claims abstract description 28
- -1 sodium carboxylate Chemical class 0.000 claims abstract description 141
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 21
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 19
- 239000011734 sodium Substances 0.000 claims abstract description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 125000004429 atom Chemical group 0.000 claims abstract description 7
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- RKFMOTBTFHXWCM-UHFFFAOYSA-M [AlH2]O Chemical compound [AlH2]O RKFMOTBTFHXWCM-UHFFFAOYSA-M 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 47
- 239000011347 resin Substances 0.000 claims description 47
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 32
- 239000000194 fatty acid Substances 0.000 claims description 32
- 229930195729 fatty acid Natural products 0.000 claims description 32
- 150000004665 fatty acids Chemical class 0.000 claims description 27
- 239000003963 antioxidant agent Substances 0.000 claims description 25
- 150000001875 compounds Chemical class 0.000 claims description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000000975 dye Substances 0.000 claims description 14
- 239000002667 nucleating agent Substances 0.000 claims description 14
- 239000004743 Polypropylene Substances 0.000 claims description 13
- 239000002216 antistatic agent Substances 0.000 claims description 13
- 239000003063 flame retardant Substances 0.000 claims description 13
- 229920001155 polypropylene Polymers 0.000 claims description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000000049 pigment Substances 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 239000006081 fluorescent whitening agent Substances 0.000 claims description 6
- 150000003568 thioethers Chemical class 0.000 claims description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004436 sodium atom Chemical group 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 abstract description 12
- 238000000465 moulding Methods 0.000 abstract description 9
- 125000003118 aryl group Chemical group 0.000 abstract description 5
- 150000002148 esters Chemical class 0.000 abstract description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 41
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 25
- 230000000694 effects Effects 0.000 description 22
- 229940050390 benzoate Drugs 0.000 description 20
- 229910019142 PO4 Inorganic materials 0.000 description 19
- 235000021317 phosphate Nutrition 0.000 description 19
- 229910052782 aluminium Inorganic materials 0.000 description 18
- 239000010452 phosphate Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 16
- 238000001746 injection moulding Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 15
- 230000003078 antioxidant effect Effects 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008188 pellet Substances 0.000 description 13
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 11
- 239000012964 benzotriazole Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229920001971 elastomer Polymers 0.000 description 9
- 235000021355 Stearic acid Nutrition 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical class [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 8
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 8
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 8
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 8
- 239000008117 stearic acid Substances 0.000 description 8
- 239000007983 Tris buffer Substances 0.000 description 7
- 229960001545 hydrotalcite Drugs 0.000 description 7
- 229910001701 hydrotalcite Inorganic materials 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 7
- 235000010234 sodium benzoate Nutrition 0.000 description 7
- 239000004299 sodium benzoate Substances 0.000 description 7
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- 239000000806 elastomer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 6
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 5
- 229920000515 polycarbonate Polymers 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 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 4
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 235000021314 Palmitic acid Nutrition 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- MBMBGCFOFBJSGT-KUBAVDMBSA-N all-cis-docosa-4,7,10,13,16,19-hexaenoic acid Chemical compound CC\C=C/C\C=C/C\C=C/C\C=C/C\C=C/C\C=C/CCC(O)=O MBMBGCFOFBJSGT-KUBAVDMBSA-N 0.000 description 4
- 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 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 description 4
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 4
- SECPZKHBENQXJG-FPLPWBNLSA-N palmitoleic acid Chemical compound CCCCCC\C=C/CCCCCCCC(O)=O SECPZKHBENQXJG-FPLPWBNLSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 4
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- HIBWGGKDGCBPTA-UHFFFAOYSA-N C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 HIBWGGKDGCBPTA-UHFFFAOYSA-N 0.000 description 3
- 239000005639 Lauric acid Substances 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229920000388 Polyphosphate Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- AHANXAKGNAKFSK-PDBXOOCHSA-N all-cis-icosa-11,14,17-trienoic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCCCC(O)=O AHANXAKGNAKFSK-PDBXOOCHSA-N 0.000 description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 3
- 239000008116 calcium stearate Substances 0.000 description 3
- 235000013539 calcium stearate Nutrition 0.000 description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 3
- PRHHYVQTPBEDFE-UHFFFAOYSA-N eicosatrienoic acid Natural products CCCCCC=CCC=CCCCCC=CCCCC(O)=O PRHHYVQTPBEDFE-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229960004488 linolenic acid Drugs 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- 150000004671 saturated fatty acids Chemical class 0.000 description 3
- 239000012321 sodium triacetoxyborohydride Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- YWEWWNPYDDHZDI-JJKKTNRVSA-N (1r)-1-[(4r,4ar,8as)-2,6-bis(3,4-dimethylphenyl)-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C1=C(C)C(C)=CC=C1C1O[C@H]2[C@@H]([C@H](O)CO)OC(C=3C=C(C)C(C)=CC=3)O[C@H]2CO1 YWEWWNPYDDHZDI-JJKKTNRVSA-N 0.000 description 2
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 2
- OHWBOQAWKNFLRG-UEQSERJNSA-N (3s,4s,5s,6r)-1,8-bis(4-ethylphenyl)octa-1,7-diene-2,3,4,5,6,7-hexol Chemical compound C1=CC(CC)=CC=C1C=C(O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=CC1=CC=C(CC)C=C1 OHWBOQAWKNFLRG-UEQSERJNSA-N 0.000 description 2
- YWWVWXASSLXJHU-AATRIKPKSA-N (9E)-tetradecenoic acid Chemical compound CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 2
- GGQHNQQPLWRNHD-UHFFFAOYSA-N 1,3,7,9-tetratert-butyl-11-hydroxy-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound C1C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP(O)(=O)OC2=C1C=C(C(C)(C)C)C=C2C(C)(C)C GGQHNQQPLWRNHD-UHFFFAOYSA-N 0.000 description 2
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- BVUXDWXKPROUDO-UHFFFAOYSA-N 2,6-di-tert-butyl-4-ethylphenol Chemical compound CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BVUXDWXKPROUDO-UHFFFAOYSA-N 0.000 description 2
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 2
- IKEHOXWJQXIQAG-UHFFFAOYSA-N 2-tert-butyl-4-methylphenol Chemical compound CC1=CC=C(O)C(C(C)(C)C)=C1 IKEHOXWJQXIQAG-UHFFFAOYSA-N 0.000 description 2
- ZDFKSZDMHJHQHS-UHFFFAOYSA-N 2-tert-butylbenzoic acid Chemical compound CC(C)(C)C1=CC=CC=C1C(O)=O ZDFKSZDMHJHQHS-UHFFFAOYSA-N 0.000 description 2
- ACZGCWSMSTYWDQ-UHFFFAOYSA-N 3h-1-benzofuran-2-one Chemical compound C1=CC=C2OC(=O)CC2=C1 ACZGCWSMSTYWDQ-UHFFFAOYSA-N 0.000 description 2
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Abstract
能对热塑性树脂赋予优异的透明性和物性的的组合物、含有其的热塑性树脂组合物和其成型品。一种组合物,其含有下述(A)~(D),各成分相对于(A)~(D)的总计量的比率如下:(A)35~75质量%、(B)10~40质量%、(C)0~20质量%、(D)5~35质量%,(A)为通式(1)所示的芳香族磷酸酯金属盐,其中,通式(1)中,R1~R4各自独立地表示氢原子等,R5表示碳原子数1~4的烷叉基,m为1时M1表示锂,m为2时M1为羟基铝;(B)为羧酸钠;(C)用通式(2)表示,其中,通式(2)中,R6表示由碳原子数10~30的脂肪族有机酸所导入的基团,M2表示n价的金属原子等,n为1~3的整数。
Description
技术领域
本发明涉及组合物、含有其的热塑性树脂组合物(以下,也简称为“树脂组合物”)和其成型品,详细而言,涉及能对热塑性树脂赋予优异的透明性和物性的流动性优异的组合物、含有其的热塑性树脂组合物和其成型品。
背景技术
热塑性树脂、特别是聚乙烯、聚丙烯和聚1-丁烯等烯烃系树脂由于廉价、且成型加工性、卫生性、耐热性、耐化学药品性、力学特性、低比重等优异的性质而被广泛用于建筑材料、汽车材料、家电机·电子用材料、纤维材料、包装用材料、农业用材料、家电制品的壳体材料、生活杂货用品、医疗器具、食品容器、饮料容器、薄膜、片和结构部件等各种成型品。
然而,烯烃系树脂的成型后的结晶速度慢,因此,成型循环性低,另外,由于加热成型后的结晶的进行而生成大的晶体,存在透明性、强度不足的缺点。这些缺点全部源自烯烃系树脂的结晶性,已知如果可以提高烯烃系树脂的结晶温度、使微细的晶体急速生成,则可以消除上述问题。
因此,已知有添加成核剂,作为成核剂,例如已知有:苯甲酸钠、4-叔丁基苯甲酸铝、己二酸钠和双环[2.2.1]庚烷-2,3-二羧酸二钠等羧酸金属盐、双(4-叔丁基苯基)磷酸酯钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯钠、2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂等环状有机磷酸酯金属盐、二亚苄基山梨糖醇、双(甲基亚苄基)山梨糖醇、双(3,4-二甲基亚苄基)山梨糖醇、双(对乙基亚苄基)山梨糖醇、和双(二甲基亚苄基)山梨糖醇等多元醇衍生物、N,N’,N”-三[2-甲基环己基]-1,2,3-丙烷三甲酰胺、N,N’,N”-三环己基-1,3,5-苯三甲酰胺、N,N’-二环己基萘二甲酰胺、1,3,5-三(2,2-二甲基丙酰胺)苯等酰胺化合物等。
这些化合物中,作为烯烃系树脂的透明性和物性的改良效果大的成核剂,已知有环状有机磷酸酯金属盐。例如,专利文献1中提出了一种树脂组合物,其在结晶性合成树脂中含有环状有机磷酸酯碱性铝盐和硬脂酸钠。另外,专利文献2中提出了一种树脂组合物,其在结晶性合成树脂中含有环状有机磷酸酯碱性多元金属盐和碱金属羧酸盐。
进而,专利文献3中记载了成核剂优选2,2’-亚甲基-双(4,6-二叔丁基苯氧基)磷酸酯钠、二(4-叔丁基-苯氧基)磷酸酯钠、双[2,2-亚甲基双(4,6-二叔丁基苯氧基)磷酸]羟基铝、双(2-烷基、4-烷基苯氧基)磷酸酯、双环[2,2,1]庚烷二羧酸钠或双环[2,2,1]庚烷二羧酸钙中的一种以上的、其中二种以上的混合物,且实施例中记载了添加有该成核剂和苯甲酸钠的树脂组合物。此外,专利文献4中提出了一种组合物,其混合有对叔丁基苯甲酸羟基铝和/或苯甲酸钠、与双[2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝。另外,专利文献5中提出了一种聚丙烯用透明化剂,其含有:用于取代磷酸二芳基酯的多元金属盐、和一元脂肪酸的碱金属盐。
现有技术文献
专利文献
专利文献1:日本特开平8-120116号公报
专利文献2:日本特开平5-156078号公报
专利文献3:中国公开专利102344609号公报
专利文献4:中国公开专利101845171号公报
专利文献5:中国公开专利101265347号公报
发明内容
发明要解决的问题
然而,专利文献1、2中记载了双[2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝与硬脂酸钠的组合,但这些成核剂效果尚不充分,寻求进一步的改善。另外,专利文献3中,示出改善耐蠕变性,但没有对配混了双[2,2-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝进行评价,涉及透明性和物性的评价不充分。进而,专利文献4中记载了共混有苯甲酸钠或苯甲酸钠和对叔羟基苯甲酸羟基铝、与双[2,2-亚甲基双(4,6-二叔丁基苯氧基)磷酸]羟基铝的组合物,但未提及更多内容,且未进行配混于树脂中的评价,因此,关于对透明性和物性的影响,尚留有研究的余地。此外,专利文献5中示出了一种树脂组合物,其含有:双[2,2-亚甲基双(4,6-二叔丁基苯氧基)磷酸]羟基铝;以及,硬脂酸钠、松香酸钠等羧酸钠、和/或羟基硬脂酸锂等一元脂肪酸的碱金属盐,但对于其效果并非为可满足者,寻求进一步的改善。
另外,芳香族磷酸酯金属盐具有缺乏作为粉体的流动性的缺点,从输送性、作业性、测量性的观点出发,要求改善流动性。
因此,本发明的目的在于,提供:能对热塑性树脂赋予优异的透明性和物性的流动性优异的组合物、含有其的热塑性树脂组合物和其成型品。
用于解决问题的方案
本发明人等为了解决上述课题而进行了深入研究,结果发现:通过将芳香族磷酸酯金属盐、羧酸钠、脂肪酸金属盐和脂肪酸调整为特定范围,从而可以解决上述课题,至此完成了本发明。
即,本发明的组合物为一种组合物,其特征在于,其为含有下述(A)、(B)、(C)和(D)的组合物,各成分相对于(A)+(B)+(C)+(D)的总计量的比率如下:
(A)35~75质量%、
(B)10~40质量%、
(C)0~20质量%、
(D)5~35质量%。
(A)通式(1)所示的芳香族磷酸酯金属盐,其中,通式(1)中,R1~R4各自独立地表示氢原子或碳原子数1~9的直链或具有支链的烷基,R5表示碳原子数1~4的烷叉基,m表示1或2的数,m为1时M1表示锂,m为2时M1为羟基铝
(B)羧酸钠
(C)通式(2)所示的脂肪酸金属盐,其中,通式(2)中,R6表示由碳原子数10~30的脂肪族有机酸所导入的基团,M2表示n价的金属原子(其中,不包括钠原子和钙原子)或Al(OH)3-n,n为1~3的整数
(D)脂肪酸
本发明的组合物中,前述芳香族磷酸酯金属盐优选为通式(3)所示的化合物
(通式(3)中,R1~R5表示与通式(1)相同者。)。
另外,本发明的组合物中,优选含有选自由酚系抗氧化剂、磷系抗氧化剂、硫醚系抗氧化剂、其他抗氧化剂、受阻胺化合物、紫外线吸收剂、与通式(1)所示的结构不同的成核剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、脂肪酸金属盐、抗静电剂、荧光增白剂、颜料、染料组成的组中的1种以上的添加剂。进而,本发明的组合物中,前述(B)羧酸钠优选为芳香族羧酸钠或脂肪酸钠。
进一步另外,本发明的组合物中,优选(A)为35~55质量%、(B)为20~40质量%、(C)为5~20质量%、(D)为5~35质量%。
本发明的热塑性树脂组合物的特征在于,相对于热塑性树脂100质量份,含有本发明的组合物,使得通式(1)所示的芳香族磷酸酯金属盐(A)成为0.001~10质量份。
本发明的热塑性树脂组合物中,前述热塑性树脂优选烯烃系树脂、特别优选聚丙烯。
本发明的成型品的特征在于,其是使用本发明的热塑性树脂组合物而成的。
发明的效果
根据本发明,可以提供能对热塑性树脂赋予优异的透明性和物性的流动性优异的组合物、含有其的热塑性树脂组合物和其成型品。特别是,对于聚丙烯使用了本发明的组合物的本发明的成型品不仅可以改善透明性、物性,还可以改善冲击强度、抑制成型品的着色。
具体实施方式
以下,对本发明的实施方式详细进行说明。
本发明的组合物为含有下述(A)、(B)、(C)和(D)的组合物,各成分相对于(A)+(B)+(C)+(D)的总计量的比率如下:(A)35~75质量%、(B)10~40质量%、(C)0~20质量%、(D)5~35质量%。此处,(A)为芳香族磷酸酯金属盐,其为下述通式(1)所示的芳香族磷酸酯金属盐,通式(1)中,R1~R4各自独立地表示氢原子或碳原子数1~9的直链或具有支链的烷基,R5表示碳原子数1~4的烷叉基。m表示1或2的数,m为1时M1表示锂,m为2时M1为羟基铝。
另外,(B)为羧酸钠,(C)为通式(2)所示的脂肪酸金属盐,通式(2)中,R6表示由碳原子数10~30的脂肪族有机酸所导入的基团,M2表示n价的金属原子(其中,不包括钠原子和钙原子)或Al(OH)3-n,n表示1~3的整数。
进而,(D)为脂肪酸。
首先,对(A)通式(1)所示的芳香族磷酸酯金属盐(以下,也称为(A)成分)进行说明。通式(1)中,R1~R4各自独立地表示氢原子或直链或具有支链的碳原子数1~9的烷基,R5表示碳原子数1~4的烷叉基,m表示1或2的数,m为1时M1表示锂,m为2时M1表示羟基铝。
作为通式(1)中的R1~R4所示的碳原子数1~9的直链或具有支链的烷基,例如可以举出甲基、乙基、丙基、异丙基、丁基、仲丁基、叔丁基、异丁基、戊基、叔戊基、己基、庚基、辛基、异辛基、叔辛基、2-乙基己基、壬基、异壬基等,本发明的组合物中,特别优选叔丁基。
作为通式(1)中的R5所示的碳原子数1~4的烷叉基,例如可以举出亚甲基、乙叉基、丙叉基、丁叉基等,本发明的组合物中,优选亚甲基。
作为本发明的组合物的(A)成分的制造方法,例如可以举出如下方法:使相应的结构的环状磷酸、与铝或锂的氢氧化物、氧化物、卤化物、硫酸盐、硝酸盐、醇盐化合物等化合物用根据需要使用的碱性化合物等反应剂进行反应的方法;使相应的结构的芳香族磷酸酯的碱金属盐、与铝氢氧化物、铝氧化物、铝卤化物、铝硫酸盐、铝硝酸盐、铝醇盐化合物等铝化合物用根据需要使用的反应剂进行盐交换反应的方法;将环状磷酰氯作为起始物质,通过水解生成环状磷酸,并与金属化合物反应的方法;等。
作为(A)成分的具体例,可以举出下述的化合物。其中,本发明的组合物不限定于这些化合物。
本发明的组合物中,(A)成分为通式(3)所示的化合物和2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯锂可以对热塑性树脂赋予良好的透明性和物性,故优选。
本发明的组合物中,(A)成分不受粒径、粒度分布等颗粒状态的限定,但已知粒径如果微细,则对树脂中的分散性优化,体积平均粒径优选100μm以下、更优选30μm以下、进一步优选20μm以下。需要说明的是,体积平均粒径是指,基于激光衍射·散射式粒度测定装置(MicrotracBEL Corp.制Microtrac MT3000II)的对体积进行加权而得到的平均粒径。
本发明的组合物中,(A)成分的配混量相对于(A)成分~(D)成分的总计量,为35~75质量%、优选35~55质量%、更优选38~50质量%的范围。(A)成分低于35质量%、或超过75质量%的情况下,不仅无法得到本发明的效果而且有时成型品的着色变多。
(A)成分相对于热塑性树脂的配混量相对于热塑性树脂100质量份,为0.001~10质量份、更优选0.006~5质量份。配混量低于0.001质量份的情况下,有时无法得到成核剂效果,如果超过10质量份,则对热塑性树脂中的分散变困难,有时对成型品的物性、外观造成不良影响。
接着,对(B)羧酸钠(以下,也称为(B)成分)进行说明。作为羧酸钠(B),可以举出芳香族羧酸钠和脂肪酸钠。
作为芳香族羧酸,可以举出苯甲酸、叔丁基苯甲酸、甲氧基苯甲酸、二甲氧基苯甲酸、三甲氧基苯甲酸、氯苯甲酸、二氯苯甲酸、三氯苯甲酸、乙酰氧基苯甲酸、联苯羧酸、萘羧酸、蒽羧酸、呋喃羧酸、噻吩酸等。本发明的组合物中,苯甲酸、叔丁基苯甲酸的本发明的效果变明显,故优选。
作为脂肪酸,可以举出导入了碳原子数9~29的烷基、烯基、2个以上不饱和键的脂肪酸,脂肪酸的氢原子可以被羟基所取代,可以具有支链。作为脂肪酸的具体例,可以举出癸酸、2-乙基己酸、十一烷酸、月桂酸、十三烷酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、硬脂酸、12-羟基硬脂酸、十九烷酸、花生酸、二十一烷酸、山萮酸、二十三烷酸、二十四烷酸、蜡酸、褐煤酸、蜂花酸等饱和脂肪酸、4-癸烯酸、4-十二碳烯酸、棕榈油酸、α-亚麻酸、亚油酸、γ-亚麻酸、亚麻油酸、岩芹酸、油酸、反油酸、异油酸、二十碳五烯酸、二十二碳五烯酸、二十二碳六烯酸等直链不饱和脂肪酸等。本发明的组合物中,优选碳原子数10~21的脂肪酸、更优选碳原子数12~18。特别是月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、12-羟基硬脂酸、油酸、亚油酸使本发明的效果变得明显,故特别优选。
本发明的组合物中,(B)成分的配混量相对于(A)成分~(D)成分的总计量,为10~40质量%、优选15~40质量%、更优选20~40质量%、进一步优选22~35质量%的范围。(B)成分低于10质量%、或超过40质量%的情况下,有时无法得到本发明的效果。
接着,对(C)通式(2)所示的脂肪酸金属盐(以下,也称为(C)成分)进行说明。通式(2)中,R6表示由碳原子数10~30的脂肪族有机酸所导入的基团,M2表示n价的金属原子(其中,不包括钠原子和钙原子)或Al(OH)3-n,n为1~3的整数。作为M2的n价的金属原子,可以举出锂、钾、镁、钡、锌、铝,本发明的组合物中,M2优选锂、钾、锌、铝、羟基铝,更优选锂、钾、锌。
通式(2)中,R6所示的由碳原子数10~30的脂肪族有机酸所导入的基团,可以举出导入了碳原子数9~29的烷基、烯基、2个以上的不饱和键的烃基,烷基、烯基可以具有支链,烃基的氢原子可以被羟基所取代。脂肪酸金属盐(C)的具体例可以举出羧酸钠中示例的脂肪酸的锂盐、钾盐、镁盐、钡盐、锌盐、铝盐、羟基铝盐。
本发明的组合物中,(C)成分的脂肪酸优选碳原子数10~21的脂肪酸、更优选碳原子数12~18。特别是月桂酸、肉豆蔻酸、棕榈酸、硬脂酸、12-羟基硬脂酸、油酸、亚油酸使本发明的效果变得明显,故特别优选。需要说明的是,本发明的组合物中,(C)成分可以单独使用一种化合物,也可以组合使用2种以上的化合物。
本发明的组合物中,(C)成分的配混量相对于(A)成分~(D)成分的总计量,为0~20质量%、优选5~20质量%、更优选7~18质量%的范围。如果超过20质量%,则有时从成型品渗出。
接着,对(D)脂肪酸(以下,也称为(D)成分)进行说明。本发明的组合物中,作为脂肪酸(D),例如可以举出丁酸、戊酸、己酸、庚酸、辛酸、壬酸、2-乙基己基酸、癸酸、月桂酸、肉豆蔻酸、十五烷酸、棕榈酸、十七烷酸、异硬脂酸、硬脂酸、12-羟基硬脂酸、花生酸、海藻酸、山萮酸、二十四烷酸、褐煤酸等等饱和脂肪酸、巴豆酸、肉豆蔻油酸、棕榈油酸、十六碳烯酸、油酸、反油酸、异油酸、鳕烯酸、二十烯酸、芥酸、神经酸等单不饱和脂肪酸、亚油酸、二十碳二烯酸、二十二碳二烯酸等二不饱和脂肪酸、亚麻酸、松油酸、桐油酸、二十碳三烯酸(Meadacid)、二十碳三烯酸(eicosatrienoic acid)、亚麻油酸、花生四烯酸、二十碳四烯酸、腺苷酸、二十二碳六烯酸等不饱和键为3个以上的不饱和脂肪酸。
本发明的组合物中,优选碳原子数10~21的脂肪酸、更优选碳原子数12~18。特别是肉豆蔻酸、棕榈酸、硬脂酸使发明效果变得明显,故优选。
本发明的组合物中,(D)成分的配混量相对于(A)成分~(D)成分的总计量,(D)为5~35质量%、优选7~28质量%的范围内。低于5质量%的情况下,有时无法得到本发明的效果,如果超过35质量%,则有时成型品的透明性降低,或着色增加,或从成型品渗出。
本发明的组合物在不有损本发明的效果的范围内可以使用其他添加剂。作为其他添加剂,例如可以举出酚系抗氧化剂、磷系抗氧化剂、硫醚系抗氧化剂、其他抗氧化剂、受阻胺化合物、紫外线吸收剂、与通式(1)所示的结构不同的成核剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、抗静电剂、荧光增白剂、颜料、染料等。其他添加剂的含量没有特别限制,将本发明的组合物配混于热塑性树脂时,优选为其他添加剂在热塑性树脂中以适度的浓度存在的量。
酚系抗氧化剂例如可以举出2,6-二叔丁基-4-乙基苯酚、2-叔丁基-4,6-二甲基苯酚、苯乙烯化苯酚、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、2,2’-硫代双-(6-叔丁基-4-甲基苯酚)、2,2’-硫代二亚乙基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-甲基-4,6-双(辛基硫烷基甲基)苯酚、2,2’-异丁叉基双(4,6-二甲基苯酚)、异辛基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、N,N’-己烷-1,6-二基双[3-(3,5-二叔丁基-4-羟基苯基)丙酰胺]、2,2’-草酰胺-双[乙基-3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]、2-乙基己基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯、2,2’-亚乙基双(4,6-二叔丁基苯酚)、3,5-二叔丁基-4-羟基-苯丙酸和C13-15烷基的酯、2,5-二叔戊基氢醌、受阻酚的聚合物(ADEKA POLYMERADDITIVESEUROPE SAS公司制商品名“AO.OH.98”)、2,2’-亚甲基双[6-(1-甲基环己基)-对甲酚]、2-叔丁基-6-(3-叔丁基-2-羟基-5-甲基苄基)-4-甲基苯基丙烯酸酯、2-[1-(2-羟基-3,5-二叔戊基苯基)乙基]-4,6-二叔戊基苯基丙烯酸酯、6-[3-(3-叔丁基-4-羟基-5-甲基)丙氧基]-2,4,8,10-四-叔丁基苯并[d,f][1,3,2]-二氧杂磷、六亚甲基双[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯、双[单乙基(3,5-二叔丁基-4-羟基苄基)膦酸酯]钙盐、5,7-双(1,1-二甲基乙基)-3-羟基-2(3H)-苯并呋喃酮与邻二甲苯的反应产物、2,6-二叔丁基-4-(4,6-双(辛基硫代)-1,3,5-三嗪-2-基氨基)苯酚、DL-a-生育酚(维生素E)、2,6-双(α-甲基苄基)-4-甲基苯酚、双[3,3-双-(4’-羟基-3’-叔丁基-苯基)丁酸]二醇酯、2,6-二叔丁基-对甲酚、2,6-二苯基-4-十八烷氧基苯酚、硬脂基(3,5-二叔丁基-4-羟基苯基)丙酸酯、二硬脂基(3,5-二叔丁基-4-羟基苄基)膦酸酯、十三烷基-3,5-叔丁基-4-羟基苄基硫代乙酸酯、硫代二亚乙基双[(3,5-二叔丁基-4-羟基苯基)丙酸酯]、4,4’-硫代双(6-叔丁基-间甲酚)、2-辛基硫代-4,6-二(3,5-二叔丁基-4-羟基苯氧基)-均三嗪、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、双[3,3-双(4-羟基-3-叔丁基苯基)丁酸]二醇酯、4,4’-丁叉基双(2,6-二叔丁基苯酚)、4,4’-丁叉基双(6-叔丁基-3-甲基苯酚)、2,2’-乙叉基双(4,6-二叔丁基苯酚)、1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷、双[2-叔丁基-4-甲基-6-(2-羟基-3-叔丁基-5-甲基苄基)苯基]对苯二甲酸酯、1,3,5-三(2,6-二甲基-3-羟基-4-叔丁基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)异氰脲酸酯、1,3,5-三(3,5-二叔丁基-4-羟基苄基)-2,4,6-三甲基苯、1,3,5-三[(3,5-二叔丁基-4-羟基苯基)丙酰氧基乙基]异氰脲酸酯、四[亚甲基-3-(3’,5’-叔丁基-4’-羟基苯基)丙酸酯]甲烷、2-叔丁基-4-甲基-6-(2-丙烯酰氧基-3-叔丁基-5-甲基苄基)苯酚、3,9-双[2-(3-叔丁基-4-羟基-5-甲基氢肉桂酰氧基)-1,1-二甲基乙基]-2,4,8,10-四氧杂螺[5.5]十一烷、三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]、硬脂基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、棕榈基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、肉豆蔻基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺、月桂基-3-(3,5-二叔丁基-4-羟基苯基)丙酰胺等3-(3,5-二烷基-4-羟基苯基)丙酸衍生物等。配混酚系抗氧化剂时的配混量优选以相对于热塑性树脂100质量份成为0.001~5质量份、更优选成为0.03~3质量份的方式进行调整。
磷系抗氧化剂例如可以举出亚磷酸三苯酯、亚磷酸二异辛酯、七(二丙二醇)三亚磷酸酯、亚磷酸三异癸酯、亚磷酸二苯基异辛酯、亚磷酸二异辛基苯酯、亚磷酸二苯基十三烷酯、亚磷酸三异辛酯、亚磷酸三月桂酯、亚磷酸二苯酯、三(二丙二醇)亚磷酸酯、氢化亚磷酸二油基酯、三硫代亚磷酸三月桂酯、亚磷酸双(十三烷基)酯、亚磷酸三(异癸基)酯、亚磷酸三(十三烷基)酯、亚磷酸二苯基癸酯、亚磷酸二壬基苯基双(壬基苯基)酯、聚(二丙二醇)苯基亚磷酸酯、四苯基二丙二醇二亚磷酸酯、亚磷酸三壬基苯酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三(2,4-二叔丁基-5-甲基苯基)酯、亚磷酸三〔2-叔丁基-4-(3-叔丁基-4-羟基-5-甲基苯基硫代)-5-甲基苯基〕酯、亚磷酸三(癸基)酯、亚磷酸辛基二苯酯、亚磷酸二(癸基)单苯酯、二硬脂基季戊四醇与硬脂酸钙盐的混合物、烷基(C10)双酚A亚磷酸酯、四苯基-四(十三烷基)季戊四醇四亚磷酸酯、双(2,4-二叔丁基-6-甲基苯基)乙基亚磷酸酯、四(十三烷基)异丙叉基二苯酚二亚磷酸酯、四(十三烷基)-4,4’-正丁叉基双(2-叔丁基-5-甲基苯酚)二亚磷酸酯、六(十三烷基)-1,1,3-三(2-甲基-4-羟基-5-叔丁基苯基)丁烷三亚磷酸酯、四(2,4-二叔丁基苯基)联苯基二亚磷酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、(1-甲基-1-丙烯基-3-亚基)三(1,1-二甲基乙基)-5-甲基-4,1-亚苯基)六(十三烷基)亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-2-乙基己基亚磷酸酯、2,2’-亚甲基双(4,6-二叔丁基苯基)-十八烷基亚磷酸酯、2,2’-乙叉基双(4,6-二叔丁基苯基)氟亚磷酸酯、4,4’-丁叉基双(3-甲基-6-叔丁基苯基二(十三烷基))亚磷酸酯、三(2-〔(2,4,8,10-四-叔丁基二苯并〔d,f〕〔1,3,2〕二氧杂磷杂七环-6-基)氧基乙基)胺、3,9-双(4-壬基苯氧基)-2,4,8,10-四氧杂-3,9-二磷杂螺[5,5]十一烷、2,4,6-三叔丁基苯基-2-丁基-2-乙基-1,3-丙二醇亚磷酸酯、聚4,4’-异丙叉基二苯酚C12-15醇亚磷酸酯、双(二异癸基)季戊四醇二亚磷酸酯、双(十三烷基)季戊四醇二亚磷酸酯、双(十八烷基)季戊四醇二亚磷酸酯、双(壬基苯基)季戊四醇二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,4,6-三叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)季戊四醇二亚磷酸酯、双(2,4-二枯基苯基)季戊四醇二亚磷酸酯等。配混磷系抗氧化剂时的配混量优选以相对于热塑性树脂100质量份成为0.001~10质量份、更优选成为0.01~0.5质量份的方式进行调整。
硫醚系抗氧化剂例如可以举出四[亚甲基-3-(月桂基硫代)丙酸酯]甲烷、双(甲基-4-[3-正烷基(C12/C14)硫代丙酰氧基]5-叔丁基苯基)硫醚、双十三烷基-3,3’-硫代二丙酸酯、二月桂基-3,3’-硫代二丙酸酯、二肉豆蔻基-3,3’-硫代二丙酸酯、二硬脂基-3,3’-硫代二丙酸酯、月桂基/硬脂基硫代二丙酸酯、4,4’-硫代双(6-叔丁基-间甲酚)、2,2’-硫代双(6-叔丁基-对甲酚)、二硬脂基-二硫醚。配混硫醚系抗氧化剂时的配混量优选以相对于热塑性树脂100质量份成为0.001~10质量份、更优选成为0.01~0.5质量份的方式进行调整。
作为其他抗氧化剂,可以举出N-苄基-α-苯基硝酮、N-乙基-α-甲基硝酮、N-辛基-α-庚基硝酮、N-月桂基-α-十一烷基硝酮、N-十四烷基-α-十三烷基硝酮、N-十六烷基-α-十五烷基硝酮、N-辛基-α-十七烷基硝酮、N-十六烷基-α-十七烷基硝酮、N-十八烷基-α-十五烷基硝酮、N-十七烷基-α-十七烷基硝酮、N-十八烷基-α-十七烷基硝酮等硝酮化合物、3-芳基苯并呋喃-2(3H)-酮、3-(烷氧基苯基)苯并呋喃-2-酮、3-(酰氧基苯基)苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(3,4-二甲基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-(4-羟基苯基)-苯并呋喃-2(3H)-酮、5,7-二叔丁基-3-{4-(2-羟基乙氧基)苯基}-苯并呋喃-2(3H)-酮、6-(2-(4-(5,7-二叔-2-氧代-2,3-二氢苯并呋喃-3-基)苯氧基)乙氧基)-6-氧代己基-6-((6-羟基己酰基)氧基)己酸酯、5-二叔丁基-3-(4-((15-羟基-3,6,9,13-四氧杂十五烷基)氧基)苯基)苯并呋喃-2(3H)酮等苯并呋喃化合物等。配混其他抗氧化剂时的配混量相对于热塑性树脂100质量份,优选0.001~20质量份、更优选0.01~5质量份。
作为紫外线吸收剂,例如可以举出2,4-二羟基二苯甲酮、5,5’-亚甲基双(2-羟基-4-甲氧基二苯甲酮)等2-羟基二苯甲酮类;2-(2-羟基-5-甲基苯基)苯并***、2-(2-羟基-5-叔辛基苯基)苯并***、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并***、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并***、2-(2-羟基-3,5-二枯基苯基)苯并***、2,2’-亚甲基双(4-叔辛基-6-苯并***基苯酚)、2-(2-羟基-3-叔丁基-5-羧基苯基)苯并***的聚乙二醇酯、2-〔2-羟基-3-(2-丙烯酰氧基乙基)-5-甲基苯基〕苯并***、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕苯并***、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔辛基苯基〕苯并***、2-〔2-羟基-3-(2-甲基丙烯酰氧基乙基)-5-叔丁基苯基〕-5-氯苯并***、2-〔2-羟基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并***、2-〔2-羟基-3-叔丁基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并***、2-〔2-羟基-3-叔戊基-5-(2-甲基丙烯酰氧基乙基)苯基〕苯并***、2-〔2-羟基-3-叔丁基-5-(3-甲基丙烯酰氧基丙基)苯基〕-5-氯苯并***、2-〔2-羟基-4-(2-甲基丙烯酰氧基甲基)苯基〕苯并***、2-〔2-羟基-4-(3-甲基丙烯酰氧基-2-羟基丙基)苯基〕苯并***、2-〔2-羟基-4-(3-甲基丙烯酰氧基丙基)苯基〕苯并***等2-(2-羟基苯基)苯并***类;水杨酸苯酯、间苯二酚单苯甲酸酯、2,4-二叔丁基苯基-3,5-二叔丁基-4-羟基苯甲酸酯、辛基(3,5-二叔丁基-4-羟基)苯甲酸酯、十二烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十四烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十六烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、十八烷基(3,5-二叔丁基-4-羟基)苯甲酸酯、山萮基(3,5-二叔丁基-4-羟基)苯甲酸酯等苯甲酸酯类;2-乙基-2’-乙氧基草酰苯胺、2-乙氧基-4’-十二烷基草酰苯胺等取代草酰苯胺类;乙基-α-氰基-β,β-二苯基丙烯酸酯、甲基-2-氰基-3-甲基-3-(对甲氧基苯基)丙烯酸酯等氰基丙烯酸酯类;2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-己基氧基苯酚、2-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二甲基苯基)-1,3,5-三嗪、三辛基-2,2’,2”-((1,3,5-三嗪-2,4,6-三基)三(3-羟基苯-4-,1-二基)三丙酸酯)、2-(4,6-二苯基-1,3,5-三嗪-2-基)-5-[2-(2-乙基己酰基氧基)乙氧基]苯酚、2,4,6-三(2-羟基-4-己基氧基-3-甲基苯基)-1,3,5-三嗪、1,12-双[2-[4-(4,6-二苯基-1,3,5-三嗪-2-基)-3-羟基苯氧基]乙基]十二烷二酸酯等三嗪类;各种金属盐、或金属螯合物、特别是镍、铬的盐、或螯合物类等。配混紫外线吸收剂时的配混量优选以相对于热塑性树脂100质量份成为0.001~10质量份、更优选成为0.01~0.5质量份的方式进行调整。
受阻胺化合物例如可以举出2,2,6,6-四甲基-4-哌啶基硬脂酸酯、1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、2,2,6,6-四甲基-4-哌啶基苯甲酸酯、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯、四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、双(2,2,6,6-四甲基-4-哌啶基)·二(十三烷基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)-二(十三烷基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,4,4-五甲基-4-哌啶基)-2-丁基-2-(3,5-二叔丁基-4-羟基苄基)丙二酸酯、1-(2-羟基乙基)-2,2,6,6-四甲基-4-哌啶醇/琥珀酸二乙酯缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-吗啉基-均三嗪缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-叔辛基氨基-均三嗪缩聚物、1,5,8,12-四〔2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8,12-四氮杂十二烷、1,5,8,12-四〔2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基)-均三嗪-6-基〕-1,5,8,12-四氮杂十二烷、1,6,11-三〔2,4-双(N-丁基-N-(2,2,6,6-四甲基-4-哌啶基)氨基)-均三嗪-6-基〕氨基十一烷、1,6,11-三〔2,4-双(N-丁基-N-(1,2,2,6,6-五甲基-4-哌啶基)氨基)-均三嗪-6-基〕氨基十一烷、双{4-(1-辛基氧基-2,2,6,6-四甲基)哌啶基}癸烷二酮酸酯、双{4-(2,2,6,6-四甲基-1-十一烷基氧基)哌啶基)碳酸酯等。配混受阻胺化合物时的配混量优选以相对于热塑性树脂100质量份成为0.001~10质量份、更优选成为0.01~0.5质量份的方式进行调整。
作为与通式(1)所示的结构不同的成核剂,例如可以举出苯甲酸钠、4-叔丁基苯甲酸铝盐、己二酸钠和双环[2.2.1]庚烷-2,3-二羧酸二钠等羧酸金属盐、二亚苄基山梨糖醇、双(甲基亚苄基)山梨糖醇、双(3,4-二甲基亚苄基)山梨糖醇、双(对乙基亚苄基)山梨糖醇、和双(二甲基亚苄基)山梨糖醇等多元醇衍生物、N,N’,N”-三[2-甲基环己基]-1,2,3-丙烷三甲酰胺、N,N’,N”-三环己基-1,3,5-苯三甲酰胺、N,N’-二环己基萘二甲酰胺、1,3,5-三(二甲基异丙基氨基)苯等酰胺化合物等。配混与通式(1)所示的结构不同的成核剂时的配混量以优选相对于热塑性树脂100质量份成为0.03~10质量份、更优选成为0.05~0.5质量份的方式进行调整。
阻燃剂例如可以举出磷酸三苯酯、磷酸三甲苯酯、磷酸三(二甲苯基)酯、磷酸甲苯基二苯酯、甲苯基-2,6-二(二甲苯基)磷酸酯、间苯二酚双(二苯基磷酸酯)、(1-甲基乙叉基)-4,1-亚苯基四苯基二磷酸酯、1,3-亚苯基四(2,6-二甲基苯基)磷酸酯、株式会社ADEKA制商品名“ADK STAB FP-500”、“ADK STAB FP-600”、“ADK STAB FP-800”的芳香族磷酸酯、苯基膦酸二乙烯酯、苯基膦酸二烯丙酯、苯基膦酸(1-丁烯基)酯等膦酸酯、二苯基次膦酸苯酯、二苯基次膦酸甲酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物衍生物等次膦酸酯、双(2-烯丙基苯氧基)膦腈、二甲苯基膦腈等膦腈化合物、磷酸三聚氰胺、焦磷酸三聚氰胺、聚磷酸三聚氰胺、聚磷酸蜜白胺、聚磷酸铵、磷酸哌嗪、焦磷酸哌嗪、聚磷酸哌嗪、含有磷的乙烯基苄基化合物和红磷等磷系阻燃剂、氢氧化镁、氢氧化铝等金属氢氧化物、溴化双酚A型环氧树脂、溴化苯酚酚醛清漆型环氧树脂、六溴苯、五溴甲苯、亚乙基双(五溴苯基)、亚乙基双溴邻苯二甲酰亚胺、1,2-二溴-4-(1,2-二溴乙基)环己烷、四溴环辛烷、六溴环十二烷、双(三溴苯氧基)乙烷、溴化聚亚苯基醚、溴化聚苯乙烯和2,4,6-三(三溴苯氧基)-1,3,5-三嗪、三溴苯基马来酰亚胺、三溴苯基丙烯酸酯、三溴苯基甲基丙烯酸酯、四溴双酚A型二甲基丙烯酸酯、五溴苄基丙烯酸酯、和、溴化苯乙烯等溴系阻燃剂等。这些阻燃剂优选与氟树脂等防滴剂、多元醇、水滑石等阻燃助剂组合使用。配混阻燃剂时的配混量优选以相对于热塑性树脂100质量份成为1~100质量份、更优选成为10~70质量份的方式进行调整。
润滑剂是以对成型体表面赋予润滑性,提高防划痕效果为目的而添加的。作为润滑剂,例如可列举出:油酸酰胺、芥酸酰胺等不饱和脂肪酸酰胺;山萮酸酰胺、硬脂酸酰胺等饱和脂肪酸酰胺、硬脂酸丁酯、硬脂基醇、硬脂酸单甘油酯、失水山梨醇单棕榈酸酯、失水山梨醇单硬脂酸酯、甘露糖醇、硬脂酸、氢化蓖麻油、硬脂酰胺、油酸酰胺、亚乙基二硬脂酸酰胺等。这些可以单独使用1种,还可以组合使用2种以上而使用。配混润滑剂时的配混量优选以相对于热塑性树脂100质量份成为0.01~2质量份、更优选成为0.03~0.5质量份的方式进行调整。
作为填充剂,例如可以举出滑石、云母、碳酸钙、氧化钙、氢氧化钙、碳酸镁、氢氧化镁、氧化镁、硫酸镁、氢氧化铝、硫酸钡、玻璃粉末、玻璃纤维、粘土、白云石、云母、二氧化硅、氧化铝、钛酸钾晶须、硅灰石、纤维状碱式硫酸镁等,可以适宜选择粒径(纤维状时纤维直径、纤维长度和长径比)来使用。另外,填充剂可以根据需要使用经表面处理的物质。配混填充剂时的配混量相对于热塑性树脂100质量份,优选0.01~80质量份、更优选1~50质量份。
水滑石类是作为天然物、合成物已知的、由镁、铝、羟基、碳酸基和任意结晶水形成的复合盐化合物,可以举出:镁或铝的一部分被碱金属、锌等其它金属置换而成的物质;羟基、碳酸基被其它阴离子基团置换而成的物质,具体而言,例如可列举出将由下述通式(4)表示的水滑石的金属置换为碱金属而成的物质。另外,作为Al-Li系的水滑石类,也可以使用由下述通式(5)表示的化合物。
mgx1Znx2Al2(OH)2(x1+x2)+4(CO3)pH2O (4)
此处,通式(4)中,x1和x2分别表示满足下述式0≤x2/x1<10、2≤x1+x2≤20表示的条件的数,p表示0或正数。
[Li1/3Al2/3(OH)2]·[Aq- 1/3q·pH2O] (5)
此处,通式(5)中,Aq-表示q价的阴离子,p表示0或正数。
另外,也可以为这些水滑石类中的碳酸根阴离子的一部分被其它阴离子置换而成的物质。
水滑石类可以为结晶水脱水而成的物质,也可以为用硬脂酸等高级脂肪酸、油酸碱金属盐等高级脂肪酸金属盐、十二烷基苯磺酸碱金属盐等有机磺酸金属盐、高级脂肪酸酰胺、高级脂肪酸酯或蜡等包覆而成的物质。
水滑石类可以为天然物也可以为合成品。作为这些水滑石类的合成方法,可列举出:日本特公昭46-2280号公报、日本特公昭50-30039号公报、日本特公昭51-29129号公报、日本特公平3-36839号公报、日本特开昭61-174270号公报、日本特开平5-179052号公报等中记载的公知的方法。另外,这些水滑石类可以不受其晶体结构、晶体颗粒等的限制而使用。配混水滑石类时的配混量优选以相对于热塑性树脂100质量份成为0.001~5质量份、更优选成为0.01~3质量份的方式进行调整。
抗静电剂例如可以举出脂肪酸季铵离子盐、多胺季盐等阳离子系抗静电剂;高级醇磷酸酯盐、高级醇EO加成物、聚乙二醇脂肪酸酯、阴离子型的烷基磺酸盐、高级醇硫酸酯盐、高级醇环氧乙烷加成物硫酸酯盐、高级醇环氧乙烷加成物磷酸酯盐等阴离子系抗静电剂;多元醇脂肪酸酯、聚乙二醇磷酸酯、聚氧乙烯烷基烯丙基醚等非离子系抗静电剂;烷基二甲基氨基乙酸甜菜碱等两性型烷基甜菜碱、咪唑啉型两性活性剂等两性抗静电剂、聚醚酯酰胺等高分子型抗静电剂。这些抗静电剂可以单独使用,另外,也可以将2种以上的抗静电剂组合而使用。配混抗静电剂时的配混量优选以相对于热塑性树脂100质量份成为0.03~2质量份、更优选成为0.1~0.8质量份的方式进行调整。
颜料也可以使用市售的颜料,例如可以举出颜料红1、2、3、9、10、17、22、23、31、38、41、48、49、88、90、97、112、119、122、123、144、149、166、168、169、170、171、177、179、180、184、185、192、200、202、209、215、216、217、220、223、224、226、227、228、240、254;颜料橙13、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、65、71;颜料黄1、3、12、13、14、16、17、20、24、55、60、73、81、83、86、93、95、97、98、100、109、110、113、114、117、120、125、126、127、129、137、138、139、147、148、150、151、152、153、154、166、168、175、180、185;颜料绿7、10、36;颜料蓝15、15:1、15:2、15:3、15:4、15:5、15:6、22、24、29、56、60、61、62、64;颜料紫1、15、19、23、27、29、30、32、37、40、50等。
荧光增白剂是通过吸收阳光、人工光的紫外线而将其转变为紫~蓝色的可见光线并辐射的荧光作用来促进成型体的白色度、蓝色的化合物。作为荧光增白剂,可列举出苯并恶唑系化合物C.I.Fluorescent Brightner184;香豆素系化合物C.I.FluorescentBrightner52;二氨基芪二磺酸系化合物C.I.Fluorescent Brightner24、85、71等。使用荧光增白剂时的配混量优选以相对于热塑性树脂100质量份成为0.00001~0.1质量份、更优选成为0.00005~0.05质量份的方式进行调整。
作为染料,可以举出偶氮染料、蒽醌染料、靛蓝类染料、三芳基甲烷染料、呫吨染料、茜素染料、吖啶染料、二苯乙烯染料、噻唑染料、萘酚染料、喹啉染料、硝基染料、吲达胺染料、噁嗪染料、酞菁染料、花青染料等染料等,它们可以混合多种而使用。
接着,对本发明的热塑性树脂组合物进行说明。
能用于本发明的热塑性树脂组合物的树脂只要为热塑性树脂就没有限制,但从本发明的效果变明显的观点出发,优选聚烯烃系树脂、苯乙烯系树脂、聚酯系树脂、聚醚系树脂、聚碳酸酯系树脂、聚酰胺系树脂、含卤素树脂,更优选聚烯烃系树脂。
作为聚烯烃系树脂,例如可以举出聚乙烯、低密度聚乙烯、直链状低密度聚乙烯、高密度聚乙烯、交联聚乙烯、超高分子量聚乙烯、聚丙烯、均聚聚丙烯、无规共聚物聚丙烯、嵌段共聚物聚丙烯、全同立构聚丙烯、间同立构聚丙烯、半全同立构聚丙烯、聚丁烯、环烯烃聚合物、立构嵌段聚丙烯、聚-3-甲基-1-丁烯、聚-3-甲基-1-戊烯、聚-4-甲基-1-戊烯等α-烯烃聚合物、乙烯-丙烯的嵌段或无规共聚物、抗冲共聚物聚丙烯、乙烯-甲基丙烯酸甲酯共聚物、乙烯-丙烯酸甲酯共聚物、乙烯-丙烯酸乙酯共聚物、乙烯-丙烯酸丁酯共聚物、乙烯-乙酸乙烯酯共聚物等α-烯烃共聚物、聚氟烯烃、以及聚烯烃系热塑性弹性体,还可以是它们2种以上的共聚物。
作为苯乙烯系树脂,例如可列举出含乙烯基芳香族烃单独、以及含乙烯基芳香族烃与其它单体(例如,马来酸酐、苯基马来酰亚胺、(甲基)丙烯酸酯、丁二烯、(甲基)丙烯腈等)的共聚物,例如可列举出聚苯乙烯(PS)树脂、耐冲击性聚苯乙烯(HIPS)、丙烯腈-苯乙烯(AS)树脂、丙烯腈-丁二烯-苯乙烯(ABS)树脂、甲基丙烯酸甲酯-丁二烯-苯乙烯(MBS)树脂、耐热ABS树脂、丙烯酸酯-苯乙烯-丙烯腈(ASA)树脂、丙烯腈-丙烯酸橡胶-苯乙烯(AAS)树脂、苯乙烯-马来酸酐(SMA)树脂、甲基丙烯酸酯-苯乙烯(MS)树脂、苯乙烯-异戊二烯-苯乙烯(SIS)树脂、丙烯腈-乙烯丙烯橡胶-苯乙烯(AES)树脂、苯乙烯-丁二烯-丁烯-苯乙烯(SBBS)树脂、甲基丙烯酸甲酯-丙烯腈-丁二烯-苯乙烯(MABS)树脂等热塑性树脂、以及将它们的丁二烯或异戊二烯的双键氢化而成的苯乙烯-乙烯-丁烯-苯乙烯(SEBS)树脂、苯乙烯-乙烯-丙烯-苯乙烯(SEPS)树脂、苯乙烯-乙烯-丙烯(SEP)树脂、苯乙烯-乙烯-乙烯-丙烯-苯乙烯(SEEPS)树脂等氢化苯乙烯系弹性体树脂。
作为聚酯系树脂,例如可以举出聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚对苯二甲酸环己二甲酯等聚对苯二甲酸亚烷基酯;聚萘二甲酸乙二醇酯、聚萘二甲酸丁二醇酯等聚萘二甲酸亚烷基酯等芳香族聚酯;聚对苯二甲酸四亚甲基酯等直链聚酯;和聚羟基丁酸酯、聚己内酯、聚丁二酸丁二醇酯、聚丁二酸乙二醇酯、聚乳酸、聚苹果酸、聚甘醇酸、聚二噁烷、聚(2-氧杂环丁酮)等分解性脂肪族聚酯等。
作为聚醚系树脂,可列举出聚缩醛、聚亚苯醚、聚醚酮、聚醚醚酮、聚醚酮酮、聚醚醚酮酮、聚醚砜、聚醚酰亚胺等。
作为聚碳酸酯系树脂,可列举出聚碳酸酯、聚碳酸酯/ABS树脂、聚碳酸酯/ASA树脂、聚碳酸酯/AES树脂、支链聚碳酸酯等。
作为聚酰胺系树脂,例如可列举出使ε-己内酰胺(尼龙6)、十一内酰胺(尼龙11)、十二内酰胺(尼龙12)、氨基己酸、庚内酰胺、7-氨基庚酸、11-氨基十一酸、9-氨基壬酸、α-吡咯烷酮、α-哌啶酮等聚合物;己二胺、壬二胺、壬烷亚甲基二胺、甲基戊二胺、十一烷亚甲基二胺、十二烷亚甲基二胺、间苯二甲胺等二胺与己二酸、癸二酸、对苯二甲酸、间苯二甲酸、十二烷二羧酸、戊二酸等二羧酸等羧酸化合物共聚而得到的共聚物、或它们的聚合物或共聚物的混合物等。另外,可以举出Dupont公司制商品名“Kevlar”、Dupont公司制商品名“Nomex”、帝人株式会社制商品名“Twaron”、“Conex”等芳族聚酰胺系树脂。
作为含卤素树脂,可列举出聚氯乙烯、聚偏氯乙烯、氯化聚乙烯、氯化聚丙烯、聚偏二氟乙烯、氯化橡胶、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-偏二氯乙烯共聚物、氯乙烯-偏二氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-丙烯酸酯共聚物、氯乙烯-马来酸酯共聚物、氯乙烯-环己基马来酰亚胺共聚物等。
如果进而列举热塑性树脂的例子,则例如可以使用石油树脂、香豆酮树脂、聚乙酸乙烯酯、丙烯酸类树脂、聚甲基丙烯酸甲酯、聚乙烯基醇、聚乙烯醇缩甲醛、聚乙烯醇缩丁醛、聚亚苯基硫醚、聚氨酯、纤维素系树脂、聚酰亚胺树脂、聚砜、液晶聚合物等热塑性树脂和它们的混合物。
另外,热塑性树脂可以是异戊二烯橡胶、丁二烯橡胶、丙烯腈-丁二烯共聚橡胶、苯乙烯-丁二烯共聚橡胶、氟橡胶、有机硅橡胶、聚酯系弹性体、腈系弹性体、尼龙系弹性体、氯乙烯系弹性体、聚酰胺系弹性体、聚氨酯系弹性体等弹性体,还可以组合使用。
本发明的树脂组合物中,这些热塑性树脂可以单独使用,还可以组合使用2种以上。另外,还可以进行合金化。需要说明的是,这些热塑性树脂无论分子量、聚合度、密度、软化点、不溶成分在溶剂中的比例、立构规整性的程度、催化剂残渣的有无、作为原料的单体种类或配混比率、聚合催化剂的种类(例如,齐格勒催化剂、茂金属催化剂等)等如何均可以使用。
本发明的热塑性树脂组合物中,从发明的效果变得明显的方面出发,优选使用聚烯烃系树脂。
将本发明的组合物配混于热塑性树脂的方法不受特别限制,可以举出如下通常使用的方法:例如将热塑性树脂粉末或粒料、与本发明的组合物进行干混的方法;或,制作以高浓度含有本发明的组合物的母料,将其添加至热塑性树脂的方法;将本发明的组合物加工成粒料形状,并添加至热塑性树脂中的方法。
作为加工成粒料形状的方法,例如可以通过如下方式制造:将本发明的组合物、与酚系抗氧化剂、与高分子化合物、与石油树脂等粘结剂和根据需要任意包含的添加剂的混合物进行加热,在熔融状态的粘结剂的存在下进行混合,从而可以制造。对于加工条件、加工机器等,可以没有任何限定地使用公知通常的加工方法、加工机器。作为具体的制造方法,可列举出圆盘造粒机法、挤出法等。
本发明的热塑性树脂组合物是在热塑性树脂组合物中含有本发明的组合物而得到的。本发明的组合物的配混量以相对于热塑性树脂100质量份、通式(1)所示的芳香族磷酸酯金属盐成为0.001~10质量份的方式进行配混,优选0.01~0.5质量份。配混量低于0.001质量份的情况下,有时无法得到透明性改良效果,如果超过10质量份,则从成型品渗出,或无法得到添加效果,是不经济的。
本发明的热塑性树脂组合物在不明显有损发明的效果的范围内可以任意含有公知的添加剂(例如酚系抗氧化剂、磷系抗氧化剂、硫醚系抗氧化剂、其他抗氧化剂、受阻胺化合物、紫外线吸收剂、成核剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、抗静电剂、荧光增白剂、颜料、染料等)。其配混量可以举出与上述相同的配混量。
本发明的树脂组合物可以使用公知的成型方法进行成型。例如可以使用注射成型法、挤出成型法、吹塑成型法、真空成型法、吹胀成型法、压延成型法、搪塑成型法、浸渍成型法、发泡成型法等而得到成型品。
作为本发明的树脂组合物的用途,可列举出保险杠、控制板、仪表板等汽车材料、冰箱、洗衣机、吸尘器等的壳体用途、餐具、水桶、洗浴用品等家庭用品、玩具等杂货品、罐类等储藏、保存用容器等成型品、薄膜、纤维等。
实施例
以下,列举实施例对本发明进一步具体地进行说明,但本发明不受以下实施例等的任何限制。
〔实施例1-1~1-3、比较例1-1~1-3〕
相对于作为热塑性树脂的均聚丙烯(熔体流动速率8g/10分钟;依据ISO标准11332.16kg×230℃)100质量份,配混酚系抗氧化剂(四[亚甲基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯]甲烷)0.05质量份、磷系抗氧化剂(三(2,4-二叔丁基苯基)亚磷酸酯)0.1质量份、硬脂酸钙0.05质量份、和表1中记载的组合物,利用亨舍尔混合机进行1000rpm×1分钟混合后,用双螺杆挤出机,在230℃的挤出温度下进行造粒。造粒后的粒料以60℃干燥8小时后,在下述中记载的条件下,测定Haze、弯曲模量、拉伸模量、Izod冲击强度、和试验片的黄色度(Y.I.)。将得到的结果分别示于表1。需要说明的是,表中的各成分的单位为质量份。
<Haze>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型制作试验片。实施例1-1~1-3、比较例1-1~1-3中,制作尺寸60mm×60mm×2mm的试验片。试验片成型后,立即静置在23℃的恒温机中48小时以上后,用雾度等级2〔BYKAdditives&Instruments制〕,依据ISO14782测定Haze(%)。
<弯曲模量(MPa)>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作尺寸80mm×10mm×4mm的试验片,静置在23℃的恒温机中48小时以上后,用岛津制作所株式会社制弯曲试验机“AG-IS”,依据ISO178测定弯曲模量(MPa)。
<拉伸模量(MPa)>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作1A形哑铃状试验片,静置在23℃的恒温机中48小时以上后,用岛津制作所株式会社制弯曲试验机“AG-IS”,依据ISO527-2测定拉伸模量(MPa)。
<Izod冲击强度(kJ/m2)>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作80mm×10mm×4mm的试验片,静置在23℃的恒温机中48小时以上后,依据ISO180测定Izod冲击强度(kJ/m2)。
<Y.I.>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作60mm×60mm×2mm的试验片,静置在23℃的恒温机中48小时以上后,使用Suga Test Instruments Co.,Ltd.制的“多光源分光测色计”,通过反射法测定试验片的Y.I.。
[表1]
(A)-1:双[2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝
(B)-1:苯甲酸钠
(C)-1:肉豆蔻酸锂
(D)-1:硬脂酸
根据比较例1-1和比较例1-2,未配混脂肪酸(D)的成型品无法得到冲击强度的改善效果。另外,根据比较例1-3可以确认:脂肪酸(D)相对于组合物的比率如果超过30质量%,则物性、透明性的改善效果降低,进一步Haze、成型品的着色变强,有损外观。
与此相对,根据实施例1-1~1-3可以确认:使用本发明的组合物的成型品的物性、透明性的均衡性优异,进而,具有优异的冲击强度,成型品的着色少。
〔实施例2-1~实施例2-4和比较例2-1、2-2〕
对于下述表2中记载的组合物,以下述的步骤进行旋转休止角和聚集度的评价。需要说明的是,实施例2-4的组合物以以下的组成制备。
双[2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸]羟基铝:45质量%、
硬脂酸钠:28质量%、
肉豆蔻酸锂:15质量%、
硬脂酸:12质量%
<旋转休止角(度)>
在圆筒型容器(500mL)中投入表2中记载的组合物使成为圆筒容器的一半容量并盖上盖子,使用筒井理化学器械株式会社制的休止角测定器(Revolv ing CylinderTest),以2.4rpm的速度使其等速旋转来评价试样的流动性。圆筒型容器旋转时,试样沿着旋转的容器上升,试样从高的位置崩落。由该崩落的试样形成的斜面达到一定状态时,测定试样的斜面和水平面所形成的角度作为休止角。将这些结果分别示于表2。
<聚集度(%)>
用粉体测定评价装置(SEISHIN ENTERPRISE Co.,Ltd.制、Multitester MT-02),在网格开口355μm(上段)、220μm(中段)、150μm(下段)、样品重量2g、振幅1mm、振动时间100秒的条件下将样品分级,将下式的总和作为聚集度。对于这些结果,分别示于表2。
(上段的筛上样品重量/总样品重量)×100=(a)的值(%)
(中段的筛上样品重量/总样品重量)×(3/5)×100=(b)的值(%)
(下段的筛上样品重量/总样品重量)×(1/5)×100=(c)的值(%)
聚集度(%)=(a)的值(%)+(b)的值(%)+(c)的值(%)
[表2]
根据比较例2-1,未配混(D)成分的组合物的情况下,流动性差。另外,根据比较例2-2,(D)成分的比率约超过35质量%的组合物的情况下,流动性差。与此相对,根据实施例2-1~实施例2-4可以确认:(D)成分的比率为3~35质量%的范围内的本发明的组合物的流动性优异。
〔实施例3-1~3-15、比较例3-1~3-12〕
相对于作为热塑性树脂的均聚丙烯(熔体流动速率8g/10分钟;依据ISO标准11332.16kg×230℃)100质量份,配混酚系抗氧化剂(四[亚甲基-3-(3’,5’-二叔丁基-4’-羟基苯基)丙酸酯]甲烷)0.05质量份、磷系抗氧化剂(三(2,4-二叔丁基苯基)亚磷酸酯)0.1质量份、硬脂酸钙0.05质量份、和表3~6中记载的组合物,用亨舍尔混合机,进行1000rpm×1分钟混合后,用双螺杆挤出机,在230℃的挤出温度下进行造粒。其中,比较例3-12中,进行造粒而未配混组合物。造粒后的粒料以60℃干燥8小时后,在下述中记载的条件下,测定结晶温度、弯曲模量和载荷挠曲温度(HDT)。对于得到的结果,分别示于表3~6。需要说明的是,表中的各成分的单位表示质量份。
<结晶温度>
使用所得粒料,用差示扫描量热测定器(装置;Perkielmer公司制Diamond)测定结晶温度(℃)。测定方法如下:从室温以50℃/分钟的速度升温至230℃,保持10分钟后,以-10℃/分钟冷却至50℃而得到谱图,在得到的谱图中,将吸热反应成为峰顶的温度作为结晶温度(℃)。
<弯曲模量(MPa)>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作尺寸80mm×10mm×4mm的试验片,静置在23℃的恒温机中48小时以上后,用岛津制作所株式会社制弯曲试验机“AG-IS”,依据ISO178测定弯曲模量(MPa)。
<HDT>
使用所得粒料,用注射成型机(EC100-2A;东芝机械株式会社制),在模具温度50℃、树脂温度200℃的条件下进行注射成型,制作尺寸80mm×10mm×4mm的试验片,静置在23℃的恒温机中48小时以上后,用株式会社东洋精机制作所制HDT试验机“AUTO HDT Tester3A-2”,依据ISO75,测定HDT(℃)。
[表3]
(A)-2:(2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯)锂
(B)-2:硬脂酸钠
(C)-2:硬脂酸锌
(C)-3:硬脂酸镁
(C)-4:硬脂酸钾
(a)-1:(2,2’-亚甲基双(4,6-二叔丁基苯基)磷酸酯)钠
(b)-1:苯甲酸钾
[表4]
[表5]
[表6]
根据比较例3-1~3-5,(A)、(B)、(C)、(D)的组成为本发明的范围外的组合物缺乏结晶温度的改善效果。另外,根据比较例3-6和比较例3-7,(A)成分或(B)成分不同于本发明的组合物的情况下,无法满足结晶温度、弯曲模量和HDT。而且,根据比较例3-8~比较例3-11,缺少了(A)、(B)、(C)、(D)成分的一部分的组合物的情况下,缺乏结晶温度、结晶温度和弯曲模量的改善效果。
与此相对,根据实施例3-1~3-15可以确认:使用本发明的组合物的成型品的结晶温度的改善效果明显,可以得到弯曲模量、HDT优异的成型品。
Claims (9)
1.一种组合物,其特征在于,其为含有下述(A)、(B)、(C)和(D)的组合物,各成分相对于(A)+(B)+(C)+(D)的总计量的比率如下:
(A)35~75质量%、
(B)10~40质量%、
(C)0~20质量%、
(D)5~35质量%,
(A)通式(1)所示的芳香族磷酸酯金属盐,其中,通式(1)中,R1~R4各自独立地表示氢原子或碳原子数1~9的直链或具有支链的烷基,R5表示碳原子数1~4的烷叉基,m表示1或2的数,m为1时M1表示锂,m为2时M1为羟基铝;
(B)羧酸钠;
(C)通式(2)所示的脂肪酸金属盐,其中,通式(2)中,R6表示由碳原子数10~30的脂肪族有机酸所导入的基团,M2表示n价的金属原子、或Al(OH)3-n,所述金属原子不包括钠原子和钙原子,n为1~3的整数;
(D)脂肪酸。
3.根据权利要求1或2所述的组合物,其中,含有:选自由酚系抗氧化剂、磷系抗氧化剂、硫醚系抗氧化剂、其他抗氧化剂、受阻胺化合物、紫外线吸收剂、与通式(1)所示的结构不同的成核剂、阻燃剂、阻燃助剂、润滑剂、填充剂、水滑石类、抗静电剂、荧光增白剂、颜料、染料组成的组中的1种以上的添加剂。
4.根据权利要求1~3中任一项所述的组合物,其中,所述(B)羧酸钠为芳香族羧酸钠或脂肪酸钠。
5.根据权利要求1~4中任一项所述的组合物,其中,(A)为35~55质量%、(B)为20~40质量%、(C)为5~20质量%、(D)为5~35质量%。
6.一种热塑性树脂组合物,其特征在于,相对于热塑性树脂100质量份,含有权利要求1~5中任一项所述的组合物,使得通式(1)所示的芳香族磷酸酯金属盐(A)成为0.001~10质量份。
7.根据权利要求6所述的热塑性树脂组合物,其中,所述热塑性树脂为烯烃系树脂。
8.根据权利要求7所述的热塑性树脂组合物,其中,所述烯烃系树脂为聚丙烯。
9.一种成型品,其特征在于,其是使用权利要求6~8中任一项所述的热塑性树脂组合物而成的。
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