WO2011030822A1 - ホスホン酸金属塩の製造方法及びホスホン酸金属塩を含む熱可塑性樹脂組成物 - Google Patents
ホスホン酸金属塩の製造方法及びホスホン酸金属塩を含む熱可塑性樹脂組成物 Download PDFInfo
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- WO2011030822A1 WO2011030822A1 PCT/JP2010/065517 JP2010065517W WO2011030822A1 WO 2011030822 A1 WO2011030822 A1 WO 2011030822A1 JP 2010065517 W JP2010065517 W JP 2010065517W WO 2011030822 A1 WO2011030822 A1 WO 2011030822A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal salt
- phenylphosphonic acid
- metal
- thermoplastic resin
- acid metal
- Prior art date
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- 239000002184 metal Substances 0.000 title claims abstract description 186
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 41
- 239000011342 resin composition Substances 0.000 title claims abstract description 22
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- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 claims abstract description 106
- -1 phenylphosphonic acid compound Chemical class 0.000 claims abstract description 65
- 239000000203 mixture Substances 0.000 claims abstract description 46
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- 150000001875 compounds Chemical class 0.000 claims abstract description 38
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- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 38
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- 239000011575 calcium Substances 0.000 claims description 10
- 239000011701 zinc Substances 0.000 claims description 10
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
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- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
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- 239000011572 manganese Substances 0.000 claims description 2
- 239000000088 plastic resin Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 abstract description 35
- 230000008025 crystallization Effects 0.000 abstract description 35
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- VYXPIEPOZNGSJX-UHFFFAOYSA-L zinc;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Zn+2].[O-]P([O-])(=O)C1=CC=CC=C1 VYXPIEPOZNGSJX-UHFFFAOYSA-L 0.000 description 26
- 239000002667 nucleating agent Substances 0.000 description 24
- SSTALXWJLKACQG-UHFFFAOYSA-L calcium;dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [Ca+2].[O-]P([O-])(=O)C1=CC=CC=C1 SSTALXWJLKACQG-UHFFFAOYSA-L 0.000 description 21
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- 239000000126 substance Substances 0.000 description 9
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 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 2
- 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 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
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- 125000003118 aryl group Chemical group 0.000 description 2
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
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- CRPRCSYCZWFVED-UHFFFAOYSA-N (4-ethylphenyl)phosphonic acid Chemical compound CCC1=CC=C(P(O)(O)=O)C=C1 CRPRCSYCZWFVED-UHFFFAOYSA-N 0.000 description 1
- LYNDWSARZJHIKU-UHFFFAOYSA-N (4-methylphenyl)phosphonic acid Chemical compound CC1=CC=C(P(O)(O)=O)C=C1 LYNDWSARZJHIKU-UHFFFAOYSA-N 0.000 description 1
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- MGMGXZHNWAGNIS-UHFFFAOYSA-N [3,5-bis(ethoxycarbonyl)phenyl]phosphonic acid Chemical compound CCOC(=O)C1=CC(C(=O)OCC)=CC(P(O)(O)=O)=C1 MGMGXZHNWAGNIS-UHFFFAOYSA-N 0.000 description 1
- MPLIIEJXULZTBX-UHFFFAOYSA-N [3,5-bis(methoxycarbonyl)phenyl]phosphonic acid Chemical compound COC(=O)C1=CC(C(=O)OC)=CC(P(O)(O)=O)=C1 MPLIIEJXULZTBX-UHFFFAOYSA-N 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- JMGIKIHJCSKLLI-UHFFFAOYSA-N [4-(2-methylpropyl)phenyl]phosphonic acid Chemical compound CC(C)CC1=CC=C(P(O)(O)=O)C=C1 JMGIKIHJCSKLLI-UHFFFAOYSA-N 0.000 description 1
- FPWJLQXCGHQXLL-UHFFFAOYSA-N [P].OP(O)(O)=O Chemical compound [P].OP(O)(O)=O FPWJLQXCGHQXLL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920001893 acrylonitrile styrene Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- ZGNIGAHODXRWIT-UHFFFAOYSA-K aluminum;4-tert-butylbenzoate Chemical compound [Al+3].CC(C)(C)C1=CC=C(C([O-])=O)C=C1.CC(C)(C)C1=CC=C(C([O-])=O)C=C1.CC(C)(C)C1=CC=C(C([O-])=O)C=C1 ZGNIGAHODXRWIT-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
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- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-L dioxido-oxo-phenyl-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-L 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- FXDGCBFGSXNGQD-UHFFFAOYSA-L disodium;bicyclo[2.2.1]heptane-2,3-dicarboxylate Chemical class [Na+].[Na+].C1CC2C(C([O-])=O)C(C(=O)[O-])C1C2 FXDGCBFGSXNGQD-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000005010 epoxy-amino resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005042 ethylene-ethyl acrylate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- RLAWWYSOJDYHDC-BZSNNMDCSA-N lisinopril Chemical compound C([C@H](N[C@@H](CCCCN)C(=O)N1[C@@H](CCC1)C(O)=O)C(O)=O)CC1=CC=CC=C1 RLAWWYSOJDYHDC-BZSNNMDCSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- FRGLATJAXRODDV-UHFFFAOYSA-N methanesulfonic acid;1,3,5-triazine-2,4,6-triamine Chemical compound CS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 FRGLATJAXRODDV-UHFFFAOYSA-N 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- FUSRYQFNOAIOLF-UHFFFAOYSA-N phenylphosphonic acid;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)C1=CC=CC=C1 FUSRYQFNOAIOLF-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001693 poly(ether-ester) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004633 polyglycolic acid Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- UQDJGEHQDNVPGU-UHFFFAOYSA-N serine phosphoethanolamine Chemical compound [NH3+]CCOP([O-])(=O)OCC([NH3+])C([O-])=O UQDJGEHQDNVPGU-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- KYKFCSHPTAVNJD-UHFFFAOYSA-L sodium adipate Chemical compound [Na+].[Na+].[O-]C(=O)CCCCC([O-])=O KYKFCSHPTAVNJD-UHFFFAOYSA-L 0.000 description 1
- 239000001601 sodium adipate Substances 0.000 description 1
- 235000011049 sodium adipate Nutrition 0.000 description 1
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 239000004299 sodium benzoate Substances 0.000 description 1
- ZHROMWXOTYBIMF-UHFFFAOYSA-M sodium;1,3,7,9-tetratert-butyl-11-oxido-5h-benzo[d][1,3,2]benzodioxaphosphocine 11-oxide Chemical compound [Na+].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 ZHROMWXOTYBIMF-UHFFFAOYSA-M 0.000 description 1
- SNAQARSCIHDMGI-UHFFFAOYSA-M sodium;bis(4-tert-butylphenyl) phosphate Chemical compound [Na+].C1=CC(C(C)(C)C)=CC=C1OP([O-])(=O)OC1=CC=C(C(C)(C)C)C=C1 SNAQARSCIHDMGI-UHFFFAOYSA-M 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- LTURHSAEWJPFAA-UHFFFAOYSA-N sulfuric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OS(O)(=O)=O.NC1=NC(N)=NC(N)=N1 LTURHSAEWJPFAA-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- CZPRKINNVBONSF-UHFFFAOYSA-M zinc;dioxido(oxo)phosphanium Chemical compound [Zn+2].[O-][P+]([O-])=O CZPRKINNVBONSF-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3834—Aromatic acids (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3895—Pyrophosphonic acids; phosphonic acid anhydrides
-
- 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
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5317—Phosphonic compounds, e.g. R—P(:O)(OR')2
- C08K5/5333—Esters of phosphonic acids
Definitions
- the present invention relates to a method for producing a phenylphosphonic acid metal salt, a phenylphosphonic acid metal salt produced by the production method and a surplus metal salt, a surplus metal oxide or a surplus metal hydroxide, a phenylphosphonate metal salt composition,
- the present invention also relates to a thermoplastic resin composition containing the phenylphosphonic acid metal salt composition.
- Polylactic acid resin which is a thermoplastic resin, especially biodegradable polyester resin, is used for packaging materials such as containers and films, textile materials such as clothing, floor mats and automotive interior materials, and housings and parts for electrical and electronic products. Expected to be used for molding materials.
- Polyolefin resins are widely used in various industrial parts such as daily life materials and automobile interior and exterior parts. Especially, the range of use has been expanded as interior and exterior parts of automobiles such as bumpers, instrument panels, door trims and pillars.
- thermoplastic resins such as polylactic acid resins and polyolefin resins
- attempts have been made to increase the crystallization speed and crystallinity of the resins.
- the crystal nucleating agent serves as a primary crystal nucleus of a crystalline polymer and promotes crystal growth.
- the crystal nucleating agent functions to reduce the crystal size and increase the crystallization speed.
- inorganic particles composed of talc and / or boron nitride having a specific particle size or less (Patent Document 1), an amide compound represented by a specific formula (Patent Document 2), a specific formula A sorbitol derivative (Patent Document 3), a phosphoric acid ester metal salt and a basic inorganic aluminum compound (Patent Document 4), a metal salt of a phosphorus compound represented by a specific formula (such as a phenylphosphonic acid metal salt) (Patent Document 5) ) Etc.
- Patent Document 1 inorganic particles composed of talc and / or boron nitride having a specific particle size or less
- Patent Document 2 an amide compound represented by a specific formula
- Patent Document 3 an amide compound represented by a specific formula A sorbitol derivative
- Patent Document 4 a phosphoric acid ester metal salt and a basic inorganic aluminum compound
- Patent Document 5 a metal salt of a phosphorus compound represented by
- metal salts such as phosphonic acid and phosphonous acid are effective as a crystal nucleating agent for block copolymerized poly (ether ester) (Patent Document 6).
- carboxylic acid metal such as sodium benzoate, aluminum 4-tert-butylbenzoate, sodium adipate, sodium bicyclo [2.2.1] heptane-2,3-dicarboxylate Salts;
- phosphate metal salts such as sodium bis (4-tert-butylphenyl) phosphate, sodium 2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) )
- Polyhydric alcohol derivatives such as sorbitol and bis (dimethylbenzylidene) sorbitol; metal salts such as aromatic phosphonic acid and aromatic phosphonous acid (Patent Document 6).
- carboxylic acid metal such as sodium benzoate, aluminum 4-ter
- the method using a crystal nucleating agent is useful as it can increase the crystallization speed and increase the crystallinity, but in recent years has achieved higher molding processability and heat resistance, and has a wide range of applications.
- development of a more effective crystal nucleating agent is desired.
- an organic substance contained in the crystal nucleating agent is used to reduce the environmental burden. It is also desired to reduce the component content (ie, phenylphosphonic acid content).
- an object of the present invention is to provide a crystal nucleating agent suitable for promoting the crystallization of thermoplastic resins such as polylactic acid resins and polyolefin resins, and in particular, a crystal nucleating agent with reduced environmental components of petroleum-derived organic components. It is an object of the present invention to provide a method for producing a metal salt of phenylphosphonic acid which is suitable as Furthermore, the present invention provides a composition containing a metal salt of phenylphosphonic acid produced by the above production method, a crystal nucleating agent comprising the metal salt of phenylphosphonic acid, and the metal salt composition of phenylphosphonic acid and a thermoplastic resin. It aims at providing the thermoplastic resin composition containing this.
- the inventors of the present invention produced a phenylphosphonic acid metal salt useful as a crystal nucleating agent.
- the shape of the metal salt obtained (precipitated) by reacting with an oxide or a metal hydroxide (hereinafter collectively referred to as a metal source compound) is smaller than that obtained by a conventional production method.
- a metal source compound an oxide or a metal hydroxide
- the present invention provides, as a first aspect, the formula [1]
- the present invention relates to a method for producing a phenylphosphonic acid metal salt, characterized by reacting a compound (a) with a metal salt, metal oxide or metal hydroxide (b) in an amount exceeding its equivalent.
- a compound (a) with a metal salt, metal oxide or metal hydroxide (b) in an amount exceeding its equivalent.
- B is made to react, It is related with the manufacturing method as described in a 1st viewpoint.
- the metal salt, metal oxide or metal hydroxide (b) of the reaction raw material and the phenylphosphonic acid compound (a) are reacted at a molar ratio of 100: 0.01 to 100: 90. It is related with the manufacturing method according to the first aspect or the second aspect.
- species of the said metal salt, a metal oxide, or a metal hydroxide (b) is zinc or calcium.
- the present invention relates to the production method according to the fifth aspect, wherein the metal salt, metal oxide, or metal hydroxide (b) is zinc oxide or calcium carbonate.
- the metal salt, metal oxide, or metal hydroxide (b) is zinc oxide or calcium carbonate.
- phenyl phosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide produced by the production method according to any one of the first to sixth aspects The present invention relates to a phosphonic acid metal salt composition.
- the present invention relates to the phenylphosphonic acid metal salt composition according to the seventh aspect, wherein the metal species in the phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide is zinc.
- the present invention relates to the phenylphosphonic acid metal salt composition according to the seventh aspect, wherein the metal species in the phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide is calcium.
- the present invention relates to a crystal nucleating agent comprising the phenylphosphonic acid metal salt composition according to any one of the seventh to ninth aspects.
- the present invention relates to a thermoplastic resin composition comprising the phenylphosphonic acid metal salt composition according to any one of the seventh to ninth aspects and a thermoplastic resin.
- an eleventh aspect includes 0.01 to 10 parts by mass of the phenylphosphonic acid metal salt composition according to any one of the seventh to ninth aspects with respect to 100 parts by mass of the thermoplastic resin.
- the present invention relates to the thermoplastic resin composition described in the aspect.
- the present invention relates to the thermoplastic resin composition according to the eleventh aspect or the twelfth aspect, in which the thermoplastic resin is a polylactic acid resin.
- the present invention relates to the thermoplastic resin composition according to the thirteenth aspect, wherein the phenylphosphonic acid metal salt composition is the phenylphosphonic acid metal salt composition according to the eighth aspect.
- the thermoplastic resin is selected from the group consisting of polypropylene, polypropylene copolymer, polyethylene, polyethylene copolymer, polybutylene, and poly (4-methyl-1-pentene).
- the present invention relates to a thermoplastic resin composition.
- the present invention relates to the thermoplastic resin composition according to the fifteenth aspect, wherein the phenylphosphonic acid metal salt composition is the phenylphosphonic acid metal salt composition according to the ninth aspect.
- the present invention by reacting a phenylphosphonic acid compound with a metal salt, metal oxide or metal hydroxide in an amount exceeding the equivalent of the compound, in particular, said metal salt, metal oxide or metal water.
- a metal salt, metal oxide or metal hydroxide in an amount exceeding the equivalent of the compound, in particular, said metal salt, metal oxide or metal water.
- the production method of the present invention can produce a phenylphosphonic acid metal salt having a much finer shape than that according to the conventional production method, without requiring further steps such as pulverization.
- a phenylphosphonic acid metal salt formed near the surface of the metal source compound particles in the medium or other than that is a metal source is not clear, for example, a phenylphosphonic acid metal salt formed near the surface of the metal source compound particles in the medium or other than that is a metal source. It is considered that a finer shape can be obtained by crystallization on the surface of the compound particle and part or all of it is peeled off.
- a phenylphosphonic acid metal salt composition containing the metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide is used as a thermoplastic resin such as polyester resin such as polylactic acid resin or crystalline polyolefin resin.
- a thermoplastic resin such as polyester resin such as polylactic acid resin or crystalline polyolefin resin.
- FIG. FIG. 2 is a view showing a scanning microscope (SEM) image of the white powder of zinc phenylphosphonate produced in Comparative Synthesis Example 1.
- FIG. 4 is a diagram showing a scanning microscope (SEM) image of white powder of calcium phenylphosphonate produced in Comparative Synthesis Example 2.
- the method for producing a phenylphosphonic acid metal salt of the present invention comprises reacting a phenylphosphonic acid compound with a metal source compound (metal salt, metal oxide or metal hydroxide) in an amount exceeding the equivalent of the compound, particularly The reaction is carried out in a solvent that is hardly soluble in the metal source compound.
- a metal source compound metal salt, metal oxide or metal hydroxide
- the phenylphosphonic acid compound used in the production method of the present invention is a compound represented by the following general formula [1].
- R 1 and R 2 in the formula are a hydrogen atom; a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an alkyl group having 1 to 10 carbon atoms such as tert-butyl group; and an alkoxycarbonyl group having 1 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group.
- R 1 and R 2 may be the same or different.
- phenylphosphonic acid compound represented by the above formula [1] examples include phenylphosphonic acid, 4-methylphenylphosphonic acid, 4-ethylphenylphosphonic acid, 4-n-propylphenylphosphonic acid, 4-isopropylphenyl. Phosphonic acid, 4-n-butylphenylphosphonic acid, 4-isobutylphenylphosphonic acid, 4-tert-butylphenylphosphonic acid, 3,5-dimethoxycarbonylphenylphosphonic acid, 3,5-diethoxycarbonylphenylphosphonic acid, 2 , 5-dimethoxycarbonylphenylphosphonic acid, 2,5-diethoxycarbonylphenylphosphonic acid and the like. As these compounds, commercially available products can be preferably used as they are.
- metal salt used with the manufacturing method of this invention A sulfate, nitrate, chloride, carbonate, acetate etc. can be used.
- metal oxide or metal hydroxide monovalent, divalent and trivalent metals can be used.
- these metals can be used by mixing two or more kinds of metals.
- the metal species include lithium, sodium, potassium, magnesium, aluminum, calcium, barium, manganese, iron, cobalt, nickel, copper, and zinc.
- lithium, sodium, potassium, magnesium, calcium, barium, manganese, iron, cobalt, copper, and zinc are preferable as the metal species, and zinc or calcium is particularly preferable, specifically zinc oxide or calcium carbonate. It is preferable.
- metal source compounds that is, metal salts, metal oxides or metal hydroxides can also be suitably used as they are.
- the reaction of the phenylphosphonic acid compound and the metal source compound is carried out in a suitable medium using an amount of the metal source compound that exceeds the equivalent of the phenylphosphonic acid compound.
- a suitable medium used here, It is preferable that the phenylphosphonic acid compound which is a raw material is soluble from the surface of reaction efficiency.
- a metal source compound as a raw material and a solvent in which the phenylphosphonic acid metal salt is hardly soluble are preferable.
- solvents examples include water; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; nitriles such as acetonitrile; ethers such as tetrahydrofuran; alcohols such as methanol, ethanol, 1-propanol, and 2-propanol; Examples thereof include amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; sulfoxides such as dimethyl sulfoxide. These solvents may be used alone or in combination of two or more. Among these, water and alcohols are preferable, and it is more preferable to use water in consideration of ease of handling and economy.
- the total charge of the medium is preferably 0.001 to 1,000 times the total charge mass of the phenylphosphonic acid compound (a) and the metal source compound (b). More preferably, the lower limit of the total charged amount of the medium is 0.002 times, particularly preferably 0.01 times the total charged mass of the phenylphosphonic acid compound (a) and the metal source compound (b). It is. Further, the upper limit of the total charged amount of the medium is more preferably 200 times, particularly preferably 100 times the total charged mass of the phenylphosphonic acid compound (a) and the metal source compound (b). More preferably, the amount is 50 times.
- a method of adding the phenylphosphonic acid compound solution to a slurry containing the metal source compound as a raw material a method of adding the phenylphosphonic acid compound solution to the metal source compound, This is performed by a method of adding a solvent to the mixture of the metal source compound and the phenylphosphonic acid compound.
- the solvent used for the slurry or the phenylphosphonic acid compound solution and the solvent to be added include the above-mentioned medium.
- the reaction system is fully equipped with various reaction systems such as various mixers such as homomixers, Henschel mixers, and Roedige mixers, and various crushers such as ball mills, bead mills, and optimizers.
- various mixers such as homomixers, Henschel mixers, and Roedige mixers
- various crushers such as ball mills, bead mills, and optimizers.
- Any device can be used without particular limitation as long as it is fluidized.
- a mixer that excels in powder mixing capability and can be mixed or heated simultaneously or sequentially such as a Henschel mixer or a Ladige mixer, the amount of medium used for the reaction can be greatly reduced.
- the reaction and the drying described below can be performed in the same apparatus, which is industrially advantageous.
- the reaction temperature at this time may affect the magnitude
- phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide (hereinafter also referred to as surplus metal source compound).
- surplus metal source compound phenylphosphonic acid metal salt composition
- the phenylphosphonic acid metal salt composition is, to speak, a shape in which particles of phenylphosphonic acid metal salt are dispersed in a group of metal source compound particles, that is, a metal salt in which phenylphosphonic acid metal salt is dispersed, It may have the shape of a metal oxide or metal hydroxide crystalline powder, and may also include a composite in which phenylphosphonic acid metal salt is attached to all or part of the surface of the metal source compound particles.
- the drying temperature at this time can be appropriately selected depending on the type of medium, and reduced pressure conditions may be applied. When water is used as the medium, the drying temperature is preferably 100 to 500 ° C at normal pressure, more preferably 120 to 200 ° C.
- the crystal water cannot be removed at a temperature lower than 100 ° C., and it is in the form of a monohydrate of phenylphosphonic acid metal salt and is not suitable as a crystal nucleating agent for resins that dislike hydrolysis (such as polyester resins). Absent. Further, at a temperature higher than 500 ° C., there is a risk of inducing decomposition of the phenylphosphonic acid metal salt.
- the phenylphosphonic acid metal salt of the present invention obtained through the above production method has a very fine shape.
- zinc phenylphosphonate has a fine granular shape, and the average particle diameter is 0.05 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m.
- calcium phenylphosphonate has a fine needle-like shape, and the average thickness is 0.05 to 1 ⁇ m, preferably 0.05 to 0.5 ⁇ m.
- the metal salt, metal oxide or metal hydroxide in which the phenylphosphonic acid metal salt thus obtained is dispersed may be subjected to shearing force such as a homomixer, a Henschel mixer, and a Laedige mixer as necessary.
- shearing force such as a homomixer, a Henschel mixer, and a Laedige mixer as necessary.
- a further finer shape can be obtained using a pulverizer such as a mixing machine, a ball mill, a pin disc mill, a pulverizer, an inomizer, or a counter jet mill.
- a finer shape can be obtained with a wet pulverizer such as water, an organic solvent that can be mixed with water, and a ball mill, a bead mill, a sand grinder, an attritor, and an optimizer using a mixed solution thereof.
- the present invention also relates to a crystal nucleating agent comprising a phenylphosphonic acid metal salt composition containing phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide produced by the above production method.
- the present invention also provides a phenylphosphonic acid metal salt composition containing a phenylphosphonic acid metal salt and an excess metal salt, an excess metal oxide or an excess metal hydroxide produced by the production method, and a thermoplastic resin. It also relates to a plastic resin composition.
- the thermoplastic resin include general-purpose thermoplastic resins, general-purpose thermoplastic engineering plastics, and biodegradable resins including polylactic acid resins.
- thermoplastic resins examples include polyethylene (PE), polyethylene copolymer, polypropylene (PP), polypropylene copolymer, polybutylene (PB), ethylene-vinyl acetate copolymer (EVA), ethylene-ethyl acrylate copolymer (EEA), polyolefin resins such as poly (4-methyl-1-pentene), polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), acrylonitrile-butadiene-styrene copolymer Examples thereof include polystyrene resins such as coalescence (ABS), vinyl chloride resins, polyurethane resins, phenol resins, epoxy resins, amino resins, and unsaturated polyester resins.
- ABS coalescence
- ABS vinyl chloride resins
- polyurethane resins polyurethane resins
- phenol resins epoxy resins
- amino resins amino resins
- Examples of general-purpose engineering plastics include polyamide resins, polycarbonate resins, polyphenylene ether resins, modified polyphenylene ether resins, polyester resins such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT), polyacetal resins, polysulfone resins, polyphenylene sulfide resins. And polyimide resin.
- the polylactic acid resin includes a homopolymer or copolymer of polylactic acid.
- the arrangement pattern of the copolymer may be any of random copolymer, alternating copolymer, block copolymer, and graft copolymer. Further, it may be a blend polymer with other resin mainly composed of polylactic acid homopolymer or copolymer.
- the other resin include biodegradable resins other than the polylactic acid resin described later, the above-described general-purpose thermoplastic resins, and general-purpose thermoplastic engineering plastics.
- the polylactic acid resin is not particularly limited, and examples thereof include those obtained by ring-opening polymerization of lactide and those obtained by direct polycondensation of lactic acid D-form, L-form, racemic form and the like.
- the number average molecular weight of the polylactic acid resin is generally about 10,000 to 500,000.
- a polylactic acid resin obtained by crosslinking with a crosslinking agent using heat, light, radiation, or the like can also be used.
- biodegradable resins other than polylactic acid resins include poly-3-hydroxybutyric acid, polyhydroxyalkanoic acid such as a copolymer of 3-hydroxybutyric acid and 3-hydroxyhexanoic acid, polycaprolactone, and polybutylene succinate.
- polybutylene succinate / adipate polybutylene succinate / carbonate
- polyethylene succinate polyethylene succinate / adipate
- polyvinyl alcohol polyglycolic acid
- modified starch cellulose acetate, chitin, chitosan, lignin and the like.
- the amount of phenylphosphonic acid metal salt composition containing phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide in the thermoplastic resin composition is 100 parts by mass of thermoplastic resin. 0.01 to 10 parts by mass is preferable. The amount is more preferably 0.02 to 5 parts by mass, still more preferably 0.03 to 2 parts by mass. When the added amount of the phenylphosphonic acid metal salt composition is less than 0.01 parts by mass, it is difficult to sufficiently increase the crystallization rate of the thermoplastic resin. A thermoplastic resin having a high crystallization rate can be obtained even when the amount exceeds 10 parts by mass, but the crystallization rate is not further increased.
- the method of blending a phenylphosphonic acid metal salt composition containing a phenylphosphonic acid metal salt and an excess metal source compound (surplus metal salt, excess metal oxide or excess metal hydroxide) into the thermoplastic resin is particularly limited. It can carry out by a well-known method, without being carried out.
- a phenylphosphonic acid metal salt composition containing a thermoplastic resin, a phenylphosphonic acid metal salt, and an excess metal source compound may be mixed with various mixers and kneaded using a single screw or twin screw extruder. Kneading is usually performed at a temperature of about 150 to 220 ° C.
- generating the masterbatch which contains the phenylphosphonic acid metal salt composition containing a phenylphosphonic acid metal salt and an excess metal source compound in high concentration, and adding this to a thermoplastic resin is also possible.
- the phenylphosphonic acid metal salt composition containing a phenylphosphonic acid metal salt and an excess metal source compound can also be added in the polymerization stage of a thermoplastic resin.
- thermoplastic resin composition of the present invention examples thereof include glass fiber, carbon fiber, talc, mica, silica, kaolin, clay, wollastonite, glass beads, crow flakes, potassium titanate, calcium carbonate, magnesium sulfate, titanium oxide and the like.
- the shape of these inorganic fillers may be any of fibrous, granular, plate-like, needle-like, spherical, and powder. These inorganic fillers can be used within 300 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
- thermoplastic resin composition of the present invention A known flame retardant can be used for the thermoplastic resin composition of the present invention.
- halogen flame retardants such as bromine and chlorine
- antimony flame retardants such as antimony trioxide and antimony pentoxide
- inorganic flame retardants such as aluminum hydroxide, magnesium hydroxide and silicone compounds
- red phosphorus and phosphoric acid Phosphorus flame retardants such as esters, ammonium polyphosphate, phosphazene, melamine, melam, melem, melon, melamine cyanurate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate melam melem double salt, alkyl Examples include melamine phosphonate, melamine phenylphosphonate, melamine sulfate, and melamine methanesulfonate flame retardant, and fluororesin such as PTFE.
- These flame retardants can be used within 200 parts by
- heat stabilizers In addition to the above components, heat stabilizers, light stabilizers, UV absorbers, antioxidants, impact modifiers, antistatic agents, pigments, colorants, mold release agents, lubricants, plasticizers, compatibilizers, foaming
- general synthetic resins such as agents, fragrances, antibacterial and antifungal agents, various coupling agents such as silane, titanium, and aluminum, other various fillers, and other crystal nucleating agents Can be used in combination with additives.
- thermoplastic resin composition of the present invention can be applied with molding methods such as general injection molding, blow molding, vacuum molding and compression molding, and various molded products can be easily obtained through these moldings. .
- Synthesis was performed in the same manner as in Synthesis Example 1 except that the amount of phenylphosphonic acid (PPA) and water obtained using water in the amounts shown in Table 1 were used as the phenylphosphonic acid aqueous solution, and zinc phenylphosphonate was included. A white powder of zinc oxide was obtained.
- FIG. 1 shows a scanning microscope (SEM: field emission scanning electron microscope “JSM-7400F” manufactured by JEOL Ltd.) of a white powder of zinc oxide containing zinc phenylphosphonate produced in Synthesis Example 4. Show.
- Table 1 shows the phenylphosphonic acid (PPA) aqueous solution used in Synthesis Examples 1 to 8 and Comparative Synthesis Example 1, and the charged molar ratio of phenylphosphonic acid / zinc oxide.
- Synthesis Example 18 Synthesis was performed in the same manner as in Synthesis Example 17 except that 50% by mass ethanol water was changed to 75% by mass ethanol water, to obtain a zinc oxide white powder containing zinc phenylphosphonate.
- Synthesis was carried out in the same manner as in Synthesis Example 17 except that 50% by mass ethanol water was changed to 90% by mass ethanol water to obtain a zinc oxide white powder containing zinc phenylphosphonate.
- Synthesis was carried out in the same manner as in Synthesis Example 17 except that 50% by mass ethanol water was changed to ethanol, to obtain a zinc oxide white powder containing zinc phenylphosphonate.
- Table 2 shows the phenylphosphonic acid (PPA) aqueous solution and the phenylphosphonic acid / calcium carbonate charge molar ratio used in Synthesis Examples 9 to 16 and Comparative Synthesis Example 2.
- Examples 1 to 8, 30 and 31 To 100 parts by mass of polylactic acid resin [“U'z S-09” manufactured by Toyota Motor Corporation], 1,900 parts by mass of chloroform was added and dissolved to prepare a 5% by mass polylactic acid solution. To this solution (total amount), 1 part by mass of zinc oxide containing zinc phosphonate obtained in Synthesis Examples 1 to 8, 22 and 23 as a nucleating agent was added, sonicated for 30 minutes, and stirred for 3 hours. The nucleating agent was dispersed in the solution by sonicating again for 30 minutes. This solution was cast on a petri dish, and the solvent was removed on a hot plate at 50 ° C. to obtain a polylactic acid film in which the nucleating agent was dispersed.
- the sample was cut into small pieces and subjected to differential scanning calorimetry (DSC) [“ThermoPlus2 DSC8230” manufactured by Rigaku Corporation].
- DSC differential scanning calorimetry
- the temperature was raised to 200 ° C. at 10 ° C./min, held for 5 minutes, and then cooled at 5 ° C./min.
- the crystallization temperature T C was measured from the temperature at the peak of the exothermic peak derived from the crystallization of polylactic acid observed during cooling. The results are shown in Table 3.
- Example 1 A polylactic acid film was obtained in the same manner as in Example 1 except that 1 part by mass of zinc oxide [2 types (JIS standard) manufactured by Hakusui Tech Co., Ltd.] was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 3.
- Example 2 A polylactic acid film was obtained in the same manner as in Example 1 except that 1 part by mass of zinc phenylphosphonate obtained in Comparative Synthesis Example 1 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 3.
- Example 3 A polylactic acid film was obtained in the same manner as in Example 1 except that 0.23 parts by mass of zinc phenylphosphonate obtained in Comparative Synthesis Example 1 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 3.
- Comparative Example 4 Except for using a powder obtained by mixing 0.23 parts by mass of zinc phenylphosphonate obtained in Comparative Synthesis Example 1 and 0.77 parts by mass of zinc oxide [Hux Itec Corp. 2 types (JIS standard)] as a nucleating agent. A polylactic acid film was obtained in the same manner as in Example 1, and the crystallization temperature was measured. The results are shown in Table 3.
- Comparative Example 5 A polylactic acid film was obtained in the same manner as in Example 1 except that the nucleating agent was not added, and the crystallization temperature was measured. The results are shown in Table 3.
- Examples 25 to 29 A polylactic acid film was obtained in the same manner as in Example 1 except that 1 part by mass of zinc oxide containing zinc phenylphosphonate obtained in Synthesis Examples 17 to 21 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 4.
- Example 9 to Example 16 To 100 parts by mass of polylactic acid resin [“U'z S-09” manufactured by Toyota Motor Corporation], 1,900 parts by mass of chloroform was added and dissolved to prepare a 5% by mass polylactic acid solution. To this solution (total amount), 1 part by mass of calcium carbonate containing calcium phenylphosphonate obtained in Synthesis Examples 9 to 16 as a nucleating agent was added, sonicated for 30 minutes, stirred for 3 hours, and again for 30 minutes. The nucleating agent was dispersed in the solution by sonication. This solution was cast on a petri dish, and the solvent was removed on a hot plate at 50 ° C. to obtain a polylactic acid film in which the nucleating agent was dispersed.
- the sample was cut into small pieces and subjected to differential scanning calorimetry (DSC) [“Diamond DSC” manufactured by Perkin Elmer].
- DSC differential scanning calorimetry
- the temperature was raised to 200 ° C. at 10 ° C./min, held for 5 minutes, and then cooled at 5 ° C./min.
- the crystallization temperature T C was measured from the temperature at the peak of the exothermic peak derived from the crystallization of polylactic acid observed during cooling. The results are shown in Table 5.
- Example 6 A polylactic acid film was obtained in the same manner as in Example 9 except that 1 part by mass of calcium carbonate [“Escalon # 2300 (average particle size: 1.7 ⁇ m)” manufactured by Sankyo Flour Milling Co., Ltd.]] was used as the nucleating agent. It was measured. The results are shown in Table 5.
- Example 7 A polylactic acid film was obtained in the same manner as in Example 9 except that 1 part by mass of calcium phenylphosphonate obtained in Comparative Synthesis Example 2 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 5.
- Example 8 A polylactic acid film was obtained in the same manner as in Example 9 except that 0.18 parts by mass of calcium phenylphosphonate obtained in Comparative Synthesis Example 2 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 5.
- a nucleating agent 0.18 part by mass of calcium phenylphosphonate obtained in Comparative Synthesis Example 2 and 0.82 part by mass of calcium carbonate [“Escalon # 2300 (average particle size 1.7 ⁇ m)” manufactured by Sankyo Flour Milling Co., Ltd.]
- a polylactic acid film was obtained in the same manner as in Example 9 except that the mixed powder was used, and the crystallization temperature was measured. The results are shown in Table 5.
- a polylactic acid film was obtained in the same manner as in Example 9 except that the nucleating agent was not added, and the crystallization temperature was measured. The results are shown in Table 5.
- Examples 17 to 24 1 part by mass of calcium carbonate containing calcium phenylphosphonate obtained in Synthesis Examples 9 to 16 as a nucleating agent was added to 100 parts by mass of isotactic polypropylene [“NOVATEC MA3” manufactured by Nippon Polypro Co., Ltd.] ) The nucleating agent was dispersed in the polypropylene resin by melt-kneading for 5 minutes at 185 ° C. using “Lab plast mill ⁇ ” manufactured by Toyo Seiki Seisakusho. The sample was cut into small pieces and subjected to differential scanning calorimetry (DSC) [“Diamond DSC” manufactured by Perkin Elmer]. In the measurement, the temperature was raised to 200 ° C.
- DSC differential scanning calorimetry
- Example 11 A polypropylene sample was obtained in the same manner as in Example 17 except that 1 part by mass of calcium carbonate [“Escalon # 2300 (average particle size 1.7 ⁇ m)” manufactured by Sankyo Flour Milling Co., Ltd.]] was used as a nucleating agent, and the crystallization temperature was measured. did. The results are shown in Table 6.
- Example 12 A polypropylene sample was obtained in the same manner as in Example 17 except that 1 part by mass of calcium phenylphosphonate obtained in Comparative Synthesis Example 2 was used as a nucleating agent, and the crystallization temperature was measured. The results are shown in Table 6.
- zinc oxide containing zinc phenylphosphonate (FIG. 1) and calcium carbonate containing calcium phenylphosphonate (FIG. 3) obtained by the production method of the present invention. Is much smaller than zinc phenylphosphonate (FIG. 2) and calcium phenylphosphonate (FIG. 4) obtained by reacting a conventional phenylphosphonic acid compound with an equivalent metal salt or metal oxide. It was confirmed to have a shape.
- polylactic acid films (Examples 1 to 8) using zinc oxide white powder containing zinc phenylphosphonate obtained by the production method of the present invention, calcium phenylphosphonate
- the polylactic acid films (Examples 9 to 16) using the white powder of calcium carbonate containing, or the polypropylene samples (Examples 17 to 24) were compared with each other when compared with the substantial content of zinc phenylphosphonate or calcium phenylphosphonate. Even when the content was the same as or less than that of the example, the crystallization temperature was higher than that of the comparative example.
- polylactic acid films (Examples 25 to 27, 29) using zinc oxide white powder containing zinc phenylphosphonate obtained using ethanol water or methanol water as the solvent during synthesis are also higher than the comparative examples.
- the crystallization temperature was shown to be comparable to that of the comparative example.
- a polylactic acid film Comparative Example 4 or Comparative Example 9
- a polypropylene sample Comparative Example 14
- the production method of the present invention can provide a crystal nucleating agent with high productivity while reducing petroleum-derived components (eg, phenylphosphonic acid). Therefore, a composition containing phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide (metal salt, metal oxide or metal hydroxide in which phenylphosphonic acid metal salt is dispersed) is crystal nucleus.
- phenylphosphonic acid metal salt and surplus metal salt, surplus metal oxide or surplus metal hydroxide metal salt, metal oxide or metal hydroxide in which phenylphosphonic acid metal salt is dispersed
- it can be expected to increase the crystallization speed of the thermoplastic resin and provide a thermoplastic resin composition having excellent heat resistance and molding processability.
- JP-A-8-3432 Japanese Patent Laid-Open No. 10-87975 JP-A-10-158369 JP 2003-192883 A International Publication No. 2005/97894 Pamphlet JP 58-108249 A Japanese Patent Laid-Open No. 46-21939
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Abstract
Description
こうしたポリ乳酸樹脂やポリオレフィン樹脂をはじめとする熱可塑性樹脂の成形加工性や耐熱性を改善するにあたり、該樹脂の結晶化速度及び結晶化度を高める試みがなされており、その方法の一つとして、例えば結晶核剤を添加する方法が知られている。結晶核剤とは、結晶性高分子の一次結晶核となり結晶成長を促進し、その結果、結晶サイズを微細化すると共に、結晶化速度を高める働きをする。
またブロック共重合ポリ(エーテルエステル)の結晶核剤として、ホスホン酸、亜ホスホン酸などの金属塩が有効であることが知られている(特許文献6)。
さらにポリオレフィン用の結晶核剤として、例えば、安息香酸ナトリウム、4-tert-ブチル安息香酸アルミニウム、アジピン酸ナトリウム、ビシクロ[2.2.1]ヘプタン-2,3-ジカルボン酸ナトリウム等のカルボン酸金属塩;ナトリウムビス(4-tert-ブチルフェニル)ホスフェート、ナトリウム2,2'-メチレンビス(4,6-ジ-tert-ブチルフェニル)ホスフェート等のリン酸エステル金属塩;ジベンジリデンソルビトール、ビス(メチルベンジリデン)ソルビトール、ビス(ジメチルベンジリデン)ソルビトールなどの多価アルコール誘導体等;芳香族ホスホン酸、芳香族亜ホスホン酸等の金属塩(特許文献7)などが提案されている。
また上記結晶核剤の中でも優れた性能を有するとされているリン化合物の金属塩(例えばフェニルホスホン酸金属塩)を採用した場合に、環境負荷を低減させるため、結晶核剤中に含まれる有機成分含量(すなわちフェニルホスホン酸の含有量)を下げることも望まれている。
さらに本発明は上記製造方法によって生成されたフェニルホスホン酸金属塩を含む組成物、該フェニルホスホン酸金属塩組成物よりなる結晶核剤、並びに、該フェニルホスホン酸金属塩組成物と熱可塑性樹脂とを含む熱可塑性樹脂組成物を提供することを目的とする。
第2観点として、前記金属塩、金属酸化物又は金属水酸化物(b)に対し難溶性である溶媒中で前記フェニルホスホン酸化合物(a)と前記金属塩、金属酸化物又は金属水酸化物(b)とを反応させることを特徴とする、第1観点に記載の製造方法に関する。
第3観点として、反応原料の前記金属塩、金属酸化物又は金属水酸化物(b)とフェニルホスホン酸化合物(a)をモル比で100:0.01乃至100:90にて反応させることを特徴とする、第1観点又は第2観点に記載の製造方法に関する。
第4観点として、前記金属塩、金属酸化物又は金属水酸化物(b)の金属種が亜鉛、カルシウム又はマンガンである、第1観点乃至第3観点のうち何れか一項に記載の製造方法に関する。
第5観点として、前記金属塩、金属酸化物又は金属水酸化物(b)の金属種が亜鉛又はカルシウムである、第4観点に記載の製造方法に関する。
第6観点として、前記金属塩、金属酸化物又は金属水酸化物(b)が酸化亜鉛又は炭酸カルシウムである、第5観点に記載の製造方法に関する。
第7観点として、第1観点乃至第6観点のうち何れか一項に記載の製造方法により生成されたフェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物を含むフェニルホスホン酸金属塩組成物に関する。
第8観点として、前記フェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物における金属種が亜鉛である、第7観点に記載のフェニルホスホン酸金属塩組成物に関する。
第9観点として、前記フェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物における金属種がカルシウムである、第7観点に記載のフェニルホスホン酸金属塩組成物に関する。
第10観点として、第7観点乃至第9観点のうち何れか一項に記載のフェニルホスホン酸金属塩組成物からなる結晶核剤に関する。
第11観点として、第7観点乃至第9観点のうち何れか一項に記載のフェニルホスホン酸金属塩組成物及び熱可塑性樹脂を含む熱可塑性樹脂組成物に関する。
第12観点として、前記熱可塑性樹脂100質量部に対し、第7観点乃至第9観点のうち何れか一項に記載のフェニルホスホン酸金属塩組成物を0.01乃至10質量部含む、第11観点に記載の熱可塑性樹脂組成物に関する。
第13観点として、前記熱可塑性樹脂がポリ乳酸樹脂である、第11観点又は第12観点に記載の熱可塑性樹脂組成物に関する。
第14観点として、前記フェニルホスホン酸金属塩組成物が第8観点に記載のフェニルホスホン酸金属塩組成物である、第13観点に記載の熱可塑性樹脂組成物に関する。
第15観点として、前記熱可塑性樹脂がポリプロピレン、ポリプロピレンコポリマー、ポリエチレン、ポリエチレンコポリマー、ポリブチレン及びポリ(4-メチル-1-ペンテン)からなる群から選択される、第11観点又は第12観点に記載の熱可塑性樹脂組成物に関する。
第16観点として、前記フェニルホスホン酸金属塩組成物が第9観点に記載のフェニルホスホン酸金属塩組成物である、第15観点に記載の熱可塑性樹脂組成物に関する。
すなわち、本発明の製造方法は、さらなる粉砕等の工程を必要とすることなく、従来の製造方法に従うよりも格段により微小な形状を有するフェニルホスホン酸金属塩を製造できる。なお、従来の製造方法に比べより微小な形状で得られる理由については定かではないが、例えば、媒体中の金属源化合物粒子の表面付近又はそれ以外で生成したフェニルホスホン酸金属塩が、金属源化合物粒子の表面で結晶化し、その一部又は全部が剥がれ落ちることで、より微小な形状で得られると考えられる。
以下、本発明についてさらに詳しく説明する。
これら化合物は市販品をそのまま好適に使用できる。
金属塩、金属酸化物又は金属水酸化物で使用される金属としては、1価、2価及び3価の金属を使用することが出来る。該金属においてこれらの金属は、2種以上の金属を混合して使用することもできる。金属種の具体例としては、リチウム、ナトリウム、カリウム、マグネシウム、アルミニウム、カルシウム、バリウム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛等が挙げられる。中でも金属種として、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、バリウム、マンガン、鉄、コバルト、銅及び亜鉛が好ましく、特に亜鉛又はカルシウムであることが好ましく、具体的には酸化亜鉛又は炭酸カルシウムであることが好ましい。
これら金属源化合物、すなわち、金属塩、金属酸化物又は金属水酸化物もまた、市販品をそのまま好適に使用できる。
ここで用いられる媒体としては特に限定されないが、反応効率の面から原料であるフェニルホスホン酸化合物が可溶であることが好ましい。また、最終的な生成物を回収することを考慮すると、原料となる金属源化合物、及びフェニルホスホン酸金属塩が難溶である溶媒が好ましい。
このような溶媒としては、例えば水;アセトン、メチルエチルケトン、メチルイソブチルケトンなどのケトン類;アセトニトリルなどのニトリル類;テトラヒドロフランなどのエーテル類;メタノール、エタノール、1-プロパノール、2-プロパノールなどのアルコール類;N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドンなどのアミド類;ジメチルスルホキシドなどのスルホキシド類等を挙げることができる。これら溶媒は、1種を単独で使用しても、2種以上を混合して使用してもよい。これらの中でも水、アルコール類が好ましく、取扱いの容易さや経済性を考慮すると水を使用することがより好ましい。
なお、媒体を使用せずに、前記フェニルホスホン酸化合物(a)及び前記金属源化合物(b)を混合することも可能であるが、その場合、反応の進行が極端に遅くなり工業的に不利となる。一方、使用する媒体量が多すぎる場合には容積効率が悪くなり、やはり工業的に不利となる。
また、反応装置としては、撹拌翼を装備した反応槽の他、ホモミキサー、ヘンシェルミキサー、レーディゲミキサーなどの各種混合機、ボールミル、ビーズミル、アルティマイザーなどの各種粉砕機等、反応系を十分に流動させられる装置であれば特に限定されず使用することができる。中でも粉体の混合能力に優れ、かつ混合、加熱等が同時又は順次に行える混合機、例えばヘンシェルミキサーやレーディゲミキサー等を使用した場合、反応に使用する媒体量を大幅に削減することが可能となり、容積効率の向上が図れるだけでなく、反応及び後述の乾燥を同一装置で行え、工業的に有利となる。
生成するフェニルホスホン酸金属塩が、余剰となった原料の金属源化合物に均一に分散した粉末を得るためには、前記スラリー、前記金属源化合物又は前記混合物を撹拌翼などで撹拌しながら、前記溶液又は前記溶媒を滴下又は一括で添加するのが好ましい。
なお、このときの反応温度は、生成されるフェニルホスホン酸金属塩の大きさに影響を及ぼし得る。すなわち、反応温度が高温になるほど、析出したフェニルホスホン酸金属塩の溶解度が高まることとなり、これは再結晶時のサイズの増大につながる。従って、微小な形状のフェニルホスホン酸金属塩を得る本発明の目的の達成のためには、上記反応の温度は30℃以下に保つことが望ましい。
このときの乾燥温度としては、媒体の種類によって適宜選択でき、また、減圧条件を適用してもよい。
媒体として水を用いた場合、乾燥温度は常圧では100乃至500℃であることが好ましく、より好ましくは120乃至200℃である。100℃より低い温度では結晶水を除去しきれず、フェニルホスホン酸金属塩の一水和物の形態をとり、加水分解を嫌う樹脂(例えばポリエステル樹脂等)の結晶核剤としては適さないことから好ましくない。また500℃より高い温度では、フェニルホスホン酸金属塩の分解を誘発する虞がある。
上記熱可塑性樹脂としては汎用の熱可塑性樹脂、汎用の熱可塑性エンジニアリングプラスチック、ポリ乳酸樹脂をはじめとする生分解性樹脂等を挙げることができる。
汎用のエンジニアリングプラスチックの例としては、ポリアミド樹脂、ポリカーボネート樹脂、ポリフェニレンエーテル樹脂、変性ポリフェニレンエーテル樹脂、ポリエチレンテレフタレート(PET)又はポリブチレンテレフタレート(PBT)などのポリエステル樹脂、ポリアセタール樹脂、ポリスルホン樹脂、ポリフェニレンサルファイド樹脂、ポリイミド樹脂などが挙げられる。
ポリ乳酸樹脂としては特に限定されるものではないが、例えばラクチドを開環重合させたものや、乳酸のD体、L体、ラセミ体などを直接重縮合させたものが挙げられる。ポリ乳酸樹脂の数平均分子量は、一般に10,000から500,000程度である。またポリ乳酸樹脂を熱、光、放射線などを利用して架橋剤で架橋させたものも使用できる。
撹拌機を装備した300ml容量の反応フラスコに、酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]10.0g(123mmol)と、水90.0gを仕込み、酸化亜鉛の水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]13.6g(86mmol)を水77.0gに溶解した水溶液をゆっくりと滴下し、1時間反応させた。その後、スラリーを濾過し、ウェットケーキを水で充分に洗い流した。その後、120℃で12時間以上乾燥することで、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
フェニルホスホン酸水溶液として、表1に記載の量のフェニルホスホン酸(PPA)及び水を用いて得られたものを使用した以外は、合成例1と同様に合成を行い、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
なお、合成例4で製造したフェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末の走査型顕微鏡(SEM:日本電子(株)製、電界放出形走査電子顕微鏡「JSM-7400F」)像を図1に示す。
撹拌機を装備した300ml容量の反応フラスコに、酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]10.0g(123mmol)と、水90.0gを仕込み、酸化亜鉛の水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]19.4g(123mmol)を水110.0gに溶解した水溶液をゆっくりと滴下し5時間反応させた。その後、スラリーを濾過し、ウェットケーキを水で充分に洗い流した。その後、120℃で12時間以上乾燥することで、フェニルホスホン酸亜鉛の白色粉末を得た。なお、得られたフェニルホスホン酸亜鉛の白色粉末の走査型顕微鏡(SEM:日本電子(株)製、電界放出形走査電子顕微鏡「JSM-7400F」)像を図2に示す。
撹拌機を装備した300ml容量の反応フラスコに、酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]10.0g(123mmol)と、50質量%エタノール水90.0gを仕込み、酸化亜鉛のエタノール水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]1.9g(12mmol)を50質量%エタノール水11.0gに溶解した溶液をゆっくりと滴下し、1時間反応させた。その後、スラリーを濾過し、ウェットケーキをエタノールで充分に洗い流した。その後、120℃で12時間以上乾燥することで、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
50質量%エタノール水を75質量%エタノール水に変更した以外は合成例17と同様に合成を行い、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
50質量%エタノール水を90質量%エタノール水に変更した以外は合成例17と同様に合成を行い、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
50質量%エタノール水をエタノールに変更した以外は合成例17と同様に合成を行い、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
撹拌機を装備した300ml容量の反応フラスコに、酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]10.0g(123mmol)と、50質量%メタノール水90.0gを仕込み、酸化亜鉛のメタノール水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]1.9g(12mmol)を50質量%メタノール水11.0gに溶解した溶液をゆっくりと滴下し、1時間反応させた。その後、スラリーを濾過し、ウェットケーキをメタノールで充分に洗い流した。その後、120℃で12時間以上乾燥することで、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
レーディゲミキサー[レーディゲ社製、M-20型(全容量20L)]に、酸化亜鉛粉末[ハクスイテック(株)製 2種(JIS規格)]5.67kg(70mol)、及びフェニルホスホン酸粉末[日産化学工業(株)製]1.11kg(7mol)を投入した。これらの粉末を混合しているところへ水0.72kgを1分間かけて噴霧し(全混合物中の固形分濃度90質量%)、さらに5分間混合した。その後、装置外層のジャケットに150℃のスチームを流しながら混合を続け90分間乾燥することで、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
レーディゲミキサー[レーディゲ社製、M-20型(全容量20L)]に、酸化亜鉛粉末[ハクスイテック(株)製 2種(JIS規格)]8.51kg(105mol)を投入した。そこへフェニルホスホン酸[日産化学工業(株)製]1.67kg(10.5mol)を水9.43kgに溶解させた水溶液を加え(全混合物中の固形分濃度52質量%)、これらの混合物を5分間混合した。その後、装置外層のジャケットに150℃のスチームを流しながら混合を続け60分間乾燥し、さらに減圧し70分間乾燥することで、フェニルホスホン酸亜鉛を含む酸化亜鉛の白色粉末を得た。
撹拌機を装備した300ml容量の反応フラスコに、炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]10.0g(100mmol)と、水90.0gを仕込み、炭酸カルシウムの水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]11.1g(70mmol)を水62.7gに溶解した水溶液をゆっくりと滴下し1時間反応させた。その後、スラリーを濾過し、ウェットケーキを水で充分に洗い流した。その後、200℃で12時間以上乾燥することで、フェニルホスホン酸カルシウムを含む炭酸カルシウムの白色粉末を得た。
フェニルホスホン酸水溶液として、表2に記載の量のフェニルホスホン酸(PPA)及び水を用いて得られたものを使用した以外は、合成例9と同様に合成を行い、フェニルホスホン酸カルシウムを含む炭酸カルシウムの白色粉末を得た。
なお、合成例12で製造したフェニルホスホン酸カルシウムを含む炭酸カルシウムの白色粉末の走査型顕微鏡(SEM:日本電子(株)製、電界放出形走査電子顕微鏡「JSM-7400F」)像を図3に示す。
撹拌機を装備した300ml容量の反応フラスコに、炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]10.0g(100mmol)と、水90.0gを仕込み、炭酸カルシウムの水スラリーを調製した。このスラリーに撹拌下、室温(およそ25℃)で、フェニルホスホン酸[日産化学工業(株)製]15.8g(100mmol)を水89.5gに溶解した水溶液をゆっくりと滴下し1時間反応させた。その後、スラリーを濾過し、ウェットケーキを水で充分に洗い流した。その後、200℃で12時間以上乾燥することで、フェニルホスホン酸カルシウムの白色粉末を得た。なお、得られたフェニルホスホン酸カルシウムの白色粉末の走査型顕微鏡(SEM:日本電子(株)製、電界放出形走査電子顕微鏡「JSM-7400F」)像を図4に示す。
ポリ乳酸樹脂[トヨタ自動車(株)製「U’z S-09」]100質量部に対し、クロロホルム1,900質量部を加えて溶解させ、5質量%ポリ乳酸溶液を調製した。この溶液(全量)に対し、核剤として合成例1乃至8、22及び23で得られたフェニルホスホン酸亜鉛を含む酸化亜鉛を1質量部加え、30分間超音波処理し、3時間撹拌した後、再度30分間超音波処理を施すことで核剤を溶液に分散させた。この溶液をシャーレ上にキャストし、ホットプレート上50℃で溶媒を除去し、核剤が分散されたポリ乳酸フィルムを得た。このサンプルを小片に切り取り、示差走査熱量測定(DSC)[(株)リガク製「ThermoPlus2 DSC8230」]を行った。測定は、10℃/分で200℃まで昇温し、そのまま5分間保持し、その後5℃/分で冷却した。冷却時に観測されるポリ乳酸の結晶化に由来する発熱ピーク頂点の温度から結晶化温度TCを測定した。結果を表3に示す。
核剤として酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]を1質量部用いた以外は実施例1と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表3に示す。
[比較例2]
核剤として比較合成例1で得られたフェニルホスホン酸亜鉛を1質量部用いた以外は実施例1と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表3に示す。
[比較例3]
核剤として比較合成例1で得られたフェニルホスホン酸亜鉛を0.23質量部用いた以外は実施例1と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表3に示す。
[比較例4]
核剤として比較合成例1で得られたフェニルホスホン酸亜鉛0.23質量部と酸化亜鉛[ハクスイテック(株)製 2種(JIS規格)]0.77質量部を混合した粉末を用いた以外は実施例1と同様ポリ乳酸フィルムを得、結晶化温度を測定した。結果を表3に示す。
[比較例5]
核剤を加えなかったこと以外は実施例1と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表3に示す。
核剤として合成例17乃至21で得られたフェニルホスホン酸亜鉛を含む酸化亜鉛を1質量部用いた以外は実施例1と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表4に示す。
ポリ乳酸樹脂[トヨタ自動車(株)製「U'z S-09」]100質量部に対し、クロロホルム1,900質量部を加え溶解させ、5質量%ポリ乳酸溶液を調製した。この溶液(全量)に対し、核剤として合成例9乃至16で得られたフェニルホスホン酸カルシウムを含む炭酸カルシウムを1質量部加え、30分間超音波処理し、3時間撹拌した後、再度30分間超音波処理を施すことで核剤を溶液に分散させた。この溶液をシャーレ上にキャストし、ホットプレート上50℃で溶媒を除去し、核剤が分散されたポリ乳酸フィルムを得た。このサンプルを小片に切り取り、示差走査熱量測定(DSC)[パーキンエルマー製「Diamond DSC」]を行った。測定は、10℃/分で200℃まで昇温し、そのまま5分間保持し、その後5℃/分で冷却した。冷却時に観測されるポリ乳酸の結晶化に由来する発熱ピーク頂点の温度から結晶化温度TCを測定した。結果を表5に示す。
核剤として炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]を1質量部用いた以外は実施例9と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表5に示す。
[比較例7]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウムを1質量部用いた以外は実施例9と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表5に示す。
[比較例8]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウムを0.18質量部用いた以外は実施例9と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表5に示す。
[比較例9]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウム0.18質量部と炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]0.82質量部を混合した粉末を用いた以外は実施例9と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表5に示す。
[比較例10]
核剤を加えなかったこと以外は実施例9と同様にポリ乳酸フィルムを得、結晶化温度を測定した。結果を表5に示す。
アイソタクチックポリプロピレン[日本ポリプロ(株)製「NOVATEC MA3」]100質量部に対し、核剤として合成例9乃至16で得られたフェニルホスホン酸カルシウムを含む炭酸カルシウムを1質量部加え、(株)東洋精機製作所製「ラボプラストミルμ」を用いて185℃で5分間溶融混練することにより、ポリプロピレン樹脂中に核剤を分散させた。このサンプルを小片に切り取り、示差走査熱量測定(DSC)[パーキンエルマー製「Diamond DSC」]を行った。測定は、10℃/分で200℃まで昇温し、そのまま5分間保持し、その後5℃/分で冷却した。冷却時に観測されるポリプロピレンの結晶化に由来する発熱ピーク頂点の温度から結晶化温度TCを測定した。結果を表6に示す。
核剤として炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]を1質量部用いた以外は実施例17と同様にポリプロピレンサンプルを得、結晶化温度を測定した。結果を表6に示す。
[比較例12]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウムを1質量部用いた以外は実施例17と同様にポリプロピレンサンプルを得、結晶化温度を測定した。結果を表6に示す。
[比較例13]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウムを0.18質量部用いた以外は実施例17と同様にポリプロピレンサンプルを得、結晶化温度を測定した。結果を表6に示す。
[比較例14]
核剤として比較合成例2で得られたフェニルホスホン酸カルシウム0.18質量部と炭酸カルシウム[三共製粉(株)製「エスカロン #2300(平均粒径 1.7μm)」]0.82質量部を混合した粉末を用いた以外は実施例17と同様にポリプロピレンサンプルを得、結晶化温度を測定した。結果を表6に示す。
[比較例15]
核剤を加えなかったこと以外は実施例17と同様にポリプロピレンサンプルを得、結晶化温度を測定した。結果を表6に示す。
また、単にフェニルホスホン酸金属塩と金属塩又は金属酸化物を混合した粉末を用いてポリ乳酸フィルム(比較例4又は比較例9)又はポリプロピレンサンプル(比較例14)を製造しても、本発明の製造方法で得られたフェニルホスホン酸金属塩を含む金属塩又は金属酸化物(実施例4、12、20)の結晶化温度には及ばないとする結果が得られた。
すなわち、これら実施例に用いたフェニルホスホン酸亜鉛を含む酸化亜鉛、或いは、フェニルホスホン酸カルシウムを含む炭酸カルシウムは、結晶核剤として従来のフェニルホスホン酸化合物とその当量の金属塩又は金属酸化物と反応させて得られた化合物と比べて優れた性能を持つとする結果が得られた。
したがって、フェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物を含む組成物(フェニルホスホン酸金属塩が分散した金属塩、金属酸化物又は金属水酸化物)を結晶核剤として添加することにより、熱可塑性樹脂の結晶化速度を高め、耐熱性、成形加工性に優れた熱可塑性樹脂組成物を提供することが期待できる。
Claims (16)
- 前記金属塩、金属酸化物又は金属水酸化物(b)に対し難溶性である溶媒中で前記フェニルホスホン酸化合物(a)と前記金属塩、金属酸化物又は金属水酸化物(b)とを反応させることを特徴とする、請求項1に記載の製造方法。
- 反応原料の前記金属塩、金属酸化物又は金属水酸化物(b)とフェニルホスホン酸化合物(a)をモル比で100:0.01乃至100:90にて反応させることを特徴とする、請求項1又は請求項2に記載の製造方法。
- 前記金属塩、金属酸化物又は金属水酸化物(b)の金属種が亜鉛、カルシウム又はマンガンである、請求項1乃至請求項3のうち何れか一項に記載の製造方法。
- 前記金属塩、金属酸化物又は金属水酸化物(b)の金属種が亜鉛又はカルシウムである、請求項4に記載の製造方法。
- 前記金属塩、金属酸化物又は金属水酸化物(b)が酸化亜鉛又は炭酸カルシウムである、請求項5に記載の製造方法。
- 請求項1乃至請求項6のうち何れか一項に記載の製造方法により生成されたフェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物を含むフェニルホスホン酸金属塩組成物。
- 前記フェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物における金属種が亜鉛である、請求項7に記載のフェニルホスホン酸金属塩組成物。
- 前記フェニルホスホン酸金属塩及び余剰金属塩、余剰金属酸化物又は余剰金属水酸化物における金属種がカルシウムである、請求項7に記載のフェニルホスホン酸金属塩組成物。
- 請求項7乃至請求項9のうち何れか一項に記載のフェニルホスホン酸金属塩組成物からなる結晶核剤。
- 請求項7乃至請求項9のうち何れか一項に記載のフェニルホスホン酸金属塩組成物及び熱可塑性樹脂を含む熱可塑性樹脂組成物。
- 前記熱可塑性樹脂100質量部に対し、請求項7乃至請求項9のうち何れか一項に記載のフェニルホスホン酸金属塩組成物を0.01乃至10質量部含む、請求項11に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂がポリ乳酸樹脂である、請求項11又は請求項12に記載の熱可塑性樹脂組成物。
- 前記フェニルホスホン酸金属塩組成物が請求項8に記載のフェニルホスホン酸金属塩組成物である、請求項13に記載の熱可塑性樹脂組成物。
- 前記熱可塑性樹脂がポリプロピレン、ポリプロピレンコポリマー、ポリエチレン、ポリエチレンコポリマー、ポリブチレン及びポリ(4-メチル-1-ペンテン)からなる群から選択される、請求項11又は請求項12に記載の熱可塑性樹脂組成物。
- 前記フェニルホスホン酸金属塩組成物が請求項9に記載のフェニルホスホン酸金属塩組成物である、請求項15に記載の熱可塑性樹脂組成物。
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JP2018506623A (ja) * | 2015-01-26 | 2018-03-08 | ランクセス ソリューションズ ユーエス インコーポレイテッド | 熱処理したリン化合物およびメラムを含む難燃性ポリマー組成物 |
CN106280337A (zh) * | 2015-03-18 | 2017-01-04 | 中广核三角洲(苏州)新材料研发有限公司 | 用于快速成型的高耐热聚乳酸材料 |
WO2017135189A1 (ja) * | 2016-02-01 | 2017-08-10 | 日産化学工業株式会社 | フェニルホスホン酸化合物の金属塩を含むポリアミド樹脂組成物 |
JPWO2017135189A1 (ja) * | 2016-02-01 | 2018-11-22 | 日産化学株式会社 | フェニルホスホン酸化合物の金属塩を含むポリアミド樹脂組成物 |
CN113956640A (zh) * | 2021-12-15 | 2022-01-21 | 中化泉州能源科技有限责任公司 | 一种生物降解pla薄膜及其制备方法 |
CN113956640B (zh) * | 2021-12-15 | 2023-02-21 | 中化泉州能源科技有限责任公司 | 一种生物降解pla薄膜及其制备方法 |
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KR20120079085A (ko) | 2012-07-11 |
TW201124424A (en) | 2011-07-16 |
EP2479181B1 (en) | 2016-04-20 |
TWI488859B (zh) | 2015-06-21 |
EP2479181A4 (en) | 2014-01-15 |
JPWO2011030822A1 (ja) | 2013-02-07 |
EP2479181A1 (en) | 2012-07-25 |
JP5761519B2 (ja) | 2015-08-12 |
KR101763646B1 (ko) | 2017-08-01 |
CN102482303B (zh) | 2015-07-22 |
CN102482303A (zh) | 2012-05-30 |
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