JP2011048926A - Wire coating material - Google Patents
Wire coating material Download PDFInfo
- Publication number
- JP2011048926A JP2011048926A JP2009194209A JP2009194209A JP2011048926A JP 2011048926 A JP2011048926 A JP 2011048926A JP 2009194209 A JP2009194209 A JP 2009194209A JP 2009194209 A JP2009194209 A JP 2009194209A JP 2011048926 A JP2011048926 A JP 2011048926A
- Authority
- JP
- Japan
- Prior art keywords
- polyester composition
- thermoplastic polyester
- dimer diol
- dicarboxylic acid
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 24
- 239000011248 coating agent Substances 0.000 title claims abstract description 14
- 238000000576 coating method Methods 0.000 title claims abstract description 14
- 229920000728 polyester Polymers 0.000 claims abstract description 90
- 239000000203 mixture Substances 0.000 claims abstract description 66
- 239000000539 dimer Substances 0.000 claims abstract description 44
- 150000002009 diols Chemical class 0.000 claims abstract description 44
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 18
- 230000014759 maintenance of location Effects 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims abstract 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 230000000717 retained effect Effects 0.000 claims 1
- 230000007062 hydrolysis Effects 0.000 abstract description 9
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 9
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000000806 elastomer Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 229920001169 thermoplastic Polymers 0.000 description 38
- 239000004416 thermosoftening plastic Substances 0.000 description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 37
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 32
- -1 polybutylene terephthalate Polymers 0.000 description 23
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 18
- 235000019589 hardness Nutrition 0.000 description 18
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 17
- 238000006068 polycondensation reaction Methods 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 14
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 150000003609 titanium compounds Chemical class 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 7
- 238000005809 transesterification reaction Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 125000005907 alkyl ester group Chemical group 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 235000019256 formaldehyde Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- HPCCWDVOHHFCKM-UHFFFAOYSA-M lithium;hydrogen sulfate Chemical compound [Li+].OS([O-])(=O)=O HPCCWDVOHHFCKM-UHFFFAOYSA-M 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical compound OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 235000016337 monopotassium tartrate Nutrition 0.000 description 2
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- KYKNRZGSIGMXFH-ZVGUSBNCSA-M potassium bitartrate Chemical compound [K+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O KYKNRZGSIGMXFH-ZVGUSBNCSA-M 0.000 description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- IZUPJOYPPLEPGM-UHFFFAOYSA-M sodium;hydron;phthalate Chemical compound [Na+].OC(=O)C1=CC=CC=C1C([O-])=O IZUPJOYPPLEPGM-UHFFFAOYSA-M 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RQALKBLYTUKBFV-UHFFFAOYSA-N 1,4-dioxa-7-thiaspiro[4.4]nonane Chemical compound O1CCOC11CSCC1 RQALKBLYTUKBFV-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 1
- JXPHLUCMHXXHEJ-UHFFFAOYSA-N 2-(aminomethyl)-4-bromoaniline Chemical compound NCC1=CC(Br)=CC=C1N JXPHLUCMHXXHEJ-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- JTNCEQNHURODLX-UHFFFAOYSA-N 2-phenylethanimidamide Chemical compound NC(=N)CC1=CC=CC=C1 JTNCEQNHURODLX-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- WVDRSXGPQWNUBN-UHFFFAOYSA-N 4-(4-carboxyphenoxy)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C=C1 WVDRSXGPQWNUBN-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- MOMKYJPSVWEWPM-UHFFFAOYSA-N 4-(chloromethyl)-2-(4-methylphenyl)-1,3-thiazole Chemical compound C1=CC(C)=CC=C1C1=NC(CCl)=CS1 MOMKYJPSVWEWPM-UHFFFAOYSA-N 0.000 description 1
- NTJPVVKEZMOHNU-UHFFFAOYSA-N 6-(oxan-4-yl)-1h-indazole Chemical compound C1COCCC1C1=CC=C(C=NN2)C2=C1 NTJPVVKEZMOHNU-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CBOCVOKPQGJKKJ-UHFFFAOYSA-L Calcium formate Chemical compound [Ca+2].[O-]C=O.[O-]C=O CBOCVOKPQGJKKJ-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- KJLDTYUGZVCMRD-UHFFFAOYSA-L [dodecanoyloxy(diphenyl)stannyl] dodecanoate Chemical compound C=1C=CC=CC=1[Sn+2]C1=CC=CC=C1.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O KJLDTYUGZVCMRD-UHFFFAOYSA-L 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
- 235000020661 alpha-linolenic acid Nutrition 0.000 description 1
- 235000011126 aluminium potassium sulphate Nutrition 0.000 description 1
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- NXMNIHPHNSDPTN-UHFFFAOYSA-N didodecyl(oxo)tin Chemical compound CCCCCCCCCCCC[Sn](=O)CCCCCCCCCCCC NXMNIHPHNSDPTN-UHFFFAOYSA-N 0.000 description 1
- CSNCOKSAYUDNIE-UHFFFAOYSA-N diethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OCC)C=CC2=CC(C(=O)OCC)=CC=C21 CSNCOKSAYUDNIE-UHFFFAOYSA-N 0.000 description 1
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- VNSVQJIXVXZDJF-UHFFFAOYSA-L dilithium;phthalate Chemical compound [Li+].[Li+].[O-]C(=O)C1=CC=CC=C1C([O-])=O VNSVQJIXVXZDJF-UHFFFAOYSA-L 0.000 description 1
- DOFDKNLHJKJCMO-UHFFFAOYSA-N diphenyl naphthalene-2,6-dicarboxylate Chemical compound C=1C=C2C=C(C(=O)OC=3C=CC=CC=3)C=CC2=CC=1C(=O)OC1=CC=CC=C1 DOFDKNLHJKJCMO-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
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- UZLGHNUASUZUOR-UHFFFAOYSA-L dipotassium;3-carboxy-3-hydroxypentanedioate Chemical compound [K+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O UZLGHNUASUZUOR-UHFFFAOYSA-L 0.000 description 1
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- GOMCKELMLXHYHH-UHFFFAOYSA-L dipotassium;phthalate Chemical compound [K+].[K+].[O-]C(=O)C1=CC=CC=C1C([O-])=O GOMCKELMLXHYHH-UHFFFAOYSA-L 0.000 description 1
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 description 1
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- CEYULKASIQJZGP-UHFFFAOYSA-L disodium;2-(carboxymethyl)-2-hydroxybutanedioate Chemical compound [Na+].[Na+].[O-]C(=O)CC(O)(C(=O)O)CC([O-])=O CEYULKASIQJZGP-UHFFFAOYSA-L 0.000 description 1
- HQWKKEIVHQXCPI-UHFFFAOYSA-L disodium;phthalate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C([O-])=O HQWKKEIVHQXCPI-UHFFFAOYSA-L 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
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- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
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- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
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- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
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- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 1
- WAHQBNXSPALNEA-UHFFFAOYSA-L lithium succinate Chemical compound [Li+].[Li+].[O-]C(=O)CCC([O-])=O WAHQBNXSPALNEA-UHFFFAOYSA-L 0.000 description 1
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- ZPPPLBXXTCVBNC-ZVGUSBNCSA-M lithium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Li+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O ZPPPLBXXTCVBNC-ZVGUSBNCSA-M 0.000 description 1
- ZOTSUVWAEYHZRI-JJKGCWMISA-M lithium;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanoate Chemical compound [Li+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O ZOTSUVWAEYHZRI-JJKGCWMISA-M 0.000 description 1
- ZPPPLBXXTCVBNC-UHFFFAOYSA-M lithium;2,3-dihydroxybutanedioate;hydron Chemical compound [H+].[Li+].[O-]C(=O)C(O)C(O)C([O-])=O ZPPPLBXXTCVBNC-UHFFFAOYSA-M 0.000 description 1
- LJURPJZOPVZKTQ-UHFFFAOYSA-M lithium;2-carboxybenzoate Chemical compound [Li+].OC(=O)C1=CC=CC=C1C([O-])=O LJURPJZOPVZKTQ-UHFFFAOYSA-M 0.000 description 1
- GKQWYZBANWAFMQ-UHFFFAOYSA-M lithium;2-hydroxypropanoate Chemical compound [Li+].CC(O)C([O-])=O GKQWYZBANWAFMQ-UHFFFAOYSA-M 0.000 description 1
- WNCZOFYWLAPNSS-UHFFFAOYSA-M lithium;3-carboxy-3,5-dihydroxy-5-oxopentanoate Chemical compound [Li+].OC(=O)CC(O)(C(O)=O)CC([O-])=O WNCZOFYWLAPNSS-UHFFFAOYSA-M 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- WIAVVDGWLCNNGT-UHFFFAOYSA-M lithium;butanoate Chemical compound [Li+].CCCC([O-])=O WIAVVDGWLCNNGT-UHFFFAOYSA-M 0.000 description 1
- SNKMVYBWZDHJHE-UHFFFAOYSA-M lithium;dihydrogen phosphate Chemical compound [Li+].OP(O)([O-])=O SNKMVYBWZDHJHE-UHFFFAOYSA-M 0.000 description 1
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
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- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
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- UHNWOJJPXCYKCG-UHFFFAOYSA-L magnesium oxalate Chemical compound [Mg+2].[O-]C(=O)C([O-])=O UHNWOJJPXCYKCG-UHFFFAOYSA-L 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
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- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
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- GMDNUWQNDQDBNQ-UHFFFAOYSA-L magnesium;diformate Chemical compound [Mg+2].[O-]C=O.[O-]C=O GMDNUWQNDQDBNQ-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- ZMCZWKGAWRLZNP-UHFFFAOYSA-N methyl-oxo-phenyltin Chemical compound C[Sn](=O)C1=CC=CC=C1 ZMCZWKGAWRLZNP-UHFFFAOYSA-N 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- HWPKGOGLCKPRLZ-UHFFFAOYSA-M monosodium citrate Chemical compound [Na+].OC(=O)CC(O)(C([O-])=O)CC(O)=O HWPKGOGLCKPRLZ-UHFFFAOYSA-M 0.000 description 1
- 239000002524 monosodium citrate Substances 0.000 description 1
- 235000018342 monosodium citrate Nutrition 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019321 monosodium tartrate Nutrition 0.000 description 1
- 125000005487 naphthalate group Chemical group 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl 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])[H] 0.000 description 1
- 125000002347 octyl 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])[H] 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 229940050271 potassium alum Drugs 0.000 description 1
- GNHOJBNSNUXZQA-UHFFFAOYSA-J potassium aluminium sulfate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GNHOJBNSNUXZQA-UHFFFAOYSA-J 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000004300 potassium benzoate Substances 0.000 description 1
- 235000010235 potassium benzoate Nutrition 0.000 description 1
- 229940103091 potassium benzoate Drugs 0.000 description 1
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- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
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- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229960002816 potassium chloride Drugs 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000004224 potassium gluconate Substances 0.000 description 1
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- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- JMTCDHVHZSGGJA-UHFFFAOYSA-M potassium hydrogenoxalate Chemical compound [K+].OC(=O)C([O-])=O JMTCDHVHZSGGJA-UHFFFAOYSA-M 0.000 description 1
- 229940086065 potassium hydrogentartrate Drugs 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- PHZLMBHDXVLRIX-UHFFFAOYSA-M potassium lactate Chemical compound [K+].CC(O)C([O-])=O PHZLMBHDXVLRIX-UHFFFAOYSA-M 0.000 description 1
- 235000011085 potassium lactate Nutrition 0.000 description 1
- 239000001521 potassium lactate Substances 0.000 description 1
- 229960001304 potassium lactate Drugs 0.000 description 1
- 239000001415 potassium malate Substances 0.000 description 1
- SVICABYXKQIXBM-UHFFFAOYSA-L potassium malate Chemical compound [K+].[K+].[O-]C(=O)C(O)CC([O-])=O SVICABYXKQIXBM-UHFFFAOYSA-L 0.000 description 1
- 235000011033 potassium malate Nutrition 0.000 description 1
- OQZCJRJRGMMSGK-UHFFFAOYSA-M potassium metaphosphate Chemical compound [K+].[O-]P(=O)=O OQZCJRJRGMMSGK-UHFFFAOYSA-M 0.000 description 1
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- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- 235000017281 sodium acetate 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
- 239000004299 sodium benzoate Substances 0.000 description 1
- 235000010234 sodium benzoate Nutrition 0.000 description 1
- 229940119126 sodium bitartrate Drugs 0.000 description 1
- MFBOGIVSZKQAPD-UHFFFAOYSA-M sodium butyrate Chemical compound [Na+].CCCC([O-])=O MFBOGIVSZKQAPD-UHFFFAOYSA-M 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000000176 sodium gluconate Substances 0.000 description 1
- 235000012207 sodium gluconate Nutrition 0.000 description 1
- 229940005574 sodium gluconate Drugs 0.000 description 1
- 239000001394 sodium malate Substances 0.000 description 1
- 235000019983 sodium metaphosphate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- NKAAEMMYHLFEFN-ZVGUSBNCSA-M sodium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound [Na+].OC(=O)[C@H](O)[C@@H](O)C([O-])=O NKAAEMMYHLFEFN-ZVGUSBNCSA-M 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- UJRAXLUXHBUNDO-UHFFFAOYSA-M sodium;hydron;oxalate Chemical compound [Na+].OC(=O)C([O-])=O UJRAXLUXHBUNDO-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- RWWNQEOPUOCKGR-UHFFFAOYSA-N tetraethyltin Chemical compound CC[Sn](CC)(CC)CC RWWNQEOPUOCKGR-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- LOAWHQCNQSFKDK-UHFFFAOYSA-N triethyltin Chemical compound CC[Sn](CC)CC.CC[Sn](CC)CC LOAWHQCNQSFKDK-UHFFFAOYSA-N 0.000 description 1
- OLBXOAKEHMWSOV-UHFFFAOYSA-N triethyltin;hydrate Chemical compound O.CC[Sn](CC)CC OLBXOAKEHMWSOV-UHFFFAOYSA-N 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 235000015870 tripotassium citrate Nutrition 0.000 description 1
- 229910000404 tripotassium phosphate Inorganic materials 0.000 description 1
- 235000019798 tripotassium phosphate Nutrition 0.000 description 1
- DOOPOMANTWCTIB-UHFFFAOYSA-M tris(2-methylpropyl)stannanylium;acetate Chemical compound CC([O-])=O.CC(C)C[Sn+](CC(C)C)CC(C)C DOOPOMANTWCTIB-UHFFFAOYSA-M 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
Abstract
Description
本発明は、熱可塑性ポリエステルエラストマーに関し、耐熱性、耐加水分解性、低温特性、耐薬品性等に優れた熱可塑性ポリエステル組成物からなる電線被覆材に関する。さらに詳しくは、パッキン、チューブなどの成形体に適しており、自動車や家電製品などの耐熱性、耐加水分解性、低温特性等が要求される用途などに有用なポリエステルエラストマーからなる電線被覆材等に関するものである。 The present invention relates to a thermoplastic polyester elastomer, and more particularly to an electric wire covering material comprising a thermoplastic polyester composition excellent in heat resistance, hydrolysis resistance, low temperature characteristics, chemical resistance and the like. More specifically, it is suitable for molded products such as packings and tubes, and is a wire covering material made of polyester elastomer that is useful for applications that require heat resistance, hydrolysis resistance, low temperature characteristics, etc., such as automobiles and home appliances. It is about.
電線被覆材には、塩化ビニル系樹脂やオレフィン系樹脂、さらにはポリエステル樹脂などの汎用樹脂から構成されているのは公知である。しかしながら、電線被覆材に使用される塩化ビニル系樹脂やオレフィン系樹脂は融点が低く、耐熱性が劣るといった問題が生じている。また、比較的融点の高いポリエステル樹脂では耐湿熱性が劣るために、屋外など比較的湿度の高いところで使用する際には大きな問題となる。これらの問題を解決するために、熱可塑性ポリエステルエラストマーが使用されていることが知られている。 It is well known that the wire covering material is composed of a general-purpose resin such as a vinyl chloride resin, an olefin resin, or a polyester resin. However, the vinyl chloride resin and olefin resin used for the wire covering material have a problem that the melting point is low and the heat resistance is poor. Further, since a polyester resin having a relatively high melting point is inferior in heat-and-moisture resistance, it becomes a serious problem when used in a place with relatively high humidity such as outdoors. In order to solve these problems, it is known that a thermoplastic polyester elastomer is used.
この熱可塑性ポリエステルエラストマーとして、ポリブチレンテレフタレート(ＰＢＴ)やポリブチレンナフタレート（ＰＢＮ）など結晶性のポリエステルをハードセグメント成分とし、さらにポリテトラメチレングリコール（ＰＴＭＧ）やポリカプロラクトンジオール（ＰＣＬＤ）などをソフトセグメント成分として用いられていることが知られている。 As this thermoplastic polyester elastomer, crystalline polyester such as polybutylene terephthalate (PBT) or polybutylene naphthalate (PBN) is used as a hard segment component, and polytetramethylene glycol (PTMG) or polycaprolactone diol (PCLD) is used as soft. It is known that it is used as a segment component.
しかしながら、ソフトセグメント成分にポリテトラメチレングリコールを用いたポリエーテル系エラストマーは耐水性や低温特性には優れるものの、耐湿熱性に劣るためにこれまでの熱可塑性ポリエステルエラストマーでは、市場要求を満足することはできなかった。 However, although polyether-based elastomers using polytetramethylene glycol as the soft segment component are excellent in water resistance and low-temperature properties, the conventional thermoplastic polyester elastomers are inferior in heat-and-moisture resistance, so that the conventional thermoplastic polyester elastomers do not satisfy market requirements. could not.
本発明は、従来の熱可塑性ポリエステルエラストマーよりも耐熱性、耐熱老化性、耐加水分解性、耐候性、耐薬品性に優れたポリエステルエラストマーを電線被覆材として用いた電線を提供することにある。 An object of the present invention is to provide an electric wire using a polyester elastomer, which is superior in heat resistance, heat aging resistance, hydrolysis resistance, weather resistance, and chemical resistance, as a wire coating material, compared to conventional thermoplastic polyester elastomers.
本発明者は、上記課題を解決するために鋭意検討した結果、上記の課題が解決されることを見出し本発明に到達した。即ち、本発明はポリブチレンナフタレートからなるポリエステルとダイマージオールからなるポリエステル組成物を含む電線被覆材であって、ポリエステルとダイマージオールの合計量１００質量部に対して、ダイマージオールを５〜３５質量部配合してなることを特徴とするポリエステル組成物を含む電線被覆材である。好ましくはダイマージオールとして以下に示す化合物を用いることである。 As a result of intensive studies to solve the above-mentioned problems, the present inventor has found that the above-mentioned problems can be solved, and has reached the present invention. That is, the present invention is an electric wire covering material comprising a polyester composition comprising a polyester composed of polybutylene naphthalate and a dimer diol, and the dimer diol is contained in an amount of 5 to 35 masses per 100 mass parts of the total amount of the polyester and dimer diol. It is an electric wire covering material containing the polyester composition characterized by being partly blended. Preferably, the following compounds are used as the dimer diol.
本発明のポリエステル組成物からなる成形品により、成形品の耐熱性、耐熱老化性、耐加水分解性、耐候性、耐薬品性に優れ、電線被覆材に好適に用いることができる。 The molded article comprising the polyester composition of the present invention is excellent in heat resistance, heat aging resistance, hydrolysis resistance, weather resistance, and chemical resistance of the molded article, and can be suitably used for a wire coating material.
本発明におけるポリエステルエラストマーはポリブチレンナフタレートとダイマージオールからなり、ポリブチレンナフタレートは芳香族ジカルボン酸および／またはそのエステル形成性誘導体を主とする芳香族ジカルボン酸成分と脂肪族および／または脂環族のジヒドロキシ化合物を主とするグリコール成分とから構成されたポリエステルからなっており、ダイマージオールは数平均分子量が５００〜２０００のダイマージオールである。これらの種類・配合量の調整により熱可塑性ポリエステルエラストマーとして機能する場合がある。 The polyester elastomer in the present invention comprises polybutylene naphthalate and dimer diol, and the polybutylene naphthalate is composed of an aromatic dicarboxylic acid component and an aliphatic and / or alicyclic ring mainly composed of an aromatic dicarboxylic acid and / or an ester-forming derivative thereof. The dimer diol is a dimer diol having a number average molecular weight of 500 to 2,000. It may function as a thermoplastic polyester elastomer by adjusting these types and amounts.
本発明におけるポリエステル組成物［以下、熱可塑性ポリエステルエラストマーと称することがある。］を構成するポリエステルはポリブチレンナフタレートからなり、それを構成する芳香族ジカルボン酸成分としては、主として２，６−ナフタレンジカルボン酸または２，７−ナフタレンジカルボン酸を挙げることができる。中でも全芳香族ジカルボン酸成分中７０モル％以上、好ましくは８０モル％が２，６−ナフタレンジカルボン酸で構成される。他の芳香族ジカルボン酸成分としては、例えばテレフタル酸、イソフタル酸、４，４′−ジフェニルジカルボン酸、ジフェノキシエタン−４，４′−ジカルボン酸、ジフェニルスルホン−４，４′−ジカルボン酸、ジフェニルエーテル−４，４′−ジカルボン酸等より選ばれる一種もしくは二種以上の組み合わせを用いることが好ましい。 Polyester composition in the present invention [hereinafter sometimes referred to as thermoplastic polyester elastomer. ] Comprises polybutylene naphthalate, and examples of the aromatic dicarboxylic acid component constituting it include mainly 2,6-naphthalenedicarboxylic acid or 2,7-naphthalenedicarboxylic acid. Among them, 70 mol% or more, preferably 80 mol%, of the total aromatic dicarboxylic acid component is composed of 2,6-naphthalenedicarboxylic acid. Examples of other aromatic dicarboxylic acid components include terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenyl ether It is preferable to use one or a combination of two or more selected from -4,4'-dicarboxylic acid and the like.
その他の非芳香族の酸成分としてはアジピン酸、セバシン酸、コハク酸、シュウ酸等の脂肪族ジカルボン酸、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸等が挙げられ、これらの一種もしくは二種以上を用いてもよく、目的によって任意に選ぶことができる。これらの酸成分は全酸成分に対して３０モル％未満、好ましくは２０モル％未満である。 Examples of other non-aromatic acid components include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, and oxalic acid, and alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. May be used and can be arbitrarily selected according to the purpose. These acid components are less than 30 mol%, preferably less than 20 mol%, based on the total acid components.
本発明における熱可塑性ポリエステルエラストマーのポリエステルを構成する芳香族ジカルボン酸のエステル形成性誘導体としては、例えば、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、４，４′−ジフェニルジカルボン酸、ジフェノキシエタン−４，４′−ジカルボン酸、ジフェニルスルホン−４，４′−ジカルボン酸、ジフェニルエーテル−４，４′−ジカルボン酸等の低級アルキルエステルより選ばれる一種もしくは二種以上の組み合わせを用いることが好ましい。その低級アルキルエステルとしてはジメチルエステル、ジエチルエステル、ジプロピルエステル、ジブチルエステル等の一種もしくは二種以上の組み合わせを用いることが好ましく、より好ましくはジメチルエステルである。より好ましくは２，６−ナフタレンジカルボン酸の低級アルキルエステルを挙げることができる。より具体的には２，６−ナフタレンジカルボン酸ジメチルエステル、２，６−ナフタレンジカルボン酸ジエチルエステル、２，６−ナフタレンジカルボン酸ジフェニルエステルである。芳香族ジカルボン酸のエステル形成性誘導体は全酸成分のエステル形成性誘導体の７０モル％以上、好ましくは８０モル％以上であることが好ましい。 Examples of the ester-forming derivative of aromatic dicarboxylic acid constituting the polyester of the thermoplastic polyester elastomer in the present invention include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 4, One or two selected from lower alkyl esters such as 4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid It is preferable to use a combination of more than one species. As the lower alkyl ester, it is preferable to use one or a combination of two or more of dimethyl ester, diethyl ester, dipropyl ester, dibutyl ester and the like, more preferably dimethyl ester. More preferable examples include lower alkyl esters of 2,6-naphthalenedicarboxylic acid. More specifically, 2,6-naphthalenedicarboxylic acid dimethyl ester, 2,6-naphthalenedicarboxylic acid diethyl ester, and 2,6-naphthalenedicarboxylic acid diphenyl ester. The ester-forming derivative of aromatic dicarboxylic acid is 70 mol% or more, preferably 80 mol% or more of the ester-forming derivative of all acid components.
その他の酸成分のエステル形成性誘導体としては、シクロヘキサンジカルボン酸等の脂環式ジカルボン酸の低級アルキルエステル、アジピン酸、セバシン酸、コハク酸、シュウ酸等の脂肪族ジカルボン酸の低級アルキルエステルより選ばれる一種もしくは二種以上を用いてもよく、目的によって任意に選ぶことができる。これらの酸のエステル形成性誘導体成分は、全酸成分のエステル形成性誘導体の３０モル％未満、好ましくは２０モル％未満である。 The ester-forming derivative of the other acid component is selected from lower alkyl esters of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and lower alkyl esters of aliphatic dicarboxylic acids such as adipic acid, sebacic acid, succinic acid, and oxalic acid. One kind or two or more kinds may be used and can be arbitrarily selected according to the purpose. The ester-forming derivative component of these acids is less than 30 mol%, preferably less than 20 mol% of the ester-forming derivative of the total acid component.
本発明における熱可塑性ポリエステルエラストマーのポリエステルを構成する芳香族ジカルボン酸に対して少量のトリメリット酸のような三官能性以上のカルボン酸成分を用いてもよく、無水トリメリット酸のような酸無水物を少量用いてもよい。また、乳酸、グリコール酸のようなヒドロキシカルボン酸またはそのアルキルエステル等を少量用いてもよく、目的によって任意に選ぶことができる。 A trifunctional or higher carboxylic acid component such as trimellitic acid may be used in a small amount relative to the aromatic dicarboxylic acid constituting the polyester of the thermoplastic polyester elastomer in the present invention, and an acid anhydride such as trimellitic anhydride. A small amount may be used. Further, a small amount of hydroxycarboxylic acid such as lactic acid or glycolic acid or an alkyl ester thereof may be used and can be arbitrarily selected depending on the purpose.
本発明における熱可塑性ポリエステルエラストマーのポリエステルはポリブチレンナフタレートからなり、それを構成するグリコール成分としては、１，４−ブタンジオールまたはテトラメチレングリコールを挙げることができる。中でもグリコール成分中７０モル％以上、好ましくは８０モル％が１，４−ブタンジオールで構成される。他のグリコール成分としては、例えば、エチレングリコール、１，３−プロピレングリコール、ネオペンチルグリコール、ヘキサメチレングリコール、デカメチレングリコール、シクロヘキサンジメタノール、ジエチレングリコール、トリエチレングリコール、ポリ（オキシ）エチレングリコール、ポリテトラメチレングリコール、ポリメチレングリコール等のアルキレングリコールの一種もしくは二種以上の組み合わせを用いることが好ましい。 The polyester of the thermoplastic polyester elastomer in the present invention comprises polybutylene naphthalate, and examples of the glycol component constituting it include 1,4-butanediol or tetramethylene glycol. Among them, 70 mol% or more, preferably 80 mol% in the glycol component is composed of 1,4-butanediol. Examples of other glycol components include ethylene glycol, 1,3-propylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, cyclohexane dimethanol, diethylene glycol, triethylene glycol, poly (oxy) ethylene glycol, polytetra It is preferable to use one or a combination of two or more alkylene glycols such as methylene glycol and polymethylene glycol.
さらに少量のグリセリンのような多価アルコール成分を用いてもよい。また少量のエポキシ化合物を用いてもよい。これらのグリコール成分は、全グリコール成分に対して３０モル％以下、好ましくは２０モル％以下である。 Furthermore, a small amount of a polyhydric alcohol component such as glycerin may be used. A small amount of an epoxy compound may be used. These glycol components are 30 mol% or less with respect to all glycol components, Preferably they are 20 mol% or less.
かかるグリコール成分の芳香族ポリエステル製造工程における使用量は、前記芳香族ジカルボン酸もしくは芳香族ジカルボン酸のエステル形成性誘導体に対して１．１モル倍以上１．４モル倍以下であることが通常採用される。グリコール成分の使用量が１．１モル倍に満たない場合にはエステル化あるいはエステル交換反応が十分に進行せず好ましくないことがある。また、１．４モル倍以上を超える場合にも、理由は定かではないが反応速度が遅くなり、過剰のグリコール成分からのテトラヒドロフランの副生量が大となり好ましくないことがある。 The amount of the glycol component used in the aromatic polyester production process is usually 1.1 mol times or more and 1.4 mol times or less with respect to the aromatic dicarboxylic acid or the ester-forming derivative of aromatic dicarboxylic acid. Is done. If the amount of the glycol component used is less than 1.1 mol times, the esterification or transesterification reaction may not proceed sufficiently, which may be undesirable. When the amount exceeds 1.4 mol times or more, the reason is not clear, but the reaction rate becomes slow, and the amount of tetrahydrofuran by-produced from an excessive glycol component may be undesirably increased.
本発明における熱可塑性ポリエステルエラストマーに用いられるダイマージオールは数平均分子量が５００〜２０００であることが好ましい。そのようなダイマージオールは、例えば、不飽和脂肪酸、おもにＣ１８のオレイン酸やリノレン酸を２００℃以上の加圧反応でダイマー酸を製造した後、水素添加することで製造することができる。本発明において使用される下記式（Ｉ）で示されるダイマージオールの数平均分子量はＧＰＣ(ゲルパーミエーションクロマトグラフィー)の測定において、４００〜４０００の範囲が好ましく、５００〜２０００が特に好ましい。数平均分子量が４００未満では、得られる本発明のポリエステル組成物の分子量が十分でないために機械的強度、成形性が悪くなる傾向があり、しかも耐熱性向上効果も少なくなりがちである。また、４０００を超えると熱可塑性ポリエステルとの反応性が低くなり、十分な機能が得られない傾向にあるため電線被覆材としての機能を果たさない。 The dimer diol used in the thermoplastic polyester elastomer in the present invention preferably has a number average molecular weight of 500 to 2,000. Such a dimer diol can be produced, for example, by hydrogenating an unsaturated fatty acid, mainly C18 oleic acid or linolenic acid, by producing a dimer acid by a pressure reaction at 200 ° C. or higher. The number average molecular weight of the dimer diol represented by the following formula (I) used in the present invention is preferably in the range of 400 to 4000, particularly preferably 500 to 2000, as measured by GPC (gel permeation chromatography). If the number average molecular weight is less than 400, the resulting polyester composition of the present invention has an insufficient molecular weight, so that the mechanical strength and moldability tend to deteriorate, and the heat resistance improving effect tends to be reduced. Moreover, when it exceeds 4000, the reactivity with thermoplastic polyester will become low, and since there exists a tendency for sufficient function not to be acquired, it does not fulfill the function as a wire coating material.
これらの中で、Ｒ１〜Ｒ４の各官能基の炭素数は４個〜１０個であることが好ましい。具体的には、Ｒ１、Ｒ２はブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基であり、Ｒ３、Ｒ４はブチレン基、ペンチレン基、ヘキシル基、ヘプチル基、オクチレン基、ノニレン基、デシレン基を挙げることができる。 Among these, it is preferable number of carbon atoms of each functional group of R 1 to R 4 is 4 to 10 pieces. Specifically, R 1 and R 2 are a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group, and R 3 and R 4 are a butylene group, a pentylene group, a hexyl group, and a heptyl group. A group, an octylene group, a nonylene group, and a decylene group.
また、ダイマージオールを含むグリコールの全成分中に炭素数２〜８個のグリコール成分が含まれていることが好ましい。このようなダイマージオール以外のグリコール成分とシクロヘキサン環を有するダイマージオールを用いることで、本発明のポリエステル組成物はエラストマーとして機能しやすくなり、また驚くべきことに成形品の耐熱性、耐熱老化性、耐加水分解性、耐候性、耐薬品性に優れるなどの効果を発現することができる。 Moreover, it is preferable that the C2-C8 glycol component is contained in all the components of the glycol containing dimer diol. By using a dimer diol having a cyclohexane ring and a glycol component other than the dimer diol, the polyester composition of the present invention easily functions as an elastomer, and surprisingly, the heat resistance, heat aging resistance, Effects such as excellent hydrolysis resistance, weather resistance, and chemical resistance can be exhibited.
また、ダイマージオールの含有量はポリエステルとダイマージオールの合計質量、本発明のポリエステル組成物１００質量部に対して、５〜３５質量部配合することが必要である。５質量部より少ないと本発明の効果である成形品の表面硬度を下げるという効果が発揮できず、３５質量部を超えるとポリエステル組成物自体の強度等の力学物性が低下するので好ましくない。この数値範囲に配合を行うことで、得られる熱可塑性ポリエステルエラストマーは電線被覆材として好適に用いることができる。なお、本発明においては、ダイマージオールは末端にヒドロキシル基を有しているのでポリエステルに共重合される成分が大部分であると考えられるが、数平均分子量が多くなるに従って共重合に資する割合が減り、組成物として配合されている割合が増加すると考える。 Moreover, it is necessary to mix | blend 5-35 mass parts content of dimer diol with respect to the total mass of polyester and dimer diol, and 100 mass parts of polyester compositions of this invention. If the amount is less than 5 parts by mass, the effect of lowering the surface hardness of the molded product, which is the effect of the present invention, cannot be exhibited. By blending in this numerical range, the resulting thermoplastic polyester elastomer can be suitably used as a wire coating material. In the present invention, since the dimer diol has a hydroxyl group at the terminal, it is considered that the component copolymerized with the polyester is most, but the proportion contributing to the copolymerization increases as the number average molecular weight increases. I think that it decreases and the ratio mix | blended as a composition increases.
本発明における熱可塑性ポリエステルエラストマーにおいて重合触媒成分として用いられる化合物としてはポリエステル製造用触媒として用いられる化合物、特にポリブチレンナフタレートやポリブチレンテレフタレートで通常用いられる化合物が好ましく採用される。中でもチタン化合物が好ましくもちいられる。そのチタン化合物としては、テトラアルキルチタネートが好ましく、具体的にはテトラ−ｎ−プロピルチタネート、テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネート、テトラ−ｔ−ブチルチタネート、テトラフェニルチタネート、テトラシクロヘキシルチタネート、テトラベンジルチタネートなどが挙げられ、これらの混合チタネートとして用いても良い。これらのチタン化合物のうち、特にテトラ−ｎ−プロピルチタネート、テトライソプロピルチタネート、テトラ−ｎ−ブチルチタネートが好ましく、最も好ましいのはテトラ−ｎ−ブチルチタネートである。 As the compound used as a polymerization catalyst component in the thermoplastic polyester elastomer in the present invention, a compound used as a catalyst for producing a polyester, particularly a compound usually used in polybutylene naphthalate or polybutylene terephthalate is preferably employed. Of these, titanium compounds are preferably used. The titanium compound is preferably a tetraalkyl titanate, specifically tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetra-t-butyl titanate, tetraphenyl titanate, tetracyclohexyl titanate, tetra Examples thereof include benzyl titanate, and these may be used as a mixed titanate. Among these titanium compounds, tetra-n-propyl titanate, tetraisopropyl titanate, and tetra-n-butyl titanate are particularly preferable, and tetra-n-butyl titanate is most preferable.
チタン化合物の添加量は生成した熱可塑性ポリエステルエラストマー中のチタン原子含有量として、２００ｐｐｍ以下であることが好ましく、より好ましくは１０〜１５０ｐｐｍ、さらに好ましくは５０〜１００ｐｐｍである。熱可塑性ポリエステルエラストマー中のチタン原子含有量が２００ｐｐｍを超える場合は、本発明の熱可塑性ポリエステルエラストマーの色調および熱安定性が低下するために好ましくないことがある。またチタン原子含有量として少ない場合には、ポリエステル製造時の触媒化合物としてチタンを用いるのに充分な触媒活性を発揮できない場合がある。そのような場合には他の金属化合物を触媒として用いることになるが、熱安定性、色相、耐加水分解性などに問題を生じる場合がある。 The addition amount of the titanium compound is preferably 200 ppm or less, more preferably 10 to 150 ppm, still more preferably 50 to 100 ppm as the titanium atom content in the produced thermoplastic polyester elastomer. When the titanium atom content in the thermoplastic polyester elastomer exceeds 200 ppm, the color tone and thermal stability of the thermoplastic polyester elastomer of the present invention may be unfavorable. When the titanium atom content is small, there may be a case where the catalyst activity sufficient to use titanium as a catalyst compound at the time of producing the polyester cannot be exhibited. In such a case, other metal compounds are used as the catalyst, but problems may occur in thermal stability, hue, hydrolysis resistance, and the like.
また、本発明における熱可塑性ポリエステルエラストマーには、例えば、オクタアルキルトリチタネートもしくはヘキサアルキルジチタネートなどのテトラアルキルチタネート以外のアルキルチタネート、酢酸チタンやシュウ酸チタンなどのチタンの弱酸塩、酸化チタンなどのチタン酸化物、ジブチルスズオキサイド、メチルフェニルスズオキサイド、テトラエチルスズ、ヘキサエチルジスズオキサイド、シクロヘキサヘキシルジスズオキサイド、ジドデシルスズオキサイド、トリエチルスズハイドロオキサイド、トリフェニルスズハイドロオキサイド、トリイソブチルスズアセテート、ジブチルスズジアセテート、ジフェニルスズジラウレート、モノブチルスズトリクロライド、ジブチルスズジクロライド、トリブチルスズクロライド、ジブチルスズサルファイド、ブチルヒドロキシスズオキサイドなどの有機スズ化合物、塩化カリウム、カリウムミョウバン、ギ酸カリウム、クエン酸三カリウム、クエン酸水素二カリウム、クエン酸二水素カリウム、グルコン酸カリウム、コハク酸カリウム、酪酸カリウム、シュウ酸二カリウム、シュウ酸水素カリウム、ステアリン酸カリウム、フタル酸カリウム、フタル酸水素カリウム、メタリン酸カリウム、リンゴ酸カリウム、リン酸三カリウム、リン酸水素二カリウム、リン酸二水素カリウム、亜硝酸カリウム、安息香酸カリウム、酒石酸水素カリウム、重蓚酸カリウム、重フタル酸カリウム、重酒石酸カリウム、重硫酸カリウム、硝酸カリウム、酢酸カリウム、水酸化カリウム、炭酸カリウム、炭酸カリウムナトリウム、炭酸水素カリウム、乳酸カリウム、硫酸カリウム硫酸水素カリウム、塩化ナトリウム、ギ酸ナトリウム、クエン酸三ナトリウム、クエン酸水素二ナトリウム、クエン酸二水素ナトリウム、グルコン酸ナトリウム、コハク酸ナトリウム、酪酸ナトリウム、シュウ酸二ナトリウム、シュウ酸水素ナトリウム、ステアリン酸ナトリウム、フタル酸ナトリウム、フタル酸水素ナトリウム、メタリン酸ナトリウム、リンゴ酸ナトリウム、リン酸三ナトリウム、リン酸水素二ナトリウム、リン酸二水素ナトリウム、亜硝酸ナトリウム、安息香酸ナトリウム、酒石酸水素ナトリウム、重シュウ酸ナトリウム、重フタル酸ナトリウム、重酒石酸ナトリウム、重硫酸ナトリウム、硝酸ナトリウム、酢酸ナトリウム、水酸化ナトリウム、炭酸ナトリウム、炭酸水素ナトリウム、乳酸ナトリウム、硫酸ナトリウム、硫酸水素ナトリウム、塩化リチウム、ギ酸リチウム、クエン酸三リチウム、クエン酸水素二リチウム、クエン酸二水素リチウム、グルコン酸リチウム、コハク酸リチウム、酪酸リチウム、シュウ酸二リチウム、シュウ酸水素リチウム、ステアリン酸リチウム、フタル酸リチウム、フタル酸水素リチウム、メタリン酸リチウム、リンゴ酸リチウム、リン酸三リチウム、リン酸水素二リチウム、リン酸二水素リチウム、亜硝酸リチウム、安息香酸リチウム、酒石酸水素リチウム、重シュウ酸リチウム、重フタル酸リチウム、重酒石酸リチウム、重硫酸リチウム、硝酸リチウム、酢酸リチウム、水酸化リチウム、炭酸リチウム、炭酸水素リチウム、乳酸リチウム、硫酸リチウム、硫酸水素リチウムなどのアルカリ金属塩、塩化カルシウム、ギ酸カルシウム、コハク酸カルシウム、酪酸カルシウム、シュウ酸カルシウム、ステアリン酸カルシウム、リン酸カルシウム、硝酸カルシウム、酢酸カルシウム、水酸化カルシウム、炭酸カルシウム、乳酸カルシウム、硫酸カルシウム、塩化マグネシウム、ギ酸マグネシウム、コハク酸マグネシウム、酪酸マグネシウム、シュウ酸マグネシウム、ステアリン酸マグネシウム、リン酸マグネシウム、硝酸マグネシウム、酢酸マグネシウム、水酸化マグネシウム、炭酸マグネシウムなどのアルカリ土類金属塩の１種もしくは２種以上をチタン化合物と組み合わせても良い。 The thermoplastic polyester elastomer in the present invention includes, for example, alkyl titanates other than tetraalkyl titanates such as octaalkyltrititanate or hexaalkyldititanate, weak titanium salts such as titanium acetate and titanium oxalate, and titanium oxide. Titanium oxide, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, triphenyltin hydroxide, triisobutyltin acetate, dibutyltin Diacetate, Diphenyltin dilaurate, Monobutyltin trichloride, Dibutyltin dichloride, Tributyltin chloride, Di Organotin compounds such as tiltin sulfide, butylhydroxytin oxide, potassium chloride, potassium alum, potassium formate, tripotassium citrate, dipotassium hydrogen citrate, potassium dihydrogen citrate, potassium gluconate, potassium succinate, potassium butyrate , Dipotassium oxalate, potassium hydrogen oxalate, potassium stearate, potassium phthalate, potassium hydrogen phthalate, potassium metaphosphate, potassium malate, tripotassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, Potassium nitrate, potassium benzoate, potassium hydrogen tartrate, potassium bicarbonate, potassium biphthalate, potassium bitartrate, potassium bisulfate, potassium nitrate, potassium acetate, potassium hydroxide, potassium carbonate, potassium potassium carbonate, potassium hydrogen carbonate , Potassium lactate, potassium hydrogen sulfate potassium hydrogen sulfate, sodium chloride, sodium formate, trisodium citrate, disodium hydrogen citrate, sodium dihydrogen citrate, sodium gluconate, sodium succinate, sodium butyrate, disodium oxalate, Sodium hydrogen oxalate, sodium stearate, sodium phthalate, sodium hydrogen phthalate, sodium metaphosphate, sodium malate, trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium nitrite, sodium benzoate , Sodium hydrogen tartrate, sodium bioxalate, sodium biphthalate, sodium bitartrate, sodium bisulfate, sodium nitrate, sodium acetate, sodium hydroxide, sodium carbonate, sodium bicarbonate, milk Sodium sulfate, sodium sulfate, sodium hydrogen sulfate, lithium chloride, lithium formate, trilithium citrate, dilithium hydrogen citrate, lithium dihydrogen citrate, lithium gluconate, lithium succinate, lithium butyrate, dilithium oxalate, sulphur Lithium oxyhydrogen, lithium stearate, lithium phthalate, lithium hydrogen phthalate, lithium metaphosphate, lithium malate, trilithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, lithium nitrite, lithium benzoate, Lithium hydrogen tartrate, lithium heavy oxalate, lithium biphthalate, lithium bitartrate, lithium bisulfate, lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate, lithium hydrogen carbonate, lithium lactate, lithium sulfate, lithium hydrogen sulfate, etc. Alkaline gold Salt, calcium chloride, calcium formate, calcium succinate, calcium butyrate, calcium oxalate, calcium stearate, calcium phosphate, calcium nitrate, calcium acetate, calcium hydroxide, calcium carbonate, calcium lactate, calcium sulfate, magnesium chloride, magnesium formate, succinate A combination of one or more alkaline earth metal salts such as magnesium acid, magnesium butyrate, magnesium oxalate, magnesium stearate, magnesium phosphate, magnesium nitrate, magnesium acetate, magnesium hydroxide, magnesium carbonate, etc. with a titanium compound Also good.
本発明の熱可塑性ポリエステルエラストマーを構成するポリエステル［ポリブチレンナフタレート］は、ナフタレンジカルボン酸および／またはそのエステル形成性誘導体を主とするジカルボン酸成分と１，４−ブタンジオールを主とするグリコール成分、ダイマージオールを一括して仕込んだのちに、チタン化合物の存在下にてエステル化あるいはエステル交換反応工程と、それに続く重縮合反応工程とを経由して製造される。 The polyester [polybutylene naphthalate] constituting the thermoplastic polyester elastomer of the present invention comprises a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and / or an ester-forming derivative thereof and a glycol component mainly composed of 1,4-butanediol. After dimer diol is charged all at once, the dimer diol is produced via an esterification or transesterification reaction step and a subsequent polycondensation reaction step in the presence of a titanium compound.
エステル化あるいはエステル交換反応終了の際に１８０℃以上２２０℃以下の範囲にある事が好ましい。当該反応が２２０℃を超える場合には反応速度は大きくなるが、テトラヒドロフランの副生が多くなり好ましくない。また、１８０℃未満では反応が進行しなくなる。エステル化あるいはエステル交換反応により得られた反応生成物は、当該反応生成物を熱可塑性ポリエステルエラストマーの融点以上２６０℃以下の温度において０．４ｋＰａ（３Ｔｏｒｒ）以下の減圧下で重縮合させることが好ましい。重縮合反応温度が２６０℃を超える場合にはむしろ反応速度が低下して、着色も大となるので好ましくない。 When the esterification or transesterification reaction is completed, it is preferably in the range of 180 ° C. or higher and 220 ° C. or lower. When the reaction exceeds 220 ° C., the reaction rate increases, but tetrahydrofuran by-product increases, which is not preferable. On the other hand, if the temperature is less than 180 ° C., the reaction does not proceed. The reaction product obtained by esterification or transesterification reaction is preferably polycondensed under a reduced pressure of 0.4 kPa (3 Torr) or less at a temperature not lower than the melting point of the thermoplastic polyester elastomer and not higher than 260 ° C. . When the polycondensation reaction temperature exceeds 260 ° C., the reaction rate is rather lowered, and coloring is increased, which is not preferable.
重縮合反応において、重合触媒として通常用いられている触媒を前記チタン化合物と併用することも可能であるが、前記チタン化合物をエステル化あるいはエステル交換反応および重縮合反応の共通触媒として用いることが好ましい。他の触媒を併用すると熱可塑性ポリエステルエラストマーの着色が大となり、ひいては熱可塑性ポリエステルエラストマーの色調も低下するので好ましくない。また、重縮合反応速度も前記チタン化合物を単独にて使用した場合と比較して大差が無く、併用効果が得られない。 In the polycondensation reaction, a catalyst usually used as a polymerization catalyst can be used in combination with the titanium compound, but the titanium compound is preferably used as a common catalyst for esterification or transesterification and polycondensation reactions. . When other catalysts are used in combination, the coloring of the thermoplastic polyester elastomer is increased, and the color tone of the thermoplastic polyester elastomer is also lowered, which is not preferable. Also, the polycondensation reaction rate is not much different from the case where the titanium compound is used alone, and the combined use effect cannot be obtained.
本発明の熱可塑性ポリエステルエラストマーを構成する熱可塑性ポリエステルの末端カルボキシル基濃度は４０ｅｑ／Ｔ（４０当量／１０６ｇ）以下であり、好ましくは３５ｅｑ／Ｔ（３５当量／１０６ｇ）である。末端カルボキシル基濃度が４０ｅｑ／Ｔを超える場合には熱安定性や加水分解性が低下し、ひいては熱可塑性ポリエステルエラストマーの熱安定性や加水分解性も低下するので好ましくない。 The terminal carboxyl group concentration of the thermoplastic polyester constituting the thermoplastic polyester elastomer of the present invention is 40 eq / T (40 equivalents / 10 6 g) or less, preferably 35 eq / T (35 equivalents / 10 6 g). When the terminal carboxyl group concentration exceeds 40 eq / T, the thermal stability and hydrolyzability are lowered, and the thermal stability and hydrolyzability of the thermoplastic polyester elastomer are also lowered, which is not preferable.
本発明の熱可塑性ポリエステルエラストマーは、次の方法で製造することができる。すなわち、ポリエステル製造工程の重縮合反応が終了する以前の任意の段階でダイマージオールを添加しても良いし、ベントつき二軸押出機にポリエステルおよびダイマージオールを供給し、混練押出しにより、製造してもよい。 The thermoplastic polyester elastomer of the present invention can be produced by the following method. That is, dimer diol may be added at an arbitrary stage before the completion of the polycondensation reaction in the polyester production process, or polyester and dimer diol are supplied to a twin screw extruder with a vent and are produced by kneading and extrusion. Also good.
本発明の熱可塑性ポリエステルエラストマーは上述のように成形性に優れているので、各種成形方法に用いて、熱可塑性ポリエステルエラストマーを材料とする成形体を製造することは、非常に好ましい様態である。すなわち、本発明の熱可塑性ポリエステルエラストマー成形体の製造方法は、熱可塑性ポリエステルエラストマー組成物を材料とする成形体を製造する方法であって、本発明のポリエステル組成物を用いて押出成形、射出成形、ブロー成形、発泡成形および紡糸成形からなる群より選ばれる少なくとも１種の成形を行うことによりポリエステル成形体を得ることができる。またその中で押出成形は薄膜ダイから押出しによるフィルム製膜であっても良い。 Since the thermoplastic polyester elastomer of the present invention is excellent in moldability as described above, it is a very preferable mode to produce a molded body made of a thermoplastic polyester elastomer by using various molding methods. That is, the method for producing a thermoplastic polyester elastomer molded article of the present invention is a method for producing a molded article made of a thermoplastic polyester elastomer composition, and is formed by extrusion molding or injection molding using the polyester composition of the present invention. A polyester molded body can be obtained by performing at least one molding selected from the group consisting of blow molding, foam molding and spin molding. Among them, the extrusion may be film formation by extrusion from a thin film die.
本発明の熱可塑性ポリエステルエラストマーを用いて得られる有用な成形品としては、例えば、射出成形による中空成形体、射出成形体等が挙げられる。その具体例としては、電気・電子部品、自動車用部品、機構部品等が挙げられる。成形条件としては、シリンダー温度２４５℃、金型温度２５℃にて射出成形を行い、射出成形体を得ることができる。 Examples of useful molded articles obtained by using the thermoplastic polyester elastomer of the present invention include hollow molded bodies by injection molding, injection molded bodies, and the like. Specific examples thereof include electric / electronic parts, automobile parts, mechanism parts, and the like. As molding conditions, injection molding can be performed by performing injection molding at a cylinder temperature of 245 ° C. and a mold temperature of 25 ° C.
本発明に用いられるポリエステル組成物は、ハードセグメントがポリブチレンナフタレート単位よりなり、かつ得られるポリエステル組成物の融点が２１５〜２３０℃であることが好ましい。融点が２１５℃よりも低いと電線被覆材に成形した際の耐熱性が低下する。２３０℃を超えると、電線被覆材の成形時における品質変動が大きくなり成形品の品質の低下や成形サイクルの悪化に繋がるため好ましくない。 In the polyester composition used in the present invention, the hard segment is preferably composed of polybutylene naphthalate units, and the obtained polyester composition preferably has a melting point of 215 to 230 ° C. When the melting point is lower than 215 ° C., the heat resistance at the time of forming the wire coating material is lowered. If the temperature exceeds 230 ° C., the quality fluctuation at the time of molding the wire covering material becomes large, which leads to deterioration of the quality of the molded product and deterioration of the molding cycle.
本発明に使用される熱可塑性ポリエステル組成物中のダイマージオールの配合量はポリエステル組成物の硬度や機械的性質を決定する重要な因子であり、ポリエステル組成物の硬度や融点に大きな影響を及ぼす。一般にソフトセグメント成分の配合量が増加するにつれ成形品は柔らかくなり融点も低くなる。ダイマージオールの配合量の増加は融点の低下つまりは耐熱性の低下を意味し、ポリエステル組成物の硬度や引張強度、さらには弾性率など機械的性質の低下をも引き起こすために好ましくない。 The blending amount of the dimer diol in the thermoplastic polyester composition used in the present invention is an important factor that determines the hardness and mechanical properties of the polyester composition, and greatly affects the hardness and melting point of the polyester composition. In general, as the blending amount of the soft segment component increases, the molded product becomes softer and the melting point becomes lower. An increase in the blending amount of dimer diol means a decrease in melting point, that is, a decrease in heat resistance, and is also undesirable because it causes a decrease in mechanical properties such as hardness, tensile strength, and elastic modulus of the polyester composition.
本発明のポリエステル組成物の水存在下１７０℃で５時間保持後固有粘度保持率は、９５％以上が好ましい。数値が高くなるほど、ポリエステル組成物の加水分解性が抑えられる。固有粘度保持率が９５％よりも低くなった場合、ポリエステル組成物の加水分解率が高くなることにより電線被覆材としての役割を果たさないために好ましくない。また、ダイマージオールを５〜３５質量部配合することにより固有粘度保持率を９５％以上にすることができる。固有粘度保持率が９６％であることが好ましい。製造方法については、ポリエステル製造工程の重縮合反応が終了する以前の任意の段階でポリエステル組成物１００質量部に対し５〜３５質量部になるようにダイマージオールを添加しても良いし、ベントつき二軸押出機にポリエステルおよびダイマージオールを供給し、混練押出により製造してもよい。 The intrinsic viscosity retention after holding for 5 hours at 170 ° C. in the presence of water of the polyester composition of the present invention is preferably 95% or more. The higher the value, the less hydrolyzable the polyester composition. When the intrinsic viscosity retention rate is lower than 95%, it is not preferable because the rate of hydrolysis of the polyester composition is increased so that it does not serve as a wire coating material. Moreover, intrinsic viscosity retention can be 95% or more by mix | blending 5-35 mass parts dimer diol. The intrinsic viscosity retention is preferably 96%. As for the production method, dimer diol may be added so as to be 5 to 35 parts by mass with respect to 100 parts by mass of the polyester composition at any stage before the completion of the polycondensation reaction in the polyester production process. Polyester and dimer diol may be supplied to a twin-screw extruder and manufactured by kneading extrusion.
また、本発明の熱可塑性ポリエステル組成物の表面Ｄ硬度は、９０以下であることが好ましい。５０〜９０が好ましく、７０〜８０が特に好ましい。数値が高くなるほどポリエステル組成物の硬度が高くなる。表面Ｄ硬度が９０を超えた場合は柔軟性の低下により電線被覆材としての役割を果たさないために好ましくない。表面Ｄ硬度をこの値にするのにもダイマージオールの配合量を５〜３５質量部保つことが重要となる。 The surface D hardness of the thermoplastic polyester composition of the present invention is preferably 90 or less. 50-90 are preferable and 70-80 are especially preferable. The higher the value, the higher the hardness of the polyester composition. When the surface D hardness exceeds 90, it is not preferable because it does not serve as a wire coating material due to a decrease in flexibility. In order to obtain the surface D hardness at this value, it is important to keep the blending amount of the dimer diol at 5 to 35 parts by mass.
本発明の熱可塑性ポリエステル組成物は、電線被覆材において一層あるいは二層以上から構成される電線でも特に問題はなく、塩化ビニル系樹脂、オレフィン系樹脂、ポリエステル系樹脂、さらには熱可塑性ポリエステルエラストマーなどと任意に組み合わせることができる。本発明の硬さの異なるポリエステル系エラストマー同士を内層あるいは外層に用いても問題はない。また、２種以上の樹脂同士をアロイしたものを用いても何ら問題はない。 The thermoplastic polyester composition of the present invention is not particularly problematic even in an electric wire composed of one layer or two or more layers in a wire covering material, such as a vinyl chloride resin, an olefin resin, a polyester resin, and a thermoplastic polyester elastomer. And can be combined arbitrarily. There is no problem even if the polyester elastomers having different hardnesses of the present invention are used in the inner layer or the outer layer. Moreover, there is no problem even if an alloy of two or more kinds of resins is used.
以下、実施例により本発明をさらい詳細に説明するが、本発明はこれらに限定されるものではない。各記載中、「部」は質量部、「％」は質量％を示す。また、諸物性の測定は以下の方法により実施した。 EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In each description, “parts” indicates mass parts, and “%” indicates mass%. Various physical properties were measured by the following methods.
１）固有粘度（ＩＶ）測定
常法に従って、溶媒であるオルトクロロフェノール中、３５℃で測定した。
1) Intrinsic Viscosity (IV) Measurement It was measured at 35 ° C. in orthochlorophenol as a solvent according to a conventional method.
２）チタン原子含有量測定
熱可塑性ポリエステル中のチタン原子量は理学電機社製蛍光Ｘ線測定機ＺＳＸを用いて定量した。
2) Measurement of titanium atom content The amount of titanium atom in the thermoplastic polyester was quantified using a fluorescent X-ray measuring machine ZSX manufactured by Rigaku Corporation.
３）末端カルボキシル濃度測定（ＣＯＯＨ）
熱可塑性ポリエステルをベンジルアルコールに溶解して、０．１Ｎ−ＮａＯＨにて滴定した値であり、１×１０６ｇ（１トン）当たりのカルボキシル当量である。
3) Terminal carboxyl concentration measurement (COOH)
It is a value obtained by dissolving a thermoplastic polyester in benzyl alcohol and titrating with 0.1 N NaOH, and is a carboxyl equivalent per 1 × 10 6 g (1 ton).
４）Ｄ硬度
熱可塑性ポリエステル組成物を日精樹脂工業製ＨＭ７−Ｃの射出成形機にてシリンダー温度２４５℃、金型温度２５℃にて射出成形し、得られたプレート(３０ｍｍ×３０ｍｍ×３Ｔサイズ)をテクロック社製デュロメータＧＳ−７２０Ｈにて測定した。また、測定方法については、日本工業規格ＪＩＳ Ｋ−７２１５のタイプＤデュロメータの操作方法に準じて行った。
4) D hardness The thermoplastic polyester composition was injection-molded at a cylinder temperature of 245 ° C. and a mold temperature of 25 ° C. using an HM7-C injection molding machine manufactured by Nissei Plastic Industry, and the resulting plate (30 mm × 30 mm × 3T size) ) Was measured with a durometer GS-720H manufactured by Teclock Corporation. Moreover, about the measuring method, it carried out according to the operation method of the Japanese Industrial Standard JISK-7215 type D durometer.
５）ＩＶ保持率測定
プレッシャークッカーにて１７０℃×５時間処理後のＩＶを測定し、その保持率を算出した。
ＩＶ保持率(％)＝(処理後のＩＶ)／(処理前のＩＶ)×１００
5) Measurement of IV retention rate IV after treatment at 170 ° C for 5 hours was measured with a pressure cooker, and the retention rate was calculated.
IV retention (%) = (IV after treatment) / (IV before treatment) × 100
６）ダイマージオール
シクロ脂肪族ダイマージオールを触媒存在下、２００℃以上で加圧することで製造されるが、今回は品質の安定している市販ダイマージオール(クローダジャパンＰＲＩＰＯＬ２０３３)を使用した。このダイマージオールは上記式（Ｉ）において、Ｒ１とＲ２は炭素数７個のアルキル基であり、Ｒ３とＲ４は炭素数７個のアルキレン基である。またＲ１〜Ｒ４の官能基の炭素数の合計は３０個であり、平均数分子量は５４０であった。
6) Dimer diol The dimer diol is produced by pressurizing cycloaliphatic dimer diol at 200 ° C. or higher in the presence of a catalyst, but this time, a commercially available dimer diol (Cloda Japan PRIPOL 2033) with stable quality was used. In the dimer diol, in the above formula (I), R 1 and R 2 are alkyl groups having 7 carbon atoms, and R 3 and R 4 are alkylene groups having 7 carbon atoms. The total number of carbon atoms of the functional groups R 1 to R 4 was 30 and the average number molecular weight was 540.
７）電線被覆材としての評価
３０φの一軸押し出し機を用いて２ｍｍ２の断面積を有する銅線導体に本発明で得られた熱可塑性ポリエステルエラストマーを厚さ０．８ｍｍで被覆した。外観はこのときの亀裂や破断の有無で確認した（外観評価）。この被覆された電線を１９０℃のギアー式老化試験機で１時間加熱処理を行い亀裂や破断の有無を確認した（熱老化評価）。さらに、被覆された電線を１００℃の水に１週間浸漬させた後の亀裂の有無や曲げた際の亀裂を観察した（耐湿熱性評価）。このとき、評価結果に問題がなかったものを○とし、問題が生じたものを×とした。
7) Evaluation as an electric wire coating material A thermoplastic polyester elastomer obtained in the present invention was coated with a thickness of 0.8 mm on a copper wire conductor having a cross-sectional area of 2 mm2 using a 30φ uniaxial extruder. The appearance was confirmed by the presence or absence of cracks and breaks at this time (appearance evaluation). This coated electric wire was subjected to heat treatment for 1 hour with a gear type aging tester at 190 ° C. to confirm the presence or absence of cracks or breaks (thermal aging evaluation). Furthermore, the presence or absence of cracks after immersing the coated electric wires in water at 100 ° C. for 1 week and cracks when bent were observed (wet heat resistance evaluation). At this time, the case where there was no problem in the evaluation result was marked with ◯, and the case where the problem occurred was marked with ×.
［実施例１］
熱可塑性ポリエステル組成物の生成量が１００質量部となるように、２，６−ナフタレンジカルボン酸ジメチルエステル８１．３質量部、１，４−ブタンジオール３３．７質量部、分子量５４０のダイマージオール１０．０質量部にテトラ−ｎ−ブチルチタネート０．１１質量部をエステル交換反応槽に入れ、反応槽が１９０℃となるように昇温しながら２１０分間エステル交換反応を行った。ついで得られた反応生成物を重縮合反応槽に移して重縮合反応を開始した。
[Example 1]
Dimer diol 10 having a molecular weight of 540, 81.3 parts by weight of 2,6-naphthalenedicarboxylic acid dimethyl ester, 33.7 parts by weight of 1,4-butanediol so that the amount of the thermoplastic polyester composition produced is 100 parts by weight. 0.01 part by mass of tetra-n-butyl titanate (0.11 part by mass) was placed in a transesterification reaction vessel, and the ester exchange reaction was carried out for 210 minutes while raising the temperature of the reaction vessel to 190 ° C. Subsequently, the obtained reaction product was transferred to a polycondensation reaction tank to start a polycondensation reaction.
重縮合反応は常圧から０．１３３ｋＰａ（１Ｔｏｒｒ）以下まで４０分かけて徐々に減圧し、同時に所定の反応温度２５０℃まで昇温し、以降は所定の重合温度、０．１３３ｋＰａ（１Ｔｏｒｒ）の状態を維持して１００分間重縮合反応を行った。１００分が経過した時点で熱可塑性ポリエステル組成物を少量採取して固有粘度を測定した。固有粘度は０．７７ｄＬ／ｇであった。
得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定、電線被覆材の評価を行って、その結果を表１に示した。
In the polycondensation reaction, the pressure is gradually reduced from normal pressure to 0.133 kPa (1 Torr) or less over 40 minutes, and at the same time, the temperature is raised to a predetermined reaction temperature of 250 ° C. Thereafter, a predetermined polymerization temperature of 0.133 kPa (1 Torr) is reached. The state was maintained and a polycondensation reaction was performed for 100 minutes. When 100 minutes had passed, a small amount of the thermoplastic polyester composition was sampled and the intrinsic viscosity was measured. Intrinsic viscosity was 0.77 dL / g.
Intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, measurement of surface D hardness, evaluation of wire covering material, results Is shown in Table 1.
［実施例２］
ダイマージオールの添加量を１０．０質量部から２０．０質量部に変更し、熱可塑性ポリエステル組成物の生成量が１００質量部となるように２，６−ナフタレンジカルボン酸ジメチルエステルと１，４−ブタンジオールの仕込み量を変更した以外は、実施例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Example 2]
The addition amount of dimer diol was changed from 10.0 parts by mass to 20.0 parts by mass, and 2,6-naphthalenedicarboxylic acid dimethyl ester and 1,4 were adjusted so that the production amount of the thermoplastic polyester composition became 100 parts by mass. -A thermoplastic polyester composition was obtained in the same manner as in Example 1 except that the amount of butanediol charged was changed. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［実施例３］
ダイマージオールの添加量を１０．０質量部から３０．０質量部に変更し、熱可塑性ポリエステル組成物の生成量が１００質量部となるように２，６−ナフタレンジカルボン酸ジメチルエステルと１，４−ブタンジオールの仕込み量を変更した以外は、実施例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Example 3]
The addition amount of dimer diol was changed from 10.0 parts by weight to 30.0 parts by weight, and 2,6-naphthalenedicarboxylic acid dimethyl ester and 1,4 so that the production amount of the thermoplastic polyester composition was 100 parts by weight. -A thermoplastic polyester composition was obtained in the same manner as in Example 1 except that the amount of butanediol charged was changed. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［比較例１］
ダイマージオールの添加量を１０．０質量部から４０．０質量部に変更し、熱可塑性ポリエステル組成物の生成量が１００質量部となるように２，６−ナフタレンジカルボン酸ジメチルエステルと１，４−ブタンジオールの仕込み量を変更した以外は、実施例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Comparative Example 1]
The addition amount of dimer diol was changed from 10.0 parts by mass to 40.0 parts by mass, and 2,6-naphthalenedicarboxylic acid dimethyl ester and 1, 4 were adjusted so that the amount of the thermoplastic polyester composition produced was 100 parts by mass. -A thermoplastic polyester composition was obtained in the same manner as in Example 1 except that the amount of butanediol charged was changed. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［比較例２］
ダイマージオールの添加量を１０．０質量部から５０．０質量部に変更し、熱可塑性ポリエステル組成物の生成量が１００質量部となるように２，６−ナフタレンジカルボン酸ジメチルエステルと１，４−ブタンジオールの仕込み量を変更した以外は、実施例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Comparative Example 2]
The addition amount of dimer diol was changed from 10.0 parts by mass to 50.0 parts by mass, and 2,6-naphthalenedicarboxylic acid dimethyl ester and 1,4 were adjusted so that the amount of the thermoplastic polyester composition produced was 100 parts by mass. -A thermoplastic polyester composition was obtained in the same manner as in Example 1 except that the amount of butanediol charged was changed. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［比較例３］
熱可塑性ポリエステル組成物の生成量が１００質量部となるように、２，６−ナフタレンジカルボン酸ジメチルエステル４５．２質量部、１，４−ブタンジオール２３．４質量部、分子量１０００のポリ（テトラメチレンオキサイド）グリコール５０．０質量部にテトラ−ｎ−ブチルチタネート０．０７６質量部をエステル交換反応槽に入れ、反応槽が１９０℃となるように昇温しながら２１０分間エステル交換反応を行った。ついで得られた反応生成物を重縮合反応槽に移して重縮合反応を開始した。
[Comparative Example 3]
2,6-Naphthalenedicarboxylic acid dimethyl ester 45.2 parts by weight, 1,4-butanediol 23.4 parts by weight, and molecular weight 1000 (polytetra) Methylene oxide) Glycol 50.0 parts by mass and tetra-n-butyl titanate 0.076 parts by mass were placed in a transesterification reactor, and the ester exchange reaction was carried out for 210 minutes while raising the temperature of the reaction vessel to 190 ° C. . Subsequently, the obtained reaction product was transferred to a polycondensation reaction tank to start a polycondensation reaction.
重縮合反応は常圧から０．１３３ｋＰａ（１Ｔｏｒｒ）以下まで４０分かけて徐々に減圧し、同時に所定の反応温度２５０℃まで昇温し、以降は所定の重合温度、０．１３３ｋＰａ（１Ｔｏｒｒ）の状態を維持して１００分間重縮合反応を行った。１００分が経過した時点で熱可塑性ポリエステル組成物を少量採取して固有粘度を測定した。固有粘度は１．８５ｄＬ／ｇであった。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。 In the polycondensation reaction, the pressure is gradually reduced from normal pressure to 0.133 kPa (1 Torr) or less over 40 minutes, and at the same time, the temperature is raised to a predetermined reaction temperature of 250 ° C., and thereafter a predetermined polymerization temperature of 0.133 kPa (1 Torr). The state was maintained and a polycondensation reaction was performed for 100 minutes. When 100 minutes had elapsed, a small amount of the thermoplastic polyester composition was sampled and the intrinsic viscosity was measured. The intrinsic viscosity was 1.85 dL / g. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［比較例４］
ポリ（テトラメチレンオキサイド）グリコールの分子量を１０００から１５００に変更した以外は、比較例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Comparative Example 4]
A thermoplastic polyester composition was obtained in the same manner as in Comparative Example 1 except that the molecular weight of poly (tetramethylene oxide) glycol was changed from 1000 to 1500. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
［比較例５］
ポリ（テトラメチレンオキサイド）グリコールの分子量を１０００から２０００に変更した以外は、比較例１と同様にして熱可塑性ポリエステル組成物を得た。得られた熱可塑性ポリエステル組成物の固有粘度、熱可塑性ポリエステル組成物中のチタン原子含有量、ＩＶ保持率、末端カルボキシル基濃度、表面Ｄ硬度の測定を行って、その結果を表１に示した。
[Comparative Example 5]
A thermoplastic polyester composition was obtained in the same manner as in Comparative Example 1 except that the molecular weight of poly (tetramethylene oxide) glycol was changed from 1000 to 2000. The intrinsic viscosity of the obtained thermoplastic polyester composition, titanium atom content in the thermoplastic polyester composition, IV retention, terminal carboxyl group concentration, and surface D hardness were measured, and the results are shown in Table 1. .
本発明のポリエステル組成物からなる成形品により、成形品の耐熱性、耐熱老化性、耐加水分解性、耐候性、耐薬品性に優れ、電線被覆材に好適に用いることができる。 The molded article comprising the polyester composition of the present invention is excellent in heat resistance, heat aging resistance, hydrolysis resistance, weather resistance, and chemical resistance of the molded article, and can be suitably used for a wire coating material.
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| WO2021200715A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, film, and adhesive composition, and adhesive sheet, laminate, and printed wiring board |
| WO2021200712A1 (en) * | 2020-03-30 | 2021-10-07 | 東洋紡株式会社 | Polyester, adhesive, and film |
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| JP2022033184A (en) * | 2020-03-30 | 2022-02-28 | 東洋紡株式会社 | Polyester, adhesive agent, and film |
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| JP7136312B2 (en) | 2020-03-30 | 2022-09-13 | 東洋紡株式会社 | polyesters, adhesives and films |
| CN115210288A (en) * | 2020-03-30 | 2022-10-18 | 东洋纺株式会社 | Polyester, adhesive and film |
| CN115298244A (en) * | 2020-03-30 | 2022-11-04 | 东洋纺株式会社 | Polyester, film, adhesive composition, adhesive sheet, laminate, and printed wiring board |
| CN115298245A (en) * | 2020-03-30 | 2022-11-04 | 东洋纺株式会社 | Polyester, film, adhesive composition, adhesive sheet, laminate, and printed wiring board |
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