CN113227322A - 稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体 - Google Patents
稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体 Download PDFInfo
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- CN113227322A CN113227322A CN202080007501.6A CN202080007501A CN113227322A CN 113227322 A CN113227322 A CN 113227322A CN 202080007501 A CN202080007501 A CN 202080007501A CN 113227322 A CN113227322 A CN 113227322A
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- acid
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- vinyl chloride
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- 239000000203 mixture Substances 0.000 title claims abstract description 97
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000003381 stabilizer Substances 0.000 title claims abstract description 45
- 239000011342 resin composition Substances 0.000 title claims abstract description 33
- -1 organic acid zinc salt Chemical class 0.000 claims abstract description 146
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 239000004593 Epoxy Substances 0.000 claims abstract description 33
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims abstract description 16
- 125000004185 ester group Chemical group 0.000 claims abstract description 14
- 150000005846 sugar alcohols Chemical class 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 6
- 239000004611 light stabiliser Substances 0.000 claims description 5
- 239000002530 phenolic antioxidant Substances 0.000 claims description 5
- CABDEMAGSHRORS-UHFFFAOYSA-N oxirane;hydrate Chemical compound O.C1CO1 CABDEMAGSHRORS-UHFFFAOYSA-N 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 1
- 238000004040 coloring Methods 0.000 abstract description 39
- 150000003839 salts Chemical class 0.000 description 39
- 150000007524 organic acids Chemical class 0.000 description 26
- 229920001577 copolymer Polymers 0.000 description 25
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 24
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 20
- 239000004014 plasticizer Substances 0.000 description 19
- 125000000217 alkyl group Chemical group 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- 239000003063 flame retardant Substances 0.000 description 14
- 239000000314 lubricant Substances 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 13
- 238000002845 discoloration Methods 0.000 description 13
- 239000000835 fiber Substances 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 12
- 229910052788 barium Inorganic materials 0.000 description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 description 12
- 229960001545 hydrotalcite Drugs 0.000 description 12
- 239000011777 magnesium Substances 0.000 description 12
- 239000011575 calcium Substances 0.000 description 11
- 235000014113 dietary fatty acids Nutrition 0.000 description 11
- 239000000194 fatty acid Substances 0.000 description 11
- 229930195729 fatty acid Natural products 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 238000000465 moulding Methods 0.000 description 11
- 235000005985 organic acids Nutrition 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 10
- 229910052791 calcium Inorganic materials 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 10
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 10
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 239000005060 rubber Substances 0.000 description 10
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 10
- 150000003751 zinc Chemical class 0.000 description 10
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 9
- NZNQMPZXPUKVSQ-UHFFFAOYSA-N [O].C1CO1 Chemical compound [O].C1CO1 NZNQMPZXPUKVSQ-UHFFFAOYSA-N 0.000 description 9
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 9
- 150000007942 carboxylates Chemical class 0.000 description 9
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 9
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 9
- 150000003016 phosphoric acids Chemical class 0.000 description 9
- 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 description 8
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 125000000129 anionic group Chemical group 0.000 description 8
- 159000000009 barium salts Chemical class 0.000 description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 125000002091 cationic group Chemical group 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 8
- 239000001095 magnesium carbonate Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 150000002989 phenols Chemical class 0.000 description 8
- 239000010452 phosphate Substances 0.000 description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 8
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 8
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 8
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 150000004665 fatty acids Chemical class 0.000 description 7
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 7
- 239000012779 reinforcing material Substances 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 6
- UKJARPDLRWBRAX-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine Chemical compound C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 UKJARPDLRWBRAX-UHFFFAOYSA-N 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 6
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 6
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 6
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 6
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 6
- 239000008117 stearic acid Substances 0.000 description 6
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 6
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- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000008158 vegetable oil Substances 0.000 description 6
- 229910052725 zinc Inorganic materials 0.000 description 6
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 5
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 description 5
- CGMMPMYKMDITEA-UHFFFAOYSA-N 2-ethylbenzoic acid Chemical compound CCC1=CC=CC=C1C(O)=O CGMMPMYKMDITEA-UHFFFAOYSA-N 0.000 description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 5
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 5
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- 239000000654 additive Substances 0.000 description 5
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- 235000019441 ethanol Nutrition 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 159000000003 magnesium salts Chemical class 0.000 description 5
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
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- QJRRBVNPIKYRQJ-UHFFFAOYSA-N 10-methylundecanoic acid Chemical compound CC(C)CCCCCCCCC(O)=O QJRRBVNPIKYRQJ-UHFFFAOYSA-N 0.000 description 4
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- ILLOBGFGKYTZRO-UHFFFAOYSA-N tris(2-ethylhexyl) phosphite Chemical compound CCCCC(CC)COP(OCC(CC)CCCC)OCC(CC)CCCC ILLOBGFGKYTZRO-UHFFFAOYSA-N 0.000 description 1
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- KJWHEZXBZQXVSA-UHFFFAOYSA-N tris(prop-2-enyl) phosphite Chemical compound C=CCOP(OCC=C)OCC=C KJWHEZXBZQXVSA-UHFFFAOYSA-N 0.000 description 1
- SGKKYCDALBXNCG-UHFFFAOYSA-N tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenyl)sulfanyl-5-methylphenyl] phosphite Chemical compound CC(C)(C)C1=C(O)C(C)=CC(SC=2C(=CC(OP(OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)OC=3C(=CC(SC=4C=C(C(O)=C(C)C=4)C(C)(C)C)=C(C)C=3)C(C)(C)C)=C(C=2)C(C)(C)C)C)=C1 SGKKYCDALBXNCG-UHFFFAOYSA-N 0.000 description 1
- WRSPWQHUHVRNFV-UHFFFAOYSA-N tris[3,5-di(nonyl)phenyl] phosphite Chemical compound CCCCCCCCCC1=CC(CCCCCCCCC)=CC(OP(OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)OC=2C=C(CCCCCCCCC)C=C(CCCCCCCCC)C=2)=C1 WRSPWQHUHVRNFV-UHFFFAOYSA-N 0.000 description 1
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- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
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- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
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- 239000011667 zinc carbonate Substances 0.000 description 1
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- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- 229940105125 zinc myristate Drugs 0.000 description 1
- 229940012185 zinc palmitate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
-
- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- C08K5/07—Aldehydes; Ketones
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Abstract
本发明提供一种稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体,所述稳定剂组合物能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性、耐热着色性等,进而,在将氯乙烯系树脂用于需要透明性的用途时,能够对氯乙烯系树脂赋予优异的透明性。一种稳定剂组合物,其中,相对于(A)成分100质量份,含有5~2500质量份的(B)成分,(A)成分为1种以上的有机酸锌盐,(B)成分为1种以上的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物。
Description
技术领域
本发明涉及稳定剂组合物、含有其的氯乙烯系树脂组合物(以下也简称为“组合物”和“树脂组合物”)及其成型体,详细而言,涉及能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性、耐热着色性等,进而在将氯乙烯系树脂用于需要透明性的用途时能够对氯乙烯系树脂赋予优异的透明性的稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体。
背景技术
氯乙烯系树脂的阻燃性、耐化学品性、机械稳定性、透明性、粘接性、印刷性等优异,而且,通过添加增塑剂能够容易地使硬度从硬质到软质之间发生变化,因此在各种各样的用途中使用。特别是完全不含增塑剂的硬质或含有少量增塑剂的半硬质的氯乙烯系树脂组合物由于刚性优异而广泛用于建筑材料等。因此,它们在暴露于高温高压下的加工时期自不用说,即使制成成型品也在热稳定性、耐着色性、耐热着色性、耐候性等方面要求更高水平的性能。
另外,在硬质透明成型品的情况下,也用于要求玻璃般的透明性的容器类、工业板、装饰板、薄膜、片材等,是通用性非常高的树脂。另一方面,已知氯乙烯系树脂具有如下的缺点:对于光、热的稳定性不充分,而且在加热成型加工时、产品使用时容易发生主要由脱卤化氢导致的分解。
为了满足以上那样的性能要求并改善缺点,以往尝试了配混有机酸金属盐、有机锡化合物、有机亚磷酸酯化合物、环氧化植物油、β-二酮化合物、抗氧化剂、紫外线吸收剂等各种稳定剂来改善氯乙烯系树脂的稳定性(专利文献1和2)。作为这种稳定剂,以往从成本方面的优势性等观点出发,使用了铅、镉等重金属系稳定剂。另外,作为能够提高透明性的稳定剂,提出了锡系稳定剂(专利文献3和4)。
现有技术文献
专利文献
专利文献1:日本特开平8-183891号公报
专利文献2:日本特开平10-158449号公报
专利文献3:日本特开平7-62181号公报
专利文献4:日本特开2008-1840号公报
发明内容
发明要解决的问题
近年来,对环境问题的关注度提高,重金属等的毒性、对环境造成的影响日益成为问题。与此相伴,逐渐使用钡-锌系的复合系稳定剂、水滑石锌系的稳定剂。然而,在使用这些稳定剂的情况下,在成型加工时成型体有可能发生发泡等成型不良,存在成型体应力白化的问题。另外,从对环境造成的影响、毒性的观点出发,也不优选锡。进而,由于多种锡系稳定剂为液状,因此,在使用其的情况下,存在不仅成型加工时的熔融树脂的润滑性降低、且成型体的热变形温度(软化点)也降低的问题。像这样,寻求防止氯乙烯树脂组合物的与加热、加工、使用相伴的品质降低而不使用铅、镉、锡系稳定剂的技术。
因而,本发明的目的在于,提供稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体,所述稳定剂组合物能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性、耐热着色性等,进而,将氯乙烯系树脂用于需要透明性的用途时,能够对氯乙烯系树脂赋予优异的透明性。
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:具有下述组成的组合物能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性、耐热着色性等,进而,能够对氯乙烯系树脂赋予优异的透明性,从而完成了本发明。
即,本发明的稳定剂组合物的特征在于,相对于(A)成分100质量份,含有5~2500质量份的(B)成分,
(A)成分为1种以上的有机酸锌盐;
(B)成分为1种以上的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物。
本发明的组合物中,相对于(A)成分100质量份,优选含有5~300质量份的1种以上的β-二酮化合物作为(C)成分。另外,本发明的组合物中,相对于(A)成分100质量份,优选含有5~700质量份的1种以上的亚磷酸酯化合物作为(D)成分。进而,本发明的组合物中,相对于(A)成分100质量份,优选含有5~200质量份的1种以上的酚系抗氧化剂作为(E)成分。另外,本发明的组合物中,相对于(A)成分100质量份,优选含有1~1000质量份的1种以上的糖醇作为(F)成分。另外,本发明的组合物中,相对于(A)成分100质量份,优选含有5~200质量份的1种以上的受阻胺系光稳定剂作为(G)成分。进而,本发明的组合物中,(B)成分的环氧化合物的环氧乙烷氧浓度优选在3.0~15.0质量%的范围内。另外,本发明的组合物中,优选不含有机锡系化合物。本发明的组合物可适合地用作透明制品用的氯乙烯系树脂。
本发明的氯乙烯系树脂组合物的特征在于,其含有氯乙烯系树脂和本发明的稳定剂组合物。
本发明的树脂组合物中,相对于前述氯乙烯系树脂100质量份,前述稳定剂组合物优选为0.3~15.0质量份。
本发明的成型体的特征在于,其由本发明的氯乙烯系树脂组合物得到。
作为本发明的成型体,优选厚度为6mm时的雾度值为20.0以下的成型体。
发明的效果
根据本发明,可提供能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性、耐热着色性等,进而将氯乙烯系树脂用于需要透明性的用途时能够对氯乙烯系树脂赋予优异的透明性的稳定剂组合物、含有其的氯乙烯系树脂组合物及其成型体。
具体实施方式
以下,针对本发明的实施方式进行详细说明。
<1.稳定剂组合物>
首先,针对本发明的稳定剂组合物进行说明。本发明的组合物是相对于(A)成分100质量份含有5~2500质量份(B)成分的组合物,(A)成分为1种以上的有机酸锌盐,(B)成分为1种以上的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物。
<(A)成分>
本发明的组合物的(A)成分为1种以上的有机酸锌盐。作为该有机酸锌盐,可列举出有机羧酸、酚类或有机磷酸类等的锌盐。
作为有机羧酸,例如可列举出乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、2-乙基己酸(辛酸)、新癸酸、癸酸、十一烷酸、异十一烷酸、月桂酸、异月桂酸、十三烷酸、肉豆蔻酸、异肉豆蔻酸、棕榈酸、异棕榈酸、异硬脂酸、硬脂酸、12-羟基硬脂酸、山嵛酸、褐煤酸、叔碳酸、苯甲酸、一氯苯甲酸、4-叔丁基苯甲酸、二甲基羟基苯甲酸、3,5-二叔丁基-4-羟基苯甲酸、邻甲苯甲酸、间甲苯甲酸、对甲苯甲酸、甲苯甲酸、二甲基苯甲酸、2,4-二甲基苯甲酸、3,5-二甲基苯甲酸、2,4,6-三甲基苯甲酸、乙基苯甲酸、2-乙基苯甲酸、3-乙基苯甲酸、4-乙基苯甲酸、2,4,6-三乙基苯甲酸、4-异丙基苯甲酸、正丙基苯甲酸、氨基苯甲酸、N,N-二甲基氨基苯甲酸、乙酰氧基苯甲酸、水杨酸、对叔辛基水杨酸、反油酸、油酸、亚油酸、亚麻酸、肉豆蔻脑酸、棕榈油酸、桐酸、二十碳烯酸、二十碳二烯酸、二十碳三烯酸、二十碳四烯酸、花生四烯酸、二十二碳五烯酸、二十二碳六烯酸、蓖麻油酸、巯基乙酸、巯基丙酸、辛基巯基丙酸等一元羧酸;草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、羟基邻苯二甲酸、氯邻苯二甲酸、氨基邻苯二甲酸、马来酸、富马酸、柠康酸、中康酸、衣康酸、乌头酸、硫代二丙酸等二元羧酸或者它们的单酯或单酰胺化合物;丁烷三羧酸、丁烷四羧酸、连苯三甲酸、偏苯三甲酸、偏苯四甲酸、均苯四甲酸等三元或四元羧酸的二或三酯化合物。
作为酚类,例如可列举出叔丁基苯酚、壬基苯酚、二壬基苯酚、环己基苯酚、苯基苯酚、辛基苯酚、苯酚、甲酚、二甲苯酚、正丁基苯酚、异戊基苯酚、乙基苯酚、异丙基苯酚、异辛基苯酚、2-乙基己基苯酚、叔壬基苯酚、癸基苯酚、叔辛基苯酚、异己基苯酚、十八烷基苯酚、二异丁基苯酚、甲基丙基苯酚、二戊基苯酚、甲基异己基苯酚、甲基叔辛基苯酚等。
作为有机磷酸类,例如可列举出单或双辛基磷酸、单或双十二烷基磷酸、单或双十八烷基磷酸、单或双(壬基苯基)磷酸、膦酸壬基苯基酯、膦酸硬脂基酯等。
作为本发明的组合物的(A)成分的有机酸锌盐可以为酸性盐、中性盐、碱性盐、或者将碱性盐的一部分或全部碱用碳酸中和而得到的高碱性络合物。另外,作为本发明的组合物的(A)成分的有机酸锌盐可以由2种以上的有机酸构成。例如,由一元有机酸形成的锌盐的情况下,可以是同一有机酸形成阴离子部位,且与形成阳离子部位的2价锌形成盐,也可以是2种不同的一元有机酸形成阴离子部位,且与形成阳离子部位的2价锌形成盐。
从热稳定性、耐着色性、耐热着色性的观点出发,(A)成分的有机酸锌盐优选为有机羧酸的锌盐,更优选为苯甲酸锌、甲苯甲酸锌、4-叔丁基苯甲酸锌、硬脂酸锌、月桂酸锌、叔碳酸锌、辛酸锌、油酸锌、棕榈酸锌、肉豆蔻酸锌。它们之中,从热稳定性、耐着色性、耐热着色性的方面出发,更优选芳香族羧酸的锌盐,具体而言,更优选苯甲酸锌、甲苯甲酸锌、4-叔丁基苯甲酸锌。另外,在需要透明性的用途中,优选芳香族羧酸的锌盐,具体而言,更优选苯甲酸锌、甲苯甲酸锌、4-叔丁基苯甲酸锌。需要说明的是,(A)成分的有机酸锌盐可以仅使用1种,也可以组合使用2种以上。
<(B)成分>
本发明的组合物的(B)成分为1种以上的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物。
作为具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物,可列举出例如对苯二酚、间苯二酚、邻苯二酚、间苯三酚等单核多酚化合物的聚缩水甘油醚化合物或二缩水甘油醚化合物;二羟基萘、联苯酚、亚甲基双酚(双酚F)、亚甲基双(邻甲酚)、乙叉基双酚、异丙叉基双酚(双酚A)、氢化双酚A、异丙叉基双(邻甲酚)、四溴双酚A、1,3-双(4-羟基枯基苯)、1,4-双(4-羟基枯基苯)、1,1,3-三(4-羟基苯基)丁烷、1,1,2,2-四(4-羟基苯基)乙烷、硫代双酚、磺基双酚、氧基双酚、苯酚酚醛清漆、邻甲酚酚醛清漆、乙基苯酚酚醛清漆、丁基苯酚酚醛清漆、辛基苯酚酚醛清漆、间苯二酚酚醛清漆、萜烯苯酚等多核多酚化合物的聚缩水甘油醚化合物或二缩水甘油醚化合物;乙二醇、丙二醇、丁二醇、己二醇、二乙二醇、聚乙二醇、二丙二醇、聚丙二醇、聚二醇、硫二甘醇、甘油、三羟甲基丙烷、季戊四醇、山梨糖醇、双酚A-环氧乙烷加成物、二环戊二烯二甲醇等多元醇类的聚缩水甘油醚或二缩水甘油醚;马来酸、富马酸、衣康酸、琥珀酸、戊二酸、辛二酸、己二酸、壬二酸、癸二酸、二聚酸、三聚酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、偏苯三甲酸、均苯三甲酸、均苯四甲酸、四氢邻苯二甲酸、六氢邻苯二甲酸、内亚甲基四氢邻苯二甲酸等脂肪族、芳香族或脂环族多元酸的缩水甘油酯类、以及甲基丙烯酸聚缩水甘油酯等甲基丙烯酸缩水甘油酯的均聚物或共聚物等。
进而,若列举出具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物的例子,则可列举出正丁基缩水甘油醚、C12~C14的烷基缩水甘油醚、烯丙基缩水甘油醚、2-乙基己基缩水甘油醚、苯基缩水甘油醚、甲苯基缩水甘油醚、2-苯基苯酚缩水甘油醚、对仲丁基苯基缩水甘油醚、叔丁基苯基缩水甘油醚、甲基丙烯酸缩水甘油酯和叔羧酸缩水甘油酯等,进而,可列举出例如乙二醇二缩水甘油醚、丙二醇二缩水甘油醚、丁二醇二缩水甘油醚、1,6-己二醇二缩水甘油醚、新戊二醇二缩水甘油醚、聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚等,进而,可列举出例如三羟甲基丙烷三缩水甘油醚和甘油三缩水甘油醚等。
从热稳定性、耐着色性、耐热着色性的观点出发,(B)成分的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物优选为具有缩水甘油醚基的环氧化合物,作为具有缩水甘油醚基的环氧化合物,优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、新戊二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、碳原子数为12~13的烷基缩水甘油醚、甲苯基缩水甘油醚、2-苯基苯酚缩水甘油醚,更优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、新戊二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、2-苯基苯酚缩水甘油醚,进一步优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、新戊二醇二缩水甘油醚、2-苯基苯酚缩水甘油醚,更进一步优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、2-苯基苯酚缩水甘油醚。
另外,在需要透明性的用途中,针对透明性,优选为具有缩水甘油醚基的环氧化合物,作为具有缩水甘油醚基的环氧化合物,优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、甲苯基缩水甘油醚、新戊二醇二缩水甘油醚、2-苯基苯酚缩水甘油醚,更优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、甲苯基缩水甘油醚、2-苯基苯酚缩水甘油醚,进一步优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、2-苯基苯酚缩水甘油醚,更进一步优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚,最优选为氢化双酚A二缩水甘油醚。
考虑到热稳定性、耐着色性、耐热着色性、以及透明性、所有这些特性时,优选为具有缩水甘油醚基的环氧化合物,作为具有缩水甘油醚基的环氧化合物,优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚、三羟甲基丙烷三缩水甘油醚、2-苯基苯酚缩水甘油醚,更优选为双酚A二缩水甘油醚、氢化双酚A二缩水甘油醚,最优选为氢化双酚A二缩水甘油醚。
(B)成分的环氧化合物的结构中的缩水甘油醚基和/或缩水甘油酯基的数量可以为一个,也可以为两个以上。另外,(B)成分的环氧化合物可以仅使用1种,也可以组合使用2种以上。
(B)成分的具有缩水甘油醚基的环氧化合物可通过例如使具有酚性羟基或醇性羟基的化合物与表氯醇反应来获得。当然也可以使用市售品。此外,(B)成分的具有缩水甘油酯基的化合物可通过例如使具有羧基的化合物与表氯醇反应来获得。当然也可以使用市售品。
顺便一提,以往作为氯乙烯系树脂的稳定剂、增塑剂而使用的环氧化大豆油、环氧化亚麻籽油等环氧化植物油的结构中不含缩水甘油醚基也不含缩水甘油酯基,因此,不包括在本发明的(B)成分的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物中。本发明的组合物中,环氧化植物油是将植物油脂的双键氧化使其形成环氧乙烷环而得的,因此,其结构中不含缩水甘油醚基也不含缩水甘油酯基。
关于(B)成分的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物,从热稳定性、耐着色性、耐热着色性、以及需要透明性的用途中的透明性的观点出发,其环氧乙烷氧浓度优选在3.0~15.0质量%的范围内、更优选在4.0~14.0质量%的范围内、进一步优选在5.0~13.0质量%的范围内、特别优选在6.0~12.0质量%的范围内、最优选在7.0~11.0质量%的范围内。
需要说明的是,本发明的组合物中,环氧乙烷氧浓度是按照ASTMD1652-11e1而测得的。
本发明的组合物中的(B)成分的含量相对于(A)成分的有机酸锌盐100质量份为5~2500质量份,从热稳定性、耐着色性、耐热着色性、以及需要透明性的用途中的透明性的观点出发,优选为10质量份以上、更优选为50质量份以上、进一步优选为100质量份以上、更进一步优选为150质量份以上、再进一步优选为200质量份以上、特别优选为250质量份以上、最优选为300质量份。关于上限,若为2500质量份以上则从效果和成本的观点出发并不优选,优选为2000质量份以下、更优选为1400质量份以下、进一步优选为800质量份以下。
<(C)成分>
本发明的组合物中,从热稳定性、耐着色性、耐热着色性的观点出发,作为(C)成分,相对于(A)成分100质量份,还优选含有5~300质量份、更优选含有10~250质量份、进一步优选含有20~200质量份的1种以上的β-二酮化合物。
作为(C)成分的β-二酮化合物,例如可列举出乙酰丙酮、三乙酰甲烷、2,4,6-庚三酮、丁酰乙酰甲烷、月桂酰乙酰甲烷、棕榈酰乙酰甲烷、硬脂酰苯甲酰甲烷、棕榈酰苯甲酰甲烷、二硬脂酰甲烷、硬脂酰乙酰甲烷、苯基乙酰乙酰甲烷、二环己基羰基甲烷、苯甲酰甲酰甲烷、苯甲酰乙酰甲烷、二苯甲酰甲烷、辛基苯甲酰甲烷、双(4-辛基苯甲酰)甲烷、苯甲酰二乙酰甲烷、4-甲氧基苯甲酰苯甲酰甲烷、双(4-羧基甲基苯甲酰)甲烷、2-羧基甲基苯甲酰乙酰辛基甲烷、脱氢乙酸、乙酰乙酸乙酯、环己烷-1,3-二酮、3,6-二甲基-2,4-二氧环己烷-1-羧酸甲酯、2-乙酰环己酮、双甲酮、2-苯甲酰环己烷等,它们的金属盐也同样可以使用。作为金属盐的例子,可列举出锂盐、钠盐、钾盐、钙盐、锌盐、镁盐、铝盐。作为优选的金属盐的例子,可列举出乙酰丙酮钙盐、乙酰丙酮锌盐等。
(C)成分的β-二酮化合物可以仅使用1种,也可以组合使用2种以上。这些β-二酮化合物之中,从热稳定性、耐着色性、耐热着色性的方面出发,优选二苯甲酰甲烷、硬脂酰苯甲酰甲烷、乙酰丙酮锌盐。
<(D)成分>
本发明的组合物中,从热稳定性、耐着色性、耐热着色性的观点出发,作为(D)成分,相对于(A)成分的100质量份,还优选含有5~700质量份、更优选含有50~600质量份、进一步优选含有100~500质量份的1种以上的亚磷酸酯化合物。
作为(D)成分的亚磷酸酯化合物,可列举出亚磷酸三烷基酯、亚磷酸二烷基酯、亚磷酸二烷基单烯丙酯、亚磷酸烷基烯丙酯、亚磷酸单烷基二烯丙酯、亚磷酸二烯丙酯、亚磷酸三烯丙酯等。本发明的组合物中,三酯和二酯均可使用,但从热稳定性、耐着色性、耐热着色性的方面出发,优选使用三酯。另外,也可以使用硫酯。
作为亚磷酸酯化合物,可列举出例如亚磷酸三苯基酯、亚磷酸三甲苯基酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸三(壬基苯基)酯、亚磷酸三(二壬基苯基)酯、亚磷酸三(单-和二-混合壬基苯基)酯、亚磷酸三(2,4-二叔丁基苯基)酯、亚磷酸二苯基酯、2,2’-亚甲基双(4,6-二叔丁基苯基)辛基亚磷酸酯、2,2’-亚甲基双(4,6-叔丁基苯基)-2-乙基己基亚磷酸酯、2,2’-亚甲基双(4,6-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)氟代亚磷酸酯、亚磷酸辛基二苯基酯、亚磷酸二苯基癸基酯、亚磷酸二苯基(2-乙基己基)酯、亚磷酸二癸基单苯基酯、亚磷酸二苯基十三烷基酯、亚磷酸二苯基(C12~C15混合烷基)酯、亚磷酸苯基二异癸酯、亚磷酸苯基双(异十三烷基)酯、亚磷酸三乙酯、亚磷酸三丁酯、亚磷酸三癸酯、亚磷酸三(2-乙基己基)酯、亚磷酸三癸酯、亚磷酸三月桂酯、亚磷酸三(十三烷基)酯、亚磷酸三油基酯、亚磷酸三硬脂酯、亚磷酸二乙酯、亚磷酸二丁酯、亚磷酸二月桂酯、亚磷酸双(2-乙基己基)酯、亚磷酸二油基酯、三硫代亚磷酸三月桂酯、双(新戊二醇)-1,4-环己烷二甲基二亚磷酸酯、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、双(2,6-二叔丁基-4-甲基苯基)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(2,4-二枯基苯基)季戊四醇二亚磷酸酯、二硬脂基季戊四醇二亚磷酸酯、二(壬基苯基)季戊四醇二亚磷酸酯、二(十三烷基)季戊四醇二亚磷酸酯、苯基-4,4’-异丙叉基二苯酚/季戊四醇二亚磷酸酯、四(C12~15混合烷基)-4,4’-异丙叉基二苯基二亚磷酸酯、氢化-4,4’-异丙叉基二苯酚多亚磷酸酯、双(辛基苯基)/双〔4,4’-正丁叉基双(2-叔丁基-5-甲基苯酚)〕/1,6-己二醇/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、六(十三烷基)/1,1,3-三(2-甲基-5-叔丁基-4-羟基苯基)丁烷/三亚磷酸酯、9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物、2-丁基-2-乙基丙二醇/2,4,6-三叔丁基苯酚单亚磷酸酯、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〕亚磷酸酯、四(十三烷基)异丙叉基二苯酚二亚磷酸酯、四(2,4-二叔丁基苯基)亚联苯基二亚磷酸酯、三(2-〔(2,4,8,10-四叔丁基二苯并〔d,f〕〔1,3,2〕二氧杂磷杂庚英-6-基)氧基〕乙基)胺、2-乙基-2-丁基丙二醇与2,4,6-三叔丁基苯酚的亚磷酸酯等。
本发明的组合物中,作为(D)成分而使用的亚磷酸酯化合物可以仅使用1种,也可以组合使用2种以上。这些亚磷酸酯化合物之中,从热稳定性、耐着色性、耐热着色性的方面出发,优选使用碳原子数12~80的亚磷酸酯化合物,更优选使用碳原子数12~46的亚磷酸酯化合物,进一步优选使用碳原子数12~36的亚磷酸酯化合物,特别优选使用碳原子数18~30的亚磷酸酯化合物。
<(E)成分>
本发明的组合物中,从热稳定性、耐着色性、耐热着色性的观点出发,作为(E)成分,相对于(A)成分100质量份,还优选含有5~200质量份、更优选含有10~150质量份、进一步优选含有15~100质量份的1种以上的酚系抗氧化剂。
作为(E)成分的酚系抗氧化剂,可列举出例如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、硫二甘醇双〔(3,5-二叔丁基-4-羟基苯基)丙酸酯〕、1,6-六亚甲基双〔(3,5-二叔丁基-4-羟基苯基)丙酸酯〕、1,6-六亚甲基双〔(3,5-二叔丁基-4-羟基苯基)丙酸酰胺〕、4,4’-硫代双(6-叔丁基-间甲酚)、2,2’-亚甲基双(4-甲基-6-叔丁基苯酚)、2,2’-亚甲基双(4-乙基-6-叔丁基苯酚)、双〔3,3-双(4-羟基-3-叔丁基苯基)丁酸〕乙二醇酯、4,4’-丁叉基双(6-叔丁基-间甲酚)、2,2’-乙叉基双(4,6-二叔丁基苯酚)、2,2’-乙叉基双(4-仲丁基-6-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’-二叔丁基-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〔1,1-二甲基-2-{(3-叔丁基-4-羟基-5-甲基苯基)丙酰氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、三甘醇双〔(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯〕、季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]等。
(E)成分的酚系抗氧化剂可以仅使用1种,也可以组合使用2种以上。这些酚系抗氧化剂之中,从热稳定性、耐着色性、耐热着色性的方面出发,优选季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯]。
<(F)成分>
本发明的组合物中,从热稳定性、耐着色性、耐热着色性、尤其是透明性的观点出发,作为(F)成分,相对于(A)成分100质量份,还优选含有1~1000质量份、更优选含有2~200质量份、进一步优选含有6~100质量份、特别优选含有10~60质量份的1种以上的糖醇。
作为(F)成分的糖醇,可列举出甘露醇、麦芽糖醇、乳糖醇、山梨糖醇、赤藓醇、木糖醇、肌醇。(F)成分的糖醇可以仅使用1种,也可以组合使用2种以上。这些糖醇之中,从热稳定性、耐着色性、耐热着色性、尤其是透明性的观点出发,优选为甘露醇、麦芽糖醇、乳糖醇、山梨糖醇,特别优选为山梨糖醇。
<(G)成分>
本发明的组合物中,从热稳定性、耐着色性、耐热着色性的观点出发,作为(G)成分,相对于(A)成分100质量份,还优选含有5~200质量份、更优选含有10~150质量份、进一步优选含有20~100质量份、特别优选含有30~80质量份的1种以上的受阻胺系光稳定剂。
作为(G)成分的受阻胺系光稳定剂,只要是现有公知的受阻胺系光稳定剂,就没有特别限定,例如可列举出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、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、双(1-辛氧基-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)/双(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)/双(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)-2-丁基-2-(3,5-二叔丁基-4-羟基苄基)丙二酸酯、1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、聚〔{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}六亚甲基{(2,2,6,6-四甲基-4-哌啶基)亚氨基}〕、1,2,3,4-丁烷羧酸/2,2-双(羟基甲基)-1,3-丙二醇/3-羟基-2,2-二甲基丙醛/1,2,2,6,6-五甲基-4-哌啶基酯缩聚物、双(1,2,2,6,6-五甲基-4-哌啶基)=癸二酸酯/甲基=1,2,2,6,6-五甲基-4-哌啶基=癸二酸酯混合物、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、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/二溴乙烷缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-吗啉代均三嗪缩聚物、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、3,9-双〔1,1-二甲基-2-{三(2,2,6,6-四甲基-4-哌啶氧基羰基)丁基羰氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、3,9-双〔1,1-二甲基-2-{三(1,2,2,6,6-五甲基-4-哌啶氧基羰基)丁基羰氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、双(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)碳酸酯、2,2,6,6-四甲基-4-哌啶基十六烷酸酯、2,2,6,6-四甲基-4-哌啶基十八烷酸酯等。(G)成分的受阻胺系光稳定剂可以仅使用1种,也可以组合使用2种以上。
另外,作为(G)成分,从热稳定性、耐着色性、耐热着色性的观点出发,可优选列举出具有下述通式(1)所示基团的化合物。
此处,通式(1)中,R1表示氢原子、羟基、碳原子数1~30的烷基、碳原子数1~30的烷氧基、碳原子数1~30的羟基烷基、碳原子数1~30的羟基烷氧基、碳原子数2~30的烯基、或者氧自由基,这些烷基、烷氧基、羟基烷基、羟基烷氧基、烯基可以被氧原子、羰基中断一次或多次。另外,通式(1)的基团在通式(1)中*的位置键合。通式(1)的基团在化合物中可以具有1个或2个以上的多个。
作为通式(1)的R1可取的碳原子数1~30的烷基,可列举出直链烷基或支链烷基。直链烷基例如可列举出甲基、乙基、丙基、丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基、二十三烷基、二十四烷基、二十五烷基、二十六烷基、二十七烷基、二十八烷基、二十九烷基、三十烷基等,支链烷基可列举出将上述直链烷基的1个或2个以上氢原子用碳原子数1~9的烷基取代而成的基团。
作为通式(1)的R1可取的碳原子数1~30的烷氧基,可列举出与上述烷基对应的烷氧基。
作为通式(1)的R1可取的碳原子数1~30的羟基烷基,可列举出与上述烷基对应的羟基烷基。
作为通式(1)的R1可取的碳原子数1~30的羟基烷氧基,可列举出与上述烷氧基对应的羟基烷氧基。
作为通式(1)的R1可取的碳原子数2~30的烯基,例如可列举出乙烯基、丙烯基、丁烯基、戊烯基、己烯基、庚烯基、辛烯基、壬烯基、癸烯基、十一碳烯基、十二碳烯基、十三碳烯基、十四碳烯基、十五碳烯基、十六碳烯基、十七碳烯基、十八碳烯基、十九碳烯基、二十碳烯基、二十一碳烯基、二十二碳烯基、二十三碳烯基、二十四碳烯基、二十五碳烯基、二十六碳烯基、二十七碳烯基、二十八碳烯基、二十九碳烯基、三十碳烯基,也包括烷烃二烯基和烷烃三烯基。
作为通式(1)所示的基团,从热稳定性、耐着色性、耐热着色性的方面出发,R1优选为氢原子或碳原子数1~30的烷基,更优选为碳原子数1~30的烷基,进一步优选为碳原子数1~4的烷基,最优选甲基。
若举出具有通式(1)所示基团的(G)成分的例子,则作为通式(1)的R1为氢原子的例子,可列举出2,2,6,6-四甲基-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、双(2,2,6,6-四甲基-4-哌啶基)/双(十三烷基)-1,2,3,4-丁烷四羧酸酯、聚〔{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}六亚甲基{(2,2,6,6-四甲基-4-哌啶基)亚氨基}〕、2,2,6,6-四甲基-4-哌啶基甲基丙烯酸酯、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/二溴乙烷缩聚物、1,6-双(2,2,6,6-四甲基-4-哌啶基氨基)己烷/2,4-二氯-6-吗啉代均三嗪缩聚物、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、1,6,11-三[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、3,9-双〔1,1-二甲基-2-{三(2,2,6,6-四甲基-4-哌啶氧基羰基)丁基羰氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、2,2,6,6-四甲基-4-哌啶基十六烷酸酯、2,2,6,6-四甲基-4-哌啶基十八烷酸酯等,作为通式(1)的R1为甲基的例子,可列举出1,2,2,6,6-五甲基-4-哌啶基硬脂酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯、四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四羧酸酯、双(1,2,2,6,6-五甲基-4-哌啶基)/双(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)-2-丁基-2-(3,5-二叔丁基-4-羟基苄基)丙二酸酯、1,2,2,6,6-五甲基-4-哌啶基甲基丙烯酸酯、1,2,3,4-丁烷羧酸/2,2-双(羟基甲基)-1,3-丙二醇/3-羟基-2,2-二甲基丙醛/1,2,2,6,6-五甲基-4-哌啶基酯缩聚物、双(1,2,2,6,6-五甲基-4-哌啶基)=癸二酸酯/甲基=1,2,2,6,6-五甲基-4-哌啶基=癸二酸酯混合物、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-(1,2,2,6,6-五甲基-4-哌啶基)氨基)均三嗪-6-基氨基]十一烷、3,9-双〔1,1-二甲基-2-{三(1,2,2,6,6-五甲基-4-哌啶氧基羰基)丁基羰氧基}乙基〕-2,4,8,10-四氧杂螺〔5.5〕十一烷、1,2,2,6,6-五甲基-4-哌啶基十六烷酸酯、1,2,2,6,6-五甲基-4-哌啶基十八烷酸酯等,作为通式(1)的R1为碳原子数1~30的烷氧基的例子,可列举出双(1-辛氧基-2,2,6,6-四甲基-4-哌啶基)癸二酸酯、双(1-十一烷氧基-2,2,6,6-四甲基哌啶-4-基)碳酸酯等。它们之中,从热稳定性、耐着色性、耐热着色性的方面出发,通式(1)所示的基团的R1优选氢原子或甲基,更优选甲基。
<(H)成分>
另外,本发明的组合物中,考虑到热稳定性、耐着色性、耐热着色性,作为(H)成分,也可以还含有有机酸钡盐。含有有机酸钡盐时,相对于(A)成分100质量份,优选含有5~700质量份、更优选含有25~600质量份、进一步优选含有50~500质量份。
作为有机酸钡盐,可列举出有机羧酸、酚类或有机磷酸类等的钡盐。
作为有机羧酸,例如可列举出乙酸、丙酸、丁酸、戊酸、己酸、庚酸、辛酸、壬酸、2-乙基己酸、新癸酸、癸酸、十一烷酸、异十一烷酸、月桂酸、异月桂酸、十三烷酸、肉豆蔻酸、异肉豆蔻酸、棕榈酸、异棕榈酸、异硬脂酸、硬脂酸、12-羟基硬脂酸、山嵛酸、褐煤酸、叔碳酸、苯甲酸、一氯苯甲酸、4-叔丁基苯甲酸、二甲基羟基苯甲酸、3,5-二叔丁基-4-羟基苯甲酸、邻甲苯甲酸、间甲苯甲酸、对甲苯甲酸、甲苯甲酸、二甲基苯甲酸、2,4-二甲基苯甲酸、3,5-二甲基苯甲酸、2,4,6-三甲基苯甲酸、乙基苯甲酸、2-乙基苯甲酸、3-乙基苯甲酸、4-乙基苯甲酸、2,4,6-三乙基苯甲酸、4-异丙基苯甲酸、正丙基苯甲酸、氨基苯甲酸、N,N-二甲基氨基苯甲酸、乙酰氧基苯甲酸、水杨酸、对叔辛基水杨酸、反油酸、油酸、亚油酸、亚麻酸、肉豆蔻脑酸、棕榈油酸、桐酸、二十碳烯酸、二十碳二烯酸、二十碳三烯酸、二十碳四烯酸、花生四烯酸、二十二碳五烯酸、二十二碳六烯酸、蓖麻油酸、巯基乙酸、巯基丙酸、辛基巯基丙酸等一元羧酸;草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸、羟基邻苯二甲酸、氯邻苯二甲酸、氨基邻苯二甲酸、马来酸、富马酸、柠康酸、中康酸、衣康酸、乌头酸、硫代二丙酸等二元羧酸或它们的单酯或单酰胺化合物;丁烷三羧酸、丁烷四羧酸、连苯三甲酸、偏苯三甲酸、偏苯四甲酸、均苯四甲酸等三元或四元羧酸的二或三酯化合物。
作为酚类,例如可列举出叔丁基苯酚、壬基苯酚、二壬基苯酚、环己基苯酚、苯基苯酚、辛基苯酚、苯酚、甲酚、二甲苯酚、正丁基苯酚、异戊基苯酚、乙基苯酚、异丙基苯酚、异辛基苯酚、2-乙基己基苯酚、叔壬基苯酚、癸基苯酚、叔辛基苯酚、异己基苯酚、十八烷基苯酚、二异丁基苯酚、甲基丙基苯酚、二戊基苯酚、甲基异己基苯酚、甲基叔辛基苯酚等。
作为有机磷酸类,例如可列举出单或双辛基磷酸、单或双十二烷基磷酸、单或双十八烷基磷酸、单或双(壬基苯基)磷酸、膦酸壬基苯基酯、膦酸硬脂基酯等。
有机酸钡盐可以由2种以上有机酸构成。例如,由一元有机酸形成的钡盐的情况下,可以是同一有机酸形成阴离子部位,且与形成阳离子部位的2价钡形成盐,也可以是2种不同的一元有机酸形成阴离子部位,且与形成阳离子部位的2价钡形成盐。
本发明的组合物中,有机酸钡盐可以仅使用1种,也可以组合使用2种以上。另外,有机酸钡盐可以为酸性盐、中性盐、碱性盐。
<(I)成分>
另外,本发明的组合物中,考虑到热稳定性、耐着色性、耐热着色性,作为(I)成分,也可以还含有有机酸钙盐。含有有机酸钙盐时,相对于(A)成分的100质量份,优选含有5~700质量份,更优选含有25~600质量份,进一步优选含有50~500质量份。
作为有机酸钙盐,可列举出有机羧酸、酚类或有机磷酸类等的钙盐。
作为有机羧酸,可列举出例如在上述钡盐中例示的有机羧酸。此外,作为酚类,仍然可列举出在上述钡盐中例示的酚类。此外,作为有机磷酸类,仍然可列举出在上述钡盐中例示出的有机磷酸类。
有机酸钙盐可以由2种以上的有机酸构成。例如,有一元有机酸形成的钙盐的情况下,可以是同一有机酸形成阴离子部位,且与形成阳离子部位的2价钙形成盐,也可以是2种不同的1价有机酸形成阴离子部位,且与形成阳离子部位的2价钙形成盐。
本发明的组合物中,有机酸钙盐可以仅使用1种,也可以组合使用2种以上。另外,有机酸钙盐可以为酸性盐、中性盐、碱性盐。
<其它>
另外,考虑到热稳定性、耐着色性、耐热着色性,本发明的组合物也可以还含有高碱性碳酸钡盐。
含有高碱性碳酸钡盐时,相对于(A)成分100质量份,优选含有5~700质量份,更优选含有25~600质量份,进一步优选含有50~500质量份。其中,将高碱性碳酸钡盐配混至组合物时,在成型加工时成型体有可能发泡,因此需要注意。
高碱性碳酸钡盐是指钡的液状高碱性羧酸盐/碳酸盐络合物。该络合物不同于钡的羧酸正盐与碳酸钡的单纯混合物,它们通过某种相互作用而形成络合物,具备尽管具有高的金属含量但仍然在有机溶剂中显示均匀液态的特征。该络合物是以钡的羧酸正盐、碳酸钡、以及钡的羧酸与碳酸的复盐作为构成成分而构成的,以碳酸钡为中心且在其周围存在钡的羧酸正盐以及钡的羧酸与碳酸的复盐,可以说形成胶束那样的物质,从而在有机溶剂中显示均匀液态。这些钡的液状高碱性羧酸盐/碳酸盐络合物可以通过例如日本特开2004-238364号公报中示出的制造方法而制造。
钡的液状高碱性羧酸盐/碳酸盐络合物也可以直接使用各种市售的络合物。作为市售的络合物的代表例,例如可列举出美国AM STABILZERS公司制的“PlastistabTM 2116”(高碱性钡油酸盐/碳酸盐络合物:比重为1.42~1.53、Ba=33~36%)、“PlastistabTM2513”(高碱性钡油酸盐/碳酸盐络合物:比重为1.41~1.52、Ba=33~36%)、“PlastistabTM 2508”(高碱性钡油酸盐/碳酸盐络合物:比重为1.39~1.51、Ba=33~36%)等。
本发明的组合物中,这些高碱性碳酸钡盐可以仅使用1种,也可以组合使用2种以上。
另外,考虑到热稳定性、耐着色性、耐热着色性,本发明的组合物还可以含有高碱性碳酸钙盐。含有高碱性碳酸钙盐时,相对于(A)成分100质量份,优选含有5~700质量份、更优选含有25~600质量份、进一步优选含有50~500质量份。其中,将高碱性碳酸钙盐配混至稳定剂组合物时,在成型加工时成型体有可能发泡,因此需要注意。
高碱性碳酸钙盐是指钙的液状高碱性羧酸盐/碳酸盐络合物。该络合物不同于钙的羧酸正盐与碳酸钙的单纯混合物,它们通过某种相互作用而形成络合物,具备尽管具有高的金属含量但仍然在有机溶剂中显示均匀液态的特征。该络合物是以钙的羧酸正盐、碳酸钙、以及钙的羧酸与碳酸的复盐作为构成成分而构成的,以碳酸钙为中心且在其周围存在钙的羧酸正盐以及钙的羧酸与碳酸的复盐,可以说形成胶束那样的物质,从而在有机溶剂中显示均匀液态。
钙的液状高碱性羧酸盐/碳酸盐络合物可以通过与上述钡的液状高碱性羧酸盐/碳酸盐络合物同样的方法而制造。另外,也可以直接使用各种市售的络合物。作为市售的络合物的代表例,例如可列举出美国AM STABILZERS公司制的“PlastistabTM 2265”(高碱性钙油酸盐/碳酸盐络合物:比重为1.04~1.09、Ca=10%)。
本发明的组合物中,这些高碱性碳酸钙盐可以仅使用1种,也可以组合使用2种以上。
考虑到热稳定性、耐着色性、耐热着色性,本发明的组合物还可以含有水滑石化合物。含有水滑石化合物时,相对于(A)成分100质量份,优选含有10~500质量份、更优选含有30~400质量份、进一步优选含有50~300质量份。其中,将水滑石化合物配混至组合物时,在成型加工时成型体有可能发泡、以及成型体有可能发生应力白化,因此需要注意。
作为水滑石化合物,可列举出下述通式(2)所示的化合物。
Mgx1Znx2Al2(OH)2x1+2x2+4(CO3)1-y1/2(ClO4)y1mH2O (2)
通式(2)中,x1、x2和y1分别表示满足由下述式0≤x2/x1<10、2≤x1+x2<20、0≤y1≤2表示的条件的数,m表示0或任意的整数。
作为水滑石化合物,优选使用由镁与铝形成的复盐化合物或者由锌、镁和铝形成的复盐化合物。另外,可以为脱去了结晶水的水滑石化合物。另外,可以为用高氯酸处理过的水滑石化合物。这种水滑石化合物可以为天然物,也可以为合成品。对上述水滑石化合物的晶体结构、晶体粒径等没有限制。
另外,作为水滑石化合物,也可以使用利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覆盖了其表面的水滑石化合物。
本发明的组合物中,水滑石化合物可以仅使用1种,也可以组合使用2种以上。
本发明的组合物中,考虑到热稳定性、耐着色性、耐热着色性,也可以还含有除(F)成分的糖醇之外的多元醇化合物。含有多元醇化合物时,相对于(A)成分100质量份,优选含有0.01~100质量份、更优选含有0.1~75质量份、进一步优选含有1~50质量份。
作为多元醇化合物,可列举出例如季戊四醇、二季戊四醇、三季戊四醇、聚季戊四醇、新戊二醇、三羟甲基丙烷、二(三羟甲基)丙烷、1,3,5-三(2-羟基乙基)异氰脲酸酯、聚乙二醇、甘油、二甘油、木糖、蔗糖(sucrose)、海藻糖、肌醇、果糖、麦芽糖、乳糖等。多元醇化合物可以仅使用1种,也可以组合使用2种以上。
本发明的组合物也可以在不损害本发明效果的范围内含有溶剂。从稳定剂成分的溶解性的方面出发,溶剂优选有机溶剂,更优选沸点为100℃以上的有机溶剂,进一步优选沸点为120℃以上的有机溶剂,特别优选沸点为150℃以上的有机溶剂。若列举出优选的有机溶剂的例子,则可列举出3-甲氧基-正丁醇、2-乙基己醇、十一烷醇、十三烷醇等醇系有机溶剂;甲基二甘醇、丁基二甘醇、甲基丙二醇等二醇系有机溶剂;液体石蜡、环烷系溶剂、正链烷烃系溶剂、异链烷烃系溶剂、脂肪族系烃溶剂、芳香族系烃溶剂、矿物油等烃系溶剂等。溶剂可以仅使用1种,也可以组合使用2种以上。
关于使用溶剂时的配混量,相对于(A)成分100质量份,优选含有5~700质量份、更优选含有10~600质量份、进一步优选含有15~500质量份。
本发明的稳定剂组合物可以适宜地配混到氯乙烯系树脂中,制成氯乙烯系树脂组合物来使用。
为了得到本发明的组合物,只要将作为必需成分的(A)和(B)成分、作为根据需要而优选的任选成分的(C)~(I)成分、进而根据需要而可配混的成分、进而根据需要的溶剂进行混合即可,混合可以使用各种混合机。混合时可以加热。若列举出可使用的混合机的例子,可列举出转鼓混合机、亨舍尔混合机、螺带式混合机、V型混合机、W型混合机、超级搅拌机、诺塔混合机等。另外,可以将上述成分单独或2种以上同时直接配混到氯乙烯系树脂中,作为氯乙烯系树脂组合物来制备。
<2.氯乙烯系树脂组合物>
接着,针对氯乙烯系树脂组合物进行说明。
本发明的氯乙烯系树脂组合物含有氯乙烯系树脂和本发明的稳定剂组合物。
作为氯乙烯系树脂,对本体聚合、溶液聚合、悬浮聚合、乳液聚合等其聚合方法没有特别限定,例如可列举出聚氯乙烯、氯化聚氯乙烯、聚偏二氯乙烯、氯化聚乙烯、氯乙烯-乙酸乙烯酯共聚物、氯乙烯-乙烯共聚物、氯乙烯-丙烯共聚物、氯乙烯-苯乙烯共聚物、氯乙烯-异丁烯共聚物、氯乙烯-偏二氯乙烯共聚物、氯乙烯-苯乙烯-马来酸酐三元共聚物、氯乙烯-苯乙烯-丙烯腈共聚物、氯乙烯-丁二烯共聚物、氯乙烯-异戊二烯共聚物、氯乙烯-氯丙烯共聚物、氯乙烯-偏二氯乙烯-乙酸乙烯酯三元共聚物、氯乙烯-马来酸酯共聚物、氯乙烯-甲基丙烯酸酯共聚物、氯乙烯-丙烯腈共聚物、氯乙烯-各种乙烯基醚共聚物等氯乙烯系树脂、以及它们相互的共混品或者与其它不含氯的合成树脂、例如丙烯腈-苯乙烯共聚物、丙烯腈-丁二烯-苯乙烯共聚物、乙烯-乙酸乙烯酯共聚物、乙烯-(甲基)丙烯酸乙酯共聚物、聚酯等的共混品、嵌段共聚物、接枝共聚物等。这些氯乙烯系树脂可以为2种以上的混合物,也可以为与其它合成树脂的混合物。从热稳定性、耐着色性、耐热着色性的方面出发,使用的氯乙烯系树脂优选聚氯乙烯。
将本发明的组合物添加到氯乙烯系树脂时,考虑到加工性,优选进一步添加润滑剂。润滑剂也可以在配混到氯乙烯系树脂之前预先配混到组合物中。若列举出润滑剂的例子,则可列举出低分子蜡、固体石蜡、聚乙烯蜡、氯代烃、氟碳化合物等烃系润滑剂;巴西棕榈蜡、小烛树蜡等天然蜡系润滑剂;月桂酸、硬脂酸、山嵛酸等高级脂肪酸、或者羟基硬脂酸那样的羟基脂肪酸等脂肪酸系润滑剂;硬脂酰胺、月桂酰胺、油酰胺等脂肪族酰胺化合物或亚甲基双硬脂酰胺、亚乙基双硬脂酰胺那样的亚烷基双脂肪族酰胺等脂肪族酰胺系润滑剂;硬脂酸硬脂酯、硬脂酸丁酯、邻苯二甲酸二硬脂酯等脂肪酸一元醇酯化合物、或者甘油三硬脂酸酯、脱水山梨糖醇三硬脂酸酯、季戊四醇四硬脂酸酯、二季戊四醇六硬脂酸酯、聚甘油多蓖麻油酸酯、氢化蓖麻油等脂肪酸多元醇酯化合物、或者二季戊四醇的己二酸/硬脂酸酯那样的一元脂肪酸和多元有机酸与多元醇的复合酯化合物等脂肪酸醇酯系润滑剂;硬脂醇、月桂醇、棕榈醇等脂肪族醇系润滑剂;金属皂类;部分皂化褐煤酸酯等褐煤酸系润滑剂;丙烯酸系润滑剂;硅油等。这些润滑剂可以仅使用1种,也可以组合使用2种以上。
使用润滑剂时的添加量相对于氯乙烯系树脂100质量份优选0.01~5.0质量份,从加工性的方面出发更优选为0.05~4.0质量份、进一步优选为0.1~3.0质量份。
将本发明的组合物添加到氯乙烯系树脂中时,考虑到加工性,优选进一步添加加工助剂。加工助剂可以在配混到氯乙烯系树脂中之前,预先配混到本发明的组合物中。加工助剂可以从公知的加工助剂中适当选择。若列举出加工助剂的例子,则可列举出甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯等甲基丙烯酸烷基酯的均聚物或共聚物;上述甲基丙烯酸烷基酯与丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯等丙烯酸烷基酯的共聚物;上述甲基丙烯酸烷基酯与苯乙烯、α-甲基苯乙烯、乙烯基甲苯等芳香族乙烯基化合物的共聚物;上述甲基丙烯酸烷基酯与丙烯腈、甲基丙烯腈等乙烯基氰化合物等的共聚物等。这些加工助剂可以仅使用1种,也可以组合使用2种以上。
使用加工助剂时的添加量相对于氯乙烯系树脂100质量份优选为0.01~10质量份,更优选为0.05~5质量份。
氯乙烯系树脂中,除了本发明的组合物之外,也可以进一步在不损害本发明效果的范围内配混通常在氯乙烯系树脂中使用的其它添加剂、例如硫系抗氧化剂、除(B)成分之外的环氧化合物、增塑剂、紫外线吸收剂、冲击改良剂、加强材料、填充剂、沸石化合物、高氯酸盐类、有机酸镁盐、高碱性碳酸镁盐、发泡剂、阻燃剂、阻燃助剂等。这些各种添加剂可以在配混到氯乙烯系树脂中之前,预先配混到组合物中。
若列举出硫系抗氧化剂的例子,则可列举出硫代二丙酸的二月桂酯、二肉豆蔻基酯、肉豆蔻基硬脂基酯、二硬脂基酯等硫代二丙酸二烷基酯类;以及季戊四醇四(β-十二烷基巯基丙酸酯)等多元醇的β-烷基巯基丙酸酯类等。这些硫系抗氧化剂可以仅使用1种,也可以组合使用2种以上。
若列举出除本发明的(B)成分之外的环氧化合物的例子,则可列举出环氧化大豆油、环氧化亚麻籽油、环氧化桐油、环氧化蓖麻油、环氧化红花油等环氧化植物油。这些环氧化植物油可以仅使用1种,也可以组合使用2种以上。
若列举出增塑剂的例子,则可列举出邻苯二甲酸二丁酯、邻苯二甲酸丁基己酯、邻苯二甲酸二庚酯、邻苯二甲酸二辛酯、邻苯二甲酸二异壬酯、邻苯二甲酸二异癸酯、邻苯二甲酸二月桂酯、邻苯二甲酸二环己酯、对苯二甲酸二辛酯等苯二甲酸酯系增塑剂;己二酸二辛酯、己二酸二异壬酯、己二酸二异癸酯、二(二乙二醇丁醚)己二酸酯等己二酸酯系增塑剂;磷酸三苯基酯、磷酸三甲苯基酯、磷酸三(二甲苯)酯、磷酸三(异丙基苯基)酯、磷酸三乙酯、磷酸三丁酯、磷酸三辛酯、磷酸三(丁氧基乙基)酯、磷酸辛基二苯基酯等磷酸酯系增塑剂;使用乙二醇、二乙二醇、三乙二醇、1,2-丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-己二醇、1,6-己二醇、新戊二醇等多元醇与草酸、丙二酸、琥珀酸、戊二酸、己二酸、庚二酸、辛二酸、壬二酸、癸二酸、邻苯二甲酸、间苯二甲酸、对苯二甲酸等二元酸,并根据需要使用一元醇、单羧酸作为阻聚剂(stopper)而得到的聚酯系增塑剂;此外,四氢苯二甲酸系增塑剂、壬二酸系增塑剂、癸二酸系增塑剂、硬脂酸系增塑剂、柠檬酸系增塑剂、偏苯三甲酸系增塑剂、均苯四甲酸系增塑剂、联苯多羧酸系增塑剂等。这些增塑剂可以仅使用1种,也可以组合使用2种以上。
若列举出紫外线吸收剂的例子,则可列举出2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-辛氧基二苯甲酮、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)苯并三唑、2-(2-羟基-5-叔辛基苯基)苯并三唑、2-(2-羟基-3,5-二叔丁基苯基)-5-氯苯并三唑、2-(2-羟基-3-叔丁基-5-甲基苯基)-5-氯苯并三唑、2-(2-羟基-3,5-二枯基苯基)苯并三唑、2,2’-亚甲基双(4-叔辛基-6-苯并三唑基)苯酚、2-(2-羟基-3-叔丁基-5-羧基苯基)苯并三唑的聚乙二醇酯等2-(2-羟基苯基)苯并三唑类;水杨酸苯基酯、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、2,4-二叔戊基苯基-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-(2-羟基-4-辛氧基苯基)-4,6-双(2,4-二叔丁基苯基)-均三嗪、2-(2-羟基-4-甲氧基苯基)-4,6-二苯基-均三嗪、2-(2-羟基-4-丙氧基-5-甲基苯基)-4,6-双(2,4-二叔丁基苯基)-均三嗪等三芳基三嗪类等。这些紫外线吸收剂可以仅使用1种,也可以组合使用2种以上。
若列举出冲击改良剂的例子,则可列举出聚丁二烯、聚异戊二烯、聚氯丁二烯、氟橡胶、苯乙烯-丁二烯系共聚物橡胶、甲基丙烯酸甲酯-丁二烯-苯乙烯系共聚物、甲基丙烯酸甲酯-丁二烯-苯乙烯系接枝共聚物、丙烯腈-苯乙烯-丁二烯系共聚物橡胶、丙烯腈-苯乙烯-丁二烯系接枝共聚物、苯乙烯-丁二烯-苯乙烯嵌段共聚物橡胶、苯乙烯-异戊二烯-苯乙烯共聚物橡胶、苯乙烯-乙烯-丁烯-苯乙烯共聚物橡胶、乙烯-丙烯共聚物橡胶、乙烯-丙烯-二烯共聚物橡胶(EPDM)、含有机硅的丙烯酸系橡胶、有机硅/丙烯酸类复合橡胶系接枝共聚物、有机硅系橡胶等。需要说明的是,作为上述乙烯-丙烯-二烯共聚物橡胶(EPDM)的二烯,可列举出1,4-己二烯、二环戊二烯、亚甲基降冰片烯、乙叉基降冰片烯、丙烯基降冰片烯等。这些冲击改良剂可以仅使用1种,也可以组合使用2种以上。
加强材料可以使用通常用于加强合成树脂的纤维状、板状、粒状、粉末状的材料。具体而言,可列举出玻璃纤维、石棉纤维、碳纤维、石墨纤维、金属纤维、钛酸钾晶须、硼酸铝晶须、镁系晶须、硅系晶须、硅灰石、海泡石、石棉、矿渣纤维、硬硅钙石、硅磷灰石、石膏纤维、二氧化硅纤维、二氧化硅/氧化铝纤维、氧化锆纤维、氮化硼纤维、氮化硅纤维和硼纤维等无机纤维状加强材料;聚酯纤维、尼龙纤维、丙烯酸类纤维、再生纤维素纤维、乙酸酯纤维、红麻、苎麻、棉、黄麻、麻、剑麻、亚麻、亚麻布、丝绸、马尼拉麻、甘蔗、木浆、纸屑、废纸和羊毛等有机纤维状加强材料;玻璃鳞片、非膨胀性云母、石墨、金属箔、陶瓷珠、粘土、云母、绢云母、沸石、膨润土、白云石、高岭土、微粉硅酸、长石粉、钛酸钾、火山灰空心球(Shirasuballoon)、碳酸钙、碳酸镁、硫酸钡、氧化钙、氧化铝、氧化钛、硅酸铝、氧化硅、石膏、均密石英岩、片钠铝石和白土等板状、粒状的加强材料。这些加强材料可以用乙烯/乙酸乙烯酯共聚物等热塑性树脂、环氧树脂等热固性树脂进行了覆盖或集束处理,也可以用氨基硅烷、环氧硅烷等偶联剂等进行了处理。这些加强材料可以仅使用1种,也可以组合使用2种以上。
若列举出填充剂的例子,则可列举出碳酸钙、氧化钙、氢氧化钙、氢氧化锌、碳酸锌、硫化锌、氧化镁、氢氧化镁、碳酸镁、氧化铝、氢氧化铝、铝硅酸钠、水铝钙石、硅酸铝、硅酸镁、硅酸钙、沸石等硅酸金属盐、活性白土、滑石、粘土、氧化铁红、石棉、三氧化锑、二氧化硅、玻璃珠、云母、绢云母、玻璃鳞片、石棉、硅灰石、钛酸钾、PMF、石膏纤维、硬硅钙石、MOS、磷酸酯纤维、玻璃纤维、碳纤维、芳纶纤维等。这些填充剂可以仅使用1种,也可以组合使用2种以上。
沸石化合物为具有独特的三维沸石晶体结构的碱金属或碱土金属的铝硅酸盐,作为其代表例,可以使用A型、X型、Y型和P型沸石、丝光沸石、方沸石、方钠石族铝硅酸盐、斜发沸石、毛沸石和菱沸石等,这些沸石化合物的具有结晶水(所谓沸石水)的含水物或去除了结晶水的无水物均可,此外,可以使用其粒径为0.1~50μm的物质,特别优选0.5~10μm。这些沸石化合物可以仅使用1种,也可以组合使用2种以上。
若列举出高氯酸盐类的例子,可列举出高氯酸金属盐、高氯酸铵、高氯酸处理硅酸盐等。作为构成这些金属盐的金属,可例示出锂、钠、钾、钙、镁、锶、钡、锌、镉、铅、铝等。高氯酸金属盐可以为无水物,也可以为含水盐,此外,也可以为溶解于二乙二醇丁醚、丁基二乙二醇己二酸酯等醇系和酯系溶剂中的溶液、及其脱水物。这些高氯酸盐类可以仅使用1种,也可以组合使用2种以上。
作为有机酸镁盐,可列举出有机羧酸、酚类或有机磷酸类等的镁盐。
作为有机羧酸,例如可列举出前述有机酸钡盐中示例的有机羧酸。另外,作为酚类,例如可列举出前述有机酸钡盐中例示的酚类。另外,作为有机磷酸类,例如可列举出前述有机酸钡盐中示例的有机磷酸类。有机酸镁盐可以由2种以上的有机酸构成。例如,在由一元有机酸形成的镁盐的情况下,可以是同一有机酸形成阴离子部位,且与形成阳离子部位的2价镁形成盐,也可以是2种不同的一元有机酸形成阴离子部位,且与形成阳离子部位的2价镁形成盐。有机酸镁盐可以仅使用1种,也可以组合使用2种以上。另外,有机酸镁盐可以为酸性盐、中性盐、碱性盐。
高碱性碳酸镁盐是指,镁的液状高碱性羧酸盐/碳酸盐络合物。该络合物不同于镁与羧酸正盐与碳酸镁的单纯混合物,它们通过某种相互作用而形成络合物,具备尽管具有高的金属含量但仍然在有机溶剂中显示均匀液态的特征。该络合物是以镁的羧酸正盐、碳酸镁、以及镁的羧酸与碳酸的复盐作为构成成分而构成的,以碳酸镁为中心且在其周围存在镁的羧酸正盐和镁的羧酸与碳酸的复盐,可以说形成胶束那样的物质,从而在有机溶剂中显示均匀液态。
镁的液状高碱性羧酸盐/碳酸盐络合物可以通过与前述钡的液状高碱性羧酸盐/碳酸盐络合物同样的方法而制造。另外,也可以直接使用市售的络合物。这些高碱性碳酸镁盐可以仅使用1种,也可以组合使用2种以上。
若列举出发泡剂的例子,可列举出偶氮二甲酰胺、偶氮二异丁腈、p,p’-氧代双苯磺酰肼、n,n’-二亚硝基五亚甲基四胺、对甲苯磺酰氨基脲、三肼基三嗪等分解型有机发泡剂和碳酸氢钠、碳酸铵、碳酸氢铵、亚硝酸铵、叠氮化合物、硼氢化钠等分解型无机发泡剂。这些发泡剂可以仅使用1种,也可以组合使用2种以上。
作为阻燃剂和阻燃助剂的例子,可列举出含三嗪环的化合物、金属氢氧化物、以及无机磷、卤素系阻燃剂、硅系阻燃剂、磷酸酯系阻燃剂、缩合磷酸酯系阻燃剂、膨胀系阻燃剂、三氧化锑等锑氧化物、其它无机系阻燃助剂、有机系阻燃助剂等。
作为含三嗪环的化合物,例如可列举出三聚氰胺、三聚氰胺二酰胺、苯并胍胺、乙酰胍胺、苯二甲酰双胍胺(phthalodiguanamine)、三聚氰胺氰脲酸酯、焦磷酸三聚氰胺、亚丁基双胍胺、降冰片烯双胍胺、亚甲基双胍胺、亚乙基双三聚氰胺、三亚甲基双三聚氰胺、四亚甲基双三聚氰胺、六亚甲基双三聚氰胺、1,3-亚己基双三聚氰胺等。
作为金属氢氧化物,可列举出氢氧化镁、氢氧化铝、氢氧化钙、氢氧化钡、氢氧化锌、KISUMA 5A(氢氧化镁:协和化学工业株式会社制)等。
作为磷酸酯系阻燃剂的例子,例如可列举出磷酸三甲酯、磷酸三乙酯、磷酸三丁酯、磷酸三(丁氧基乙基)酯、磷酸三(氯乙基)酯、磷酸三(二氯丙基)酯、磷酸三苯基酯、磷酸三甲苯基酯、磷酸甲苯基二苯基酯、磷酸三(二甲苯)酯、磷酸辛基二苯基酯、磷酸二甲苯基二苯基酯、磷酸三异丙基苯基酯、磷酸2-乙基己基二苯基酯、磷酸叔丁基苯基二苯基酯、磷酸双(叔丁基苯基)苯基酯、磷酸三(叔丁基苯基)酯、磷酸异丙基苯基二苯基酯、磷酸双(异丙基苯基)二苯基酯、磷酸三(异丙基苯基)酯等。
作为缩合磷酸酯系阻燃剂的例子,可列举出1,3-亚苯基双(二苯基磷酸酯)、1,3-亚苯基双(二甲苯基磷酸酯)、双酚A双(二苯基磷酸酯)等。
作为膨胀系阻燃剂,可列举出聚磷酸铵、聚磷酸三聚氰胺、聚磷酸哌嗪、焦磷酸铵、焦磷酸三聚氰胺、焦磷酸哌嗪等(聚)磷酸的铵盐、胺盐。
作为其它无机系阻燃助剂,例如可列举出氧化钛、氧化铝、氧化镁、滑石等无机化合物及其表面处理品,例如可以使用TIPAQUE R-680(氧化钛:石原产业株式会社制)、KYOWAMAG 150(氧化镁:协和化学工业株式会社制)等各种市售品。这些阻燃剂和阻燃助剂可以仅使用1种,也可以组合使用2种以上。
另外,除了本发明的组合物之外,还可以在不损害本发明的组合物的效果的范围内添加通常在氯乙烯系树脂中使用的稳定化助剂。作为这种稳定化助剂,例如可以使用二苯基硫脲、苯胺基二硫代三嗪、三聚氰胺、苯甲酸、肉桂酸、对叔丁基苯甲酸等。进而,可以根据需要在不损害本发明效果的范围内配混通常在氯乙烯系树脂中使用的添加剂,例如交联剂、抗静电剂、防雾剂、防析出结垢剂、表面处理剂、荧光剂、抗真菌剂、杀菌剂、金属减活剂、脱模剂、二氧化钛等白色颜料、群青、酞菁蓝等蓝色颜料等颜料等。这些任选成分可以仅使用1种,也可以组合使用2种以上。这些稳定化助剂、任选成分可以在配混到氯乙烯系树脂中之前,预先配混到本发明的组合物中。
另外,在氯乙烯系树脂中使用的金属系稳定剂之中,添加铅系稳定剂、(有机)锡系稳定剂、镉系稳定剂从对环境造成的影响、毒性的方面出发不优选。
本发明的树脂组合物含有氯乙烯系树脂和本发明的组合物。氯乙烯系树脂组合物中的本发明的组合物的含量相对于氯乙烯系树脂100质量份优选为0.3~15.0质量份、更优选为0.3~10.0质量份、进一步优选为0.5~8.0质量份、更进一步优选为0.8~6.0质量份。
本发明的氯乙烯系树脂组合物中,除了本发明的组合物之外,还可以在不损害本发明效果的范围内含有上述润滑剂、加工助剂、通常在氯乙烯系树脂中使用的其它添加剂。
本发明的树脂组合物可通过例如辊加工、挤出成型加工、熔融流延法、加压成型加工、注射成型加工、压延成型等公知的成型方法进行成型。
<3.成型体>
本发明的成型体由本发明的氯乙烯系树脂组合物得到。由本发明的树脂组合物得到的成型品可用于管道、接头、配管部件等配管材料;墙体材料、地板材料、窗框、波纹板、雨水槽等建筑材料/结构材料;汽车用内外饰材料;电线用包覆材料;农业用材料;食品包装材料;包装物、衬垫、软管、片、托盘、瓶子、玩具等杂货、日用品、文具、装饰板、工业板、IC外壳等产品。
本发明的树脂组合物特别适合于硬质或半硬质用途的透明成型品用途,可以用于需要玻璃那样的透明性的容器类、工业板、装潢板、托盘、薄膜、收缩薄膜、片、建材、供水排水管、板、接头、汽车用材料、软管、IC外壳、瓶等。
作为成型体的透明性,优选厚度为6mm时雾度值(雾度)为20.0以下、更优选为15.0以下、进一步优选为10.0以下、更进一步优选为7.0以下、再进一步优选为6.0以下。需要说明的是,雾度值的测定可按照JIS K 7136进行测定。
实施例
以下,通过实施例来具体说明本发明。但本发明完全不限定于以下的实施例。
〔稳定剂组合物的制造〕
按照表1~12所示的配比来配混各种成分,制备稳定剂组合物。(B)成分的环氧化合物使用下述所示的环氧化合物1~8。需要说明的是,组合物73~80使用下述环氧化大豆油。
环氧化合物1:氢化双酚A二缩水甘油醚(环氧乙烷氧浓度为7.4质量%)
环氧化合物2:双酚A二缩水甘油醚(环氧乙烷氧浓度为8.4质量%)
环氧化合物3:三羟甲基丙烷三缩水甘油醚(环氧乙烷氧浓度为10.7质量%)
环氧化合物4:新戊二醇二缩水甘油醚(环氧乙烷氧浓度为11.4质量%)
环氧化合物5:甲苯基缩水甘油醚(环氧乙烷氧浓度为8.9质量%)
环氧化合物6:聚丙二醇二缩水甘油醚(环氧乙烷氧浓度为5.3质量%)
环氧化合物7:碳原子数12~13的烷基缩水甘油醚(环氧乙烷氧浓度为5.0质量%)
环氧化合物8:2-苯基苯酚缩水甘油醚(环氧乙烷氧浓度为7.1质量%)
比较环氧化合物:环氧化大豆油(环氧乙烷氧浓度为6.7质量%)
〔实施例1~84和比较例1~10〕
按照表13~27所示的配比,用亨舍尔混合器将氯乙烯系树脂与组合物和其它添加剂进行共混,得到各氯乙烯系树脂组合物。将所得氯乙烯系树脂组合物进行压延成型,制作片。辊混炼条件设为165℃×30rpm×0.6mm。使用所得片,通过下述试验方法,评价动态热稳定性、静态热稳定性、耐着色性、耐热着色性、透明性。将评价结果一并记载于表13~27。
<动态热稳定性试验>
将各树脂组合物65g/60cc投入至混炼条件为190℃×40rpm的LABO PLASTOMIL试验机(4C150型、株式会社东洋精机制作所制)中,测定至树脂发生分解而混炼转矩上升为止的分解时间。将结果一并记载于表13~27。分解时间越长,则可以说热稳定性越优异。
<静态热稳定性试验>
将所得片投入至190℃和200℃的齿轮烘箱中,测定黑化时间(分钟)。将结果一并记载于表13~27。黑化时间越长,则可以说热稳定性越优异。
<耐着色性试验>
将所得0.6mm厚的片进行粘合,以190℃进行5分钟的加压加工而制作1mm厚的片。按照JIS K7373来测定该片的黄色度(YI值)。将结果一并记载于表13~27。黄色度的数值越小,则可以说越不会着色,初始着色越少,耐着色性越优异。
<耐热着色性试验>
将所得0.6mm厚的片进行粘合,以190℃进行15分钟的加压加工而制作1mm厚的片。另外,将所得0.6mm厚的片进行粘合,以190℃进行45分钟的加压加工而制作1mm厚的片。按照JIS K7373来测定这些片的黄色度(YI值)。将结果一并记载于表13~27。黄色度的数值越小,则可以说越不会着色,耐热着色性越优异。黄色度的数值越大,则耐热着色性越差,更差的会发生黑化。
<透明性试验>
针对以180℃加压加工5分钟而得的6mm厚的片,使用Haze-Gard 2(株式会社东洋精机制作所制),按照JIS K 7136来测定雾度值。将结果一并记载于表13~27。
[表1]
*1:亚磷酸癸基二苯酯
*2:亚磷酸三癸酯
*3:季戊四醇四[3-(3,5-二叔丁基-4-羟基苯基)丙酸酯](株式会社ADEKA制、制品名:ADEKASTAB AO-60)
*4:山梨糖醇
*5:ADEKASTAB LA-63P(株式会社ADEKA制)
[表2]
[表3]
[表4]
[表5]
[表6]
[表7]
[表8]
[表9]
[表10]
[表11]
[表12]
[表13]
*6:信越化学工业株式会社制TK-700(聚合度为700)
*7:丙烯酸系加工助剂(株式会社KANEKA制KANEACE PA-20)
*8:复合酯系内部润滑剂(Emery Oleochemicals Japan公司制、LOXIOL G72)
[表14]
[表15]
[表16]
[表17]
[表18]
[表19]
[表20]
[表21]
[表22]
[表23]
[表24]
[表25]
[表26]
[表27]
由表1~12和表13~27所示的结果可以明确:本发明的组合物能够对氯乙烯系树脂赋予优异的热稳定性、耐着色性和耐热着色性。进而可明确:在需要透明性的透明性用途的情况下,能够赋予优异的透明性。
另外可明确:本发明的树脂组合物能够提供热稳定性、耐着色性和耐热着色性优异的成型体。进而可明确:在需要透明性的透明性用途的情况下,能够提供透明性优异的成型体。
Claims (13)
1.一种稳定剂组合物,其特征在于,相对于(A)成分100质量份,含有5~2500质量份的(B)成分,
(A)成分为1种以上的有机酸锌盐;
(B)成分为1种以上的具有缩水甘油醚基和/或缩水甘油酯基的环氧化合物。
2.根据权利要求1所述的稳定剂组合物,其中,相对于(A)成分100质量份,含有5~300质量份的1种以上的β-二酮化合物作为(C)成分。
3.根据权利要求1或2所述的稳定剂组合物,其中,相对于(A)成分100质量份,含有5~700质量份的1种以上的亚磷酸酯化合物作为(D)成分。
4.根据权利要求1~3中任一项所述的稳定剂组合物,其中,相对于(A)成分100质量份,含有5~200质量份的1种以上的酚系抗氧化剂作为(E)成分。
5.根据权利要求1~4中任一项所述的稳定剂组合物,其中,相对于(A)成分100质量份,含有1~1000质量份的1种以上的糖醇作为(F)成分。
6.根据权利要求1~5中任一项所述的稳定剂组合物,其中,相对于(A)成分100质量份,含有5~200质量份的1种以上的受阻胺系光稳定剂作为(G)成分。
7.根据权利要求1~6中任一项所述的稳定剂组合物,其中,(B)成分的环氧化合物的环氧乙烷氧浓度在3.0~15.0质量%的范围内。
8.根据权利要求1~7中任一项所述的稳定剂组合物,其不含有机锡系化合物。
9.根据权利要求1~8中任一项所述的稳定剂组合物,其用于透明制品。
10.一种氯乙烯系树脂组合物,其特征在于,其含有氯乙烯系树脂和权利要求1~9中任一项所述的稳定剂组合物。
11.根据权利要求10所述的氯乙烯系树脂组合物,其中,相对于所述氯乙烯系树脂100质量份,所述稳定剂组合物为0.3~15.0质量份。
12.一种成型体,其特征在于,其由权利要求10或11所述的氯乙烯系树脂组合物得到。
13.根据权利要求12所述的成型体,其厚度为6mm时的雾度值为20.0以下。
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