JP2023103597A - Medical molding composed of polyethylene naphthalate resin composition - Google Patents
Medical molding composed of polyethylene naphthalate resin composition Download PDFInfo
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- JP2023103597A JP2023103597A JP2022004210A JP2022004210A JP2023103597A JP 2023103597 A JP2023103597 A JP 2023103597A JP 2022004210 A JP2022004210 A JP 2022004210A JP 2022004210 A JP2022004210 A JP 2022004210A JP 2023103597 A JP2023103597 A JP 2023103597A
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- Prior art keywords
- tert
- acid
- butyl
- component
- polyethylene naphthalate
- Prior art date
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- Pending
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- -1 polyethylene naphthalate Polymers 0.000 title claims abstract description 67
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 title claims abstract description 22
- 239000011112 polyethylene naphthalate Substances 0.000 title claims abstract description 22
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 238000000465 moulding Methods 0.000 title abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000004697 Polyetherimide Substances 0.000 claims abstract description 12
- 229920001601 polyetherimide Polymers 0.000 claims abstract description 12
- 238000002834 transmittance Methods 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 33
- 239000000194 fatty acid Substances 0.000 description 33
- 229930195729 fatty acid Natural products 0.000 description 33
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 30
- 150000004665 fatty acids Chemical class 0.000 description 24
- 150000001875 compounds Chemical class 0.000 description 20
- 238000000034 method Methods 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 11
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical class OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 229920001296 polysiloxane Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 7
- 239000001993 wax Substances 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000001746 injection moulding Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 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 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- 238000005809 transesterification reaction Methods 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 4
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000001771 impaired effect Effects 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
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000013872 montan acid ester Nutrition 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 150000002989 phenols Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000005487 naphthalate group Chemical group 0.000 description 3
- WGOROJDSDNILMB-UHFFFAOYSA-N octatriacontanediamide Chemical compound NC(=O)CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O WGOROJDSDNILMB-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- HXIQYSLFEXIOAV-UHFFFAOYSA-N 2-tert-butyl-4-(5-tert-butyl-4-hydroxy-2-methylphenyl)sulfanyl-5-methylphenol Chemical compound CC1=CC(O)=C(C(C)(C)C)C=C1SC1=CC(C(C)(C)C)=C(O)C=C1C HXIQYSLFEXIOAV-UHFFFAOYSA-N 0.000 description 2
- MSXXDBCLAKQJQT-UHFFFAOYSA-N 2-tert-butyl-6-methyl-4-[3-(2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl)oxypropyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCCOP2OC3=C(C=C(C=C3C=3C=C(C=C(C=3O2)C(C)(C)C)C(C)(C)C)C(C)(C)C)C(C)(C)C)=C1 MSXXDBCLAKQJQT-UHFFFAOYSA-N 0.000 description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 description 2
- SSADPHQCUURWSW-UHFFFAOYSA-N 3,9-bis(2,6-ditert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C)=CC(C(C)(C)C)=C1OP1OCC2(COP(OC=3C(=CC(C)=CC=3C(C)(C)C)C(C)(C)C)OC2)CO1 SSADPHQCUURWSW-UHFFFAOYSA-N 0.000 description 2
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 description 2
- 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 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
- KLDXJTOLSGUMSJ-JGWLITMVSA-N Isosorbide Chemical compound O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 KLDXJTOLSGUMSJ-JGWLITMVSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229920004748 ULTEM® 1010 Polymers 0.000 description 2
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- FQUNFJULCYSSOP-UHFFFAOYSA-N bisoctrizole Chemical compound N1=C2C=CC=CC2=NN1C1=CC(C(C)(C)CC(C)(C)C)=CC(CC=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2N=C3C=CC=CC3=N2)O)=C1O FQUNFJULCYSSOP-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 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
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- UAUDZVJPLUQNMU-KTKRTIGZSA-N erucamide Chemical compound CCCCCCCC\C=C/CCCCCCCCCCCC(N)=O UAUDZVJPLUQNMU-KTKRTIGZSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229940119177 germanium dioxide Drugs 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
- 229960002479 isosorbide Drugs 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
- YJFCFSVVFTZXBL-UHFFFAOYSA-N o-[3-henicosanethioyloxy-2,2-bis(henicosanethioyloxymethyl)propyl] henicosanethioate Chemical compound CCCCCCCCCCCCCCCCCCCCC(=S)OCC(COC(=S)CCCCCCCCCCCCCCCCCCCC)(COC(=S)CCCCCCCCCCCCCCCCCCCC)COC(=S)CCCCCCCCCCCCCCCCCCCC YJFCFSVVFTZXBL-UHFFFAOYSA-N 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920001281 polyalkylene Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920001522 polyglycol ester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000005846 sugar alcohols Polymers 0.000 description 2
- 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 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N trans-sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-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
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N tristearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- JGAGDUXRCMTELL-UHFFFAOYSA-N (2,4,8,10-tetratert-butylbenzo[d][1,3,2]benzodioxaphosphepin-6-yl) 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound O1C2=C(C(C)(C)C)C=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC(C(C)(C)C)=C2OP1OC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 JGAGDUXRCMTELL-UHFFFAOYSA-N 0.000 description 1
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N (R)-alpha-Tocopherol Natural products OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 0.000 description 1
- PHJMLWHPHSYYQI-UHFFFAOYSA-N 1,1-bis(2,6-ditert-butyl-4-ethylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C(=CC(=C1)CC)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1C(C)(C)C)CC)C(C)(C)C PHJMLWHPHSYYQI-UHFFFAOYSA-N 0.000 description 1
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical class CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 1
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- GXURZKWLMYOCDX-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;dihydroxyphosphanyl dihydrogen phosphite Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO GXURZKWLMYOCDX-UHFFFAOYSA-N 0.000 description 1
- ZIUHCEIEPOPBCK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol;hexanedioic acid;octadecanoic acid Chemical compound OCC(CO)(CO)CO.OC(=O)CCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O ZIUHCEIEPOPBCK-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- NEUPRVAMTYHIQV-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)disulfanyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(SSC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 NEUPRVAMTYHIQV-UHFFFAOYSA-N 0.000 description 1
- UDFARPRXWMDFQU-UHFFFAOYSA-N 2,6-ditert-butyl-4-[(3,5-ditert-butyl-4-hydroxyphenyl)methylsulfanylmethyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CSCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 UDFARPRXWMDFQU-UHFFFAOYSA-N 0.000 description 1
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 150000003512 tertiary amines Chemical class 0.000 description 1
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- AJHKJOCIGPIJFZ-UHFFFAOYSA-N tris(2,6-ditert-butylphenyl) phosphite Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1OP(OC=1C(=CC=CC=1C(C)(C)C)C(C)(C)C)OC1=C(C(C)(C)C)C=CC=C1C(C)(C)C AJHKJOCIGPIJFZ-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- QQBLOZGVRHAYGT-UHFFFAOYSA-N tris-decyl phosphite Chemical compound CCCCCCCCCCOP(OCCCCCCCCCC)OCCCCCCCCCC QQBLOZGVRHAYGT-UHFFFAOYSA-N 0.000 description 1
- QFGXDXGDZKTYFD-UHFFFAOYSA-N tris[2,3-di(propan-2-yl)phenyl] phosphite Chemical compound CC(C)C1=CC=CC(OP(OC=2C(=C(C(C)C)C=CC=2)C(C)C)OC=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C QFGXDXGDZKTYFD-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
- Medical Preparation Storing Or Oral Administration Devices (AREA)
Abstract
Description
本発明は、透明性および耐熱性に優れたポリエチレンナフタレート樹脂組成物からなる医療用成形体に関する。 TECHNICAL FIELD The present invention relates to a molded article for medical use comprising a polyethylene naphthalate resin composition having excellent transparency and heat resistance.
ポリエチレンナフタレート樹脂はポリエチレンテレフタレート樹脂に比べ静置場での結晶化速度が遅いため射出成形により容易に透明な成形体が得られる特徴があり、透明性、耐熱性、耐薬品性が求められる医療や食品用途の透明成形体に利用されている。しかしながら、ポリエチレンナフタレート樹脂はガラス転移温度が125℃と低いため、オートクレーブ滅菌処理により熱変形し医療用成形体への展開が限定的となっていた。 Compared to polyethylene terephthalate resin, polyethylene naphthalate resin has a slower crystallization speed in a static environment, so it is characterized by the ability to easily obtain a transparent molded product by injection molding. It is used in transparent moldings for food applications. However, since polyethylene naphthalate resin has a low glass transition temperature of 125° C., it is thermally deformed by autoclave sterilization, and its application to medical moldings has been limited.
ポリエチレンナフタレート樹脂の耐熱性向上については、特許文献1にはナフタレンジカルボン酸と芳香族ジオール成分を共重合したガラス転移温度が135℃以上の共重合ポリエステルの製造方法が開示されている。しかしながら、芳香族ジオール成分を特定量共重合することによりポリエチレンナフタレート樹脂のガラス転移温度は上昇するものの到達するガラス転移温度は138℃以下であり、120℃から134℃の温度範囲にて行われるオートクレーブ滅菌処理により熱変形し耐熱性が不十分である。特許文献2には、ナフタレンジカルボン酸にイソソルビド由来の構成成分を共重合した非架橋性のポリエステル樹脂が開示されている。イソソルビド由来の構成成分を一定量以上共重合することによりガラス転移温度を150℃以上まで高めることが可能であるが、開示されている共重合ポリエステルは茶褐色であり透明性が不十分である。特許文献3には、ポリアルキレンナフタレート樹脂にポリエーテルイミド樹脂を添加することを特徴とするポリアルキレンナフタレート樹脂の蛍光防止方法が開示されている。また、特許文献4には、ポリエチレンナフタレート樹脂およびポリエーテルイミド樹脂のブレンド物からなる写真フィルムベースが開示されているが、いずれも透明性と耐熱性に関しての検証がなされていない。 As for improving the heat resistance of polyethylene naphthalate resin, Patent Document 1 discloses a method for producing a copolymerized polyester having a glass transition temperature of 135° C. or higher by copolymerizing naphthalenedicarboxylic acid and an aromatic diol component. However, although the glass transition temperature of the polyethylene naphthalate resin increases by copolymerizing a specific amount of the aromatic diol component, the glass transition temperature reached is 138°C or less, and the copolymerization is carried out in the temperature range of 120°C to 134°C. Due to heat deformation due to autoclave sterilization, the heat resistance is insufficient. Patent Document 2 discloses a non-crosslinkable polyester resin obtained by copolymerizing naphthalene dicarboxylic acid with a component derived from isosorbide. It is possible to increase the glass transition temperature to 150° C. or higher by copolymerizing a certain amount or more of a component derived from isosorbide, but the disclosed copolymerized polyester is dark brown and insufficient in transparency. Patent Document 3 discloses a method for preventing fluorescence of a polyalkylene naphthalate resin, which comprises adding a polyetherimide resin to the polyalkylene naphthalate resin. Further, Patent Document 4 discloses a photographic film base comprising a blend of polyethylene naphthalate resin and polyetherimide resin, but none of them are verified for transparency and heat resistance.
本発明の目的は、透明性および耐熱性に優れたポリエチレンナフタレート樹脂組成物からなる医療用成形体を提供することにある。 An object of the present invention is to provide a molded article for medical use comprising a polyethylene naphthalate resin composition having excellent transparency and heat resistance.
本発明者らは、上記目的を達成せんとして鋭意検討を重ねた結果、ポリエチレンナフタレート樹脂にポリエーテルイミド樹脂を特定量添加することにより、透明性と耐熱性に優れたポリエチレンナフタレート樹脂組成物からなる医療用成形体が得られることを見出し、上記課題を解決するに至った。 The present inventors have made intensive studies to achieve the above object, and have found that a polyethylene naphthalate resin composition having excellent transparency and heat resistance is obtained by adding a specific amount of a polyetherimide resin to a polyethylene naphthalate resin. The inventors have found that a molded article for medical use can be obtained, and have solved the above problems.
すなわち、本発明の課題は、(A)ポリエチレンナフタレート樹脂(A成分)100重量部に対し、(B)ポリエーテルイミド樹脂(B成分)を30~220重量部含有することを特徴とするポリエチレンナフタレート樹脂組成物からなる医療用成形体により達成される。 That is, the subject of the present invention is a polyethylene characterized by containing 30 to 220 parts by weight of (B) a polyetherimide resin (B component) with respect to 100 parts by weight of (A) a polyethylene naphthalate resin (A component). This is achieved by a medical molding made of a naphthalate resin composition.
本発明によれば、透明性と耐熱性に優れたポリエチレンナフタレート樹脂組成物からなる医療用成形体を提供することができ、本発明により得られた医療用成形体は、医薬品ボトルおよびバイアル瓶等に好適に使用することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a molded article for medical use comprising a polyethylene naphthalate resin composition having excellent transparency and heat resistance. etc. can be suitably used.
以下、更に本発明の詳細について説明する。 Further details of the present invention will be described below.
<A成分について>
本発明のA成分であるポリエチレンナフタレート樹脂は、ナフタレンジカルボン酸および/またはナフタレンジカルボン酸のエステル形成誘導体を主とするジカルボン酸成分と、エチレングリコールを主成分とするグリコール成分を用いて製造することができる。
<About A component>
The polyethylene naphthalate resin, which is component A of the present invention, is produced using a dicarboxylic acid component mainly composed of naphthalenedicarboxylic acid and/or an ester-forming derivative of naphthalenedicarboxylic acid, and a glycol component mainly composed of ethylene glycol. can be done.
ナフタレンジカルボン酸成分としては、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を主成分とするが、特性を損なわない範囲であれば、他のジカルボン酸を併用することができる。他のジカルボン酸としては、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′-ジカルボン酸等の芳香族ジカルボン酸、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1種もしくは2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。他のジカルボン酸の使用量は全酸成分に対して好ましくは30モル%以下、より好ましくは20モル%以下である。ナフタレンジカルボン酸のエステル形成性誘導体としては、2,6-ナフタレンジカルボン酸ジメチル、2,7-ナフタレンジカルボン酸ジメチルを主成分とするが、特性を損なわない範囲であれば、他のジカルボン酸のエステル形成性誘導体を併用することができる。他の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、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′-ジカルボン酸等の芳香族ジカルボン酸の低級ジアルキルエステル、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ジアルキルエステル、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ジアルキルエステル等が挙げられ、これらの1種若しくは2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。他のジカルボン酸のエステル形成性誘導体の使用量は、全ジカルボン酸のエステル形成性誘導体成分に対して好ましくは30モル%以下、より好ましくは20モル%以下である。 As the naphthalenedicarboxylic acid component, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are used as main components, but other dicarboxylic acids may be used in combination as long as the properties are not impaired. Other dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, diphenyl ether-4, Aromatic dicarboxylic acids such as 4'-dicarboxylic acid, adipic acid, sebacic acid, succinic acid, aliphatic dicarboxylic acids such as oxalic acid, alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, and the like, one or Two or more kinds may be used, and can be arbitrarily selected depending on the purpose. The amount of the other dicarboxylic acid used is preferably 30 mol % or less, more preferably 20 mol % or less, based on the total acid components. As the ester-forming derivative of naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylate and dimethyl 2,7-naphthalenedicarboxylate are used as main components, but esters of other dicarboxylic acids are used as long as the properties are not impaired. Formable derivatives can be used in combination. Other ester-forming derivatives of dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, diphenoxyethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid. acids, lower dialkyl esters of aromatic dicarboxylic acids such as diphenyl ether-4,4′-dicarboxylic acid, lower dialkyl esters of alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid, adipic acid, sebacic acid, succinic acid, oxalic acid, etc. Lower dialkyl esters of aliphatic dicarboxylic acids and the like can be mentioned, and one or more of these may be used and can be arbitrarily selected depending on the purpose. The amount of other ester-forming derivative of dicarboxylic acid to be used is preferably 30 mol % or less, more preferably 20 mol % or less, relative to the total dicarboxylic acid ester-forming derivative component.
また、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。 Also, a small amount of a tri- or higher functional carboxylic acid component such as trimellitic acid may be used, and a small amount of an acid anhydride such as trimellitic anhydride may be used. In addition, a small amount of hydroxycarboxylic acid such as lactic acid and glycolic acid or an alkyl ester thereof may be used, and can be arbitrarily selected depending on the purpose.
グリコール成分としてはエチレングリコールを主成分とするが、特性を損なわない範囲で他のグリコール成分を併用することができる。他のグリコール成分としては、例えば、1、4ブタンジオール、1,3-プロピレングリコール、1,2-プロピレングリコール、ネオペンチレングリコール、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(オキシ)テトラメチレングリコール、ポリ(オキシ)メチレングリコール等のアルキレングリコールの1種若しくは2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。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。他のグリコール成分の使用量は、全グリコール成分に対して好ましくは30モル%以下、より好ましくは20モル%以下である。 As the glycol component, ethylene glycol is used as the main component, but other glycol components can be used together as long as the properties are not impaired. Other glycol components include, for example, 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, and triethylene. One or two or more of alkylene glycols such as glycol, poly(oxy)ethylene glycol, poly(oxy)tetramethylene glycol, poly(oxy)methylene glycol, etc. may be used, and can be arbitrarily selected depending on the purpose. In addition, small amounts of polyhydric alcohol components such as glycerin may be used. A small amount of epoxy compound may also be used. The amount of other glycol components used is preferably 30 mol % or less, more preferably 20 mol % or less, based on the total glycol components.
上記のポリエチレンナフタレート樹脂は、従来公知の製造方法によって製造することができる。すなわちジカルボン酸成分とジオール成分とを直接反応させて水を留去しエステル化した後、減圧下に重縮合を行う直接エステル化法、またはジカルボン酸ジメチルエステルとジオール成分とを反応させてメチルアルコールを留去しエステル交換させた後、減圧下に重縮合を行うエステル交換法により製造される。更に極限粘度数を増大させるために固相重合を行うことができる。 Said polyethylene naphthalate resin can be manufactured by a conventionally well-known manufacturing method. That is, a direct esterification method in which a dicarboxylic acid component and a diol component are directly reacted to distill off water and esterify, followed by polycondensation under reduced pressure, or a dicarboxylic acid dimethyl ester and a diol component are reacted to form methyl alcohol. is distilled off, transesterified, and then polycondensed under reduced pressure. Solid state polymerization can be carried out to further increase the intrinsic viscosity.
上記のエステル交換反応、エステル化反応および重縮合反応時には、触媒および安定剤を使用することが好ましい。エステル交換触媒としてはMg化合物、Mn化合物、Ca化合物、Zn化合物などが使用され、例えばこれらの酢酸塩、モノカルボン酸塩、アルコラート、および酸化物などが挙げられる。またエステル化反応は触媒を添加せずに、ジカルボン酸およびジオールのみで実施することが可能であるが、後述の重縮合触媒の存在下に実施することもできる。重縮合触媒としては、Ge化合物、Ti化合物、Sb化合物などが使用可能であり、例えば二酸化ゲルマニウム、水酸化ゲルマニウム、ゲルマニウムアルコラート、チタンテトラブトキサイド、チタンテトライソプロポキサイド、および蓚酸チタンなどが挙げられる。安定剤としてはリン化合物を用いることが好ましい。好ましいリン化合物としては、リン酸およびそのエステル、亜リン酸およびそのエステル並びに次亜リン酸およびそのエステルなどが挙げられる。またエステル化反応時には、ジエチレングリコール副生を抑制するためにトリエチルアミンなどの第3級アミン、水酸化テトラエチルアンモニウムなどの水酸化第4級アンモニウム、および炭酸ナトリウムなどの塩基性化合物を添加することもできる。また得られたポリエステル樹脂には、各種の安定剤および改質剤を配合することができる。 It is preferable to use a catalyst and a stabilizer during the above transesterification, esterification and polycondensation reactions. Mg compounds, Mn compounds, Ca compounds, Zn compounds and the like are used as transesterification catalysts, and examples thereof include acetates, monocarboxylates, alcoholates and oxides thereof. The esterification reaction can be carried out using only a dicarboxylic acid and a diol without adding a catalyst, but it can also be carried out in the presence of a polycondensation catalyst, which will be described later. As polycondensation catalysts, Ge compounds, Ti compounds, Sb compounds, etc. can be used, and examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholates, titanium tetrabutoxide, titanium tetraisopropoxide, and titanium oxalate. . Phosphorus compounds are preferably used as stabilizers. Preferred phosphorus compounds include phosphoric acid and its esters, phosphorous acid and its esters, and hypophosphorous acid and its esters. Further, during the esterification reaction, a tertiary amine such as triethylamine, a quaternary ammonium hydroxide such as tetraethylammonium hydroxide, and a basic compound such as sodium carbonate can be added in order to suppress diethylene glycol by-production. Various stabilizers and modifiers can be added to the obtained polyester resin.
A成分の固有粘度は0.5~1.0dl/gであることが好ましく、より好ましくは0.55~0.85dl/gであり、さらに好ましくは0.60~0.68dl/gである。A成分の固有粘度が0.5dl/g未満では耐衝撃性に劣る場合があり、1.0dl/gを超えるとポリエチレンナフタレート樹脂の粘度が高すぎるため射出成形時の噛み込み性が悪化する場合がある。 The intrinsic viscosity of component A is preferably 0.5 to 1.0 dl/g, more preferably 0.55 to 0.85 dl/g, still more preferably 0.60 to 0.68 dl/g. . If the intrinsic viscosity of component A is less than 0.5 dl/g, the impact resistance may be poor. Sometimes.
<B成分について>
本発明のB成分であるポリエーテルイミド樹脂は、環状イミド構造を含有する樹脂であり、本発明の目的に使用できるものであれば特に限定されないが、脂肪族または芳香族系のエーテル単位と環状イミド基を繰り返し単位として含有するポリエーテルイミド樹脂が好ましい。また、本発明の効果を阻害しない範囲であれば、ポリイミドの主鎖に環状イミドおよびエーテル単位以外の構造単位、例えば、芳香族、脂肪族エステル単位、オキシカルボニル単位等が含有されても良い。
<About B component>
The polyetherimide resin, which is the component B of the present invention, is a resin containing a cyclic imide structure, and is not particularly limited as long as it can be used for the purpose of the present invention. Polyetherimide resins containing imide groups as repeating units are preferred. Further, structural units other than cyclic imide and ether units, such as aromatic and aliphatic ester units, oxycarbonyl units, etc., may be contained in the main chain of the polyimide as long as the effects of the present invention are not impaired.
本発明で好ましく使用できるポリエーテルイミド樹脂の具体例としては、下記式(1)で示されるポリエーテルイミド樹脂を挙げることができる。 Specific examples of polyetherimide resins that can be preferably used in the present invention include polyetherimide resins represented by the following formula (1).
(式(1)中、nは2以上の整数であり、R1は、6~30個の炭素原子を含有する2価の芳香族または脂肪族基、R2は6~30個の炭素原子を有する2価の芳香族残基、2~20個の炭素原子を有するアルキレン基、2~20個の炭素原子を有するシクロアルキレン基、および2~8個の炭素原子を有するアルキレン基で連鎖停止されたポリジオルガノシロキサン基からなる群より選択された2価の有機基である。) (In formula (1), n is an integer of 2 or more, R 1 is a divalent aromatic or aliphatic group containing 6 to 30 carbon atoms, R 2 is 6 to 30 carbon atoms, , alkylene groups with 2 to 20 carbon atoms, cycloalkylene groups with 2 to 20 carbon atoms, and alkylene groups with 2 to 8 carbon atoms. is a divalent organic group selected from the group consisting of polydiorganosiloxane groups selected from
上記R1、R2としては、例えば下記式(2)~(8)で示される芳香族残基およびアルキレン基を挙げることができる。 Examples of R 1 and R 2 include aromatic residues and alkylene groups represented by the following formulas (2) to (8).
(式(8)中、nは2以上の整数である。)
なお本発明では、ポリエチレンナフタレート樹脂との相容性の観点から下記式(9)で示されるポリエーテルイミド樹脂が好ましい。
(In formula (8), n is an integer of 2 or more.)
In the present invention, a polyetherimide resin represented by the following formula (9) is preferable from the viewpoint of compatibility with polyethylene naphthalate resin.
(式(9)中、nは2以上の整数である。)
このポリエーテルイミド樹脂としては、SHPPジャパン合同会社製の“ULTEM1010”等が挙げられる。
(In formula (9), n is an integer of 2 or more.)
Examples of this polyetherimide resin include "ULTEM1010" manufactured by SHPP Japan LLC.
B成分の含有量は、A成分100重量部に対し、30~220重量部であり、好ましくは45~180重量部であり、より好ましくは70~150重量部である。B成分の含有量が30重量部未満の場合、耐熱性が改善されない。一方、含有量が220重量部を超えると透明性が低下する。 The content of component B is 30 to 220 parts by weight, preferably 45 to 180 parts by weight, more preferably 70 to 150 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 30 parts by weight, heat resistance is not improved. On the other hand, when the content exceeds 220 parts by weight, the transparency is lowered.
(その他の添加剤について)
なお、本発明の樹脂組成物は、本発明の趣旨に反しない範囲で、酸化防止剤、離型剤等の各添加剤を含むことが出来る。
(About other additives)
The resin composition of the present invention can contain various additives such as antioxidants and release agents within the scope of the present invention.
<酸化防止剤>
本発明の樹脂組成物は酸化防止剤として、ヒンダードフェノール系化合物、ホスファイト系化合物、ホスホナイト系化合物およびチオエーテル系化合物からなる群より選ばれる少なくとも1種の酸化防止剤を含むことができる。酸化防止剤を配合することにより、成形加工時の色相や流動性が安定するだけでなく、耐加水分解性の向上にも効果がある。
<Antioxidant>
The resin composition of the present invention may contain, as an antioxidant, at least one antioxidant selected from the group consisting of hindered phenol compounds, phosphite compounds, phosphonite compounds and thioether compounds. The addition of an antioxidant not only stabilizes the hue and fluidity during molding, but also has the effect of improving hydrolysis resistance.
ヒンダードフェノール系化合物としては、例えば、α-トコフェロール、ブチルヒドロキシトルエン、シナピルアルコール、ビタミンE、n-オクタデシル-β-(4’-ヒドロキシ-3’,5’-ジ-tert-ブチルフェル)プロピオネート、2-tert-ブチル-6-(3’-tert-ブチル-5’-メチル-2’-ヒドロキシベンジル)-4-メチルフェニルアクリレート、2,6-ジ-tert-ブチル-4-(N,N-ジメチルアミノメチル)フェノール、3,5-ジ-tert-ブチル-4-ヒドロキシベンジルホスホネートジエチルエステル、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)、2,2’-メチレンビス(4-エチル-6-tert-ブチルフェノール)、4,4’-メチレンビス(2,6-ジ-tert-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-シクロヘキシルフェノール)、2,2’-ジメチレン-ビス(6-α-メチル-ベンジル-p-クレゾール)2,2’-エチリデン-ビス(4,6-ジ-tert-ブチルフェノール)、2,2’-ブチリデン-ビス(4-メチル-6-tert-ブチルフェノール)、4,4’-ブチリデンビス(3-メチル-6-tert-ブチルフェノール)、トリエチレングリコール-N-ビス-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート、1,6-へキサンジオールビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、ビス[2-tert-ブチル-4-メチル6-(3-tert-ブチル-5-メチル-2-ヒドロキシベンジル)フェニル]テレフタレート、3,9-ビス{2-[3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ]-1,1,-ジメチルエチル}-2,4,8,10-テトラオキサスピロ[5,5]ウンデカン、4,4’-チオビス(6-tert-ブチル-m-クレゾール)、4,4’-チオビス(3-メチル-6-tert-ブチルフェノール)、2,2’-チオビス(4-メチル-6-tert-ブチルフェノール)、ビス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)スルフィド、4,4’-ジ-チオビス(2,6-ジ-tert-ブチルフェノール)、4,4’-トリ-チオビス(2,6-ジ-tert-ブチルフェノール)、2,2-チオジエチレンビス-[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]、2,4-ビス(n-オクチルチオ)-6-(4-ヒドロキシ-3’,5’-ジ-tert-ブチルアニリノ)-1,3,5-トリアジン、N,N’-ヘキサメチレンビス-(3,5-ジ-tert-ブチル-4-ヒドロキシヒドロシンナミド)、N,N’-ビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニル]ヒドラジン、1,1,3-トリス(2-メチル-4-ヒドロキシ-5-tert-ブチルフェニル)ブタン、1,3,5-トリメチル-2,4,6-トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)ベンゼン、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)イソシアヌレート、トリス(3,5-ジ-tert-ブチル-4-ヒドロキシベンジル)イソシアヌレート、1,3,5-トリス(4-tert-ブチル-3-ヒドロキシ-2,6-ジメチルベンジル)イソシアヌレート、1,3,5-トリス2[3(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]エチルイソシアヌレート、およびテトラキス[メチレン-3-(3’,5’-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート]メタンなどが例示される。上記化合物の中でも、テトラキス[メチレン-3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオネート]メタン、オクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート、および3,9-ビス[2-{3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ}-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5,5]ウンデカンが好ましく利用される。特にオクタデシル-3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネートが好ましい。これらはいずれも入手容易である。上記ヒンダードフェノール系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Examples of hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-octadecyl-β-(4'-hydroxy-3',5'-di-tert-butylfer)propionate. , 2-tert-butyl-6-(3′-tert-butyl-5′-methyl-2′-hydroxybenzyl)-4-methylphenyl acrylate, 2,6-di-tert-butyl-4-(N, N-dimethylaminomethyl)phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2 '-dimethylene-bis(6-α-methyl-benzyl-p-cresol) 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-butylidene-bis(4-methyl -6-tert-butylphenol), 4,4′-butylidenebis(3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3-(3-tert-butyl-4-hydroxy-5-methyl phenyl)propionate, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], bis[2-tert-butyl-4-methyl 6-(3- tert-butyl-5-methyl-2-hydroxybenzyl)phenyl]terephthalate, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1, 1,-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane, 4,4′-thiobis(6-tert-butyl-m-cresol), 4,4′-thiobis( 3-methyl-6-tert-butylphenol), 2,2′-thiobis(4-methyl-6-tert-butylphenol), bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, 4, 4′-di-thiobis(2,6-di-tert-butylphenol), 4,4′-tri-thiobis(2,6-di-tert-butylphenol), 2,2-thiodiethylenebis-[3-( 3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis(n-octylthio)-6-(4-hydroxy-3′,5′-di-tert-butylanilino)-1 , 3,5-triazine, N,N′-hexamethylenebis-(3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N,N′-bis[3-(3,5-di -tert-butyl-4-hydroxyphenyl)propionyl]hydrazine, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-trimethyl-2,4 ,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxyphenyl)isocyanurate, tris(3,5-di- tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 1,3,5-tris-2[3 (3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]ethyl isocyanurate and tetrakis[methylene-3-(3′,5′-di-tert-butyl-4-hydroxyphenyl)propionate] Methane etc. are illustrated. Among the above compounds, tetrakis[methylene-3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate]methane, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl ) propionate, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10 -tetraoxaspiro[5,5]undecane is preferably utilized. Octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate is particularly preferred. All of these are readily available. The above hindered phenol compounds can be used alone or in combination of two or more.
ホスファイト系化合物としては、トリフェニルホスファイト、トリス(ノニルフェニル)ホスファイト、トリデシルホスファイト、トリオクチルホスファイト、トリオクタデシルホスファイト、ジデシルモノフェニルホスファイト、ジオクチルモノフェニルホスファイト、ジイソプロピルモノフェニルホスファイト、モノブチルジフェニルホスファイト、モノデシルジフェニルホスファイト、モノオクチルジフェニルホスファイト、トリス(ジエチルフェニル)ホスファイト、トリス(ジ-iso-プロピルフェニル)ホスファイト、トリス(ジ-n-ブチルフェニル)ホスファイト、トリス(2,4-ジ-tert-ブチルフェニル)ホスファイト、トリス(2,6-ジ-tert-ブチルフェニル)ホスファイト、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-エチルフェニル)ペンタエリスリトールジホスファイト、ビス{2,4-ビス(1-メチル-1-フェニルエチル)フェニル}ペンタエリスリトールジホスファイト、フェニルビスフェノールAペンタエリスリトールジホスファイト、ビス(ノニルフェニル)ペンタエリスリトールジホスファイト、およびジシクロヘキシルペンタエリスリトールジホスファイト等が挙げられる。さらに他のホスファイト系化合物としては二価フェノール類と反応し環状構造を有するものも使用できる。例えば、2,2’-メチレンビス(4,6-ジ-tert-ブチルフェニル)(2,4-ジ-tert-ブチルフェニル)ホスファイト、2,2’-メチレンビス(4,6-ジ-tert-ブチルフェニル)(2-tert-ブチル-4-メチルフェニル)ホスファイト、および2,2-メチレンビス(4,6-ジ-tert-ブチルフェニル)オクチルホスファイト等が挙げられる。好適なホスファイト系化合物は、ジステアリルペンタエリスリトールジホスファイト、ビス(2,4-ジ-tert-ブチルフェニル)ペンタエリスリトールジホスファイト、ビス(2,6-ジ-tert-ブチル-4-メチルフェニル)ペンタエリスリトールジホスファイト、およびビス{2,4-ビス(1-メチル-1-フェニルエチル)フェニル}ペンタエリスリトールジホスファイトである。 Phosphite compounds include triphenyl phosphite, tris(nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl mono Phenylphosphite, monobutyldiphenylphosphite, monodecyldiphenylphosphite, monooctyldiphenylphosphite, tris(diethylphenyl)phosphite, tris(di-iso-propylphenyl)phosphite, tris(di-n-butylphenyl) ) phosphite, tris(2,4-di-tert-butylphenyl)phosphite, tris(2,6-di-tert-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2,4- di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4- ethylphenyl)pentaerythritol diphosphite, bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite, and the like. Furthermore, as other phosphite-based compounds, those having a cyclic structure that react with dihydric phenols can also be used. For example, 2,2′-methylenebis(4,6-di-tert-butylphenyl)(2,4-di-tert-butylphenyl)phosphite, 2,2′-methylenebis(4,6-di-tert- butylphenyl)(2-tert-butyl-4-methylphenyl)phosphite and 2,2-methylenebis(4,6-di-tert-butylphenyl)octylphosphite. Suitable phosphite compounds include distearylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methyl phenyl)pentaerythritol diphosphite and bis{2,4-bis(1-methyl-1-phenylethyl)phenyl}pentaerythritol diphosphite.
また、例えば2,4,8,10-テトラ-t-ブチル-6-[3-(3-メチル-4-ヒドロキシ-5-t-ブチルフェニル)プロポキシ]ジベンゾ[d,f][1,3,2]ジオキサホスフェピン〔「スミライザーGP」(住友化学株式会社製)として市販されている。〕、2,10-ジメチル-4,8-ジ-t-ブチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロポキシ]-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ブチル-6-[3-(3、5-ジ-t-ブチル-4-ヒドロキシフェニル)プロポキシ]ジベンゾ[d,f][1,3,2]ジオキサホスフェピン、2,4,8,10-テトラ-t-ペンチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロポキシ]-12-メチル-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10-ジメチル-4,8-ジ-t-ブチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ペンチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-12-メチル-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ブチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオニルオキシ]-ジベンゾ[d,f][1,3,2]ジオキサホスフェピン、2,10-ジメチル-4,8-ジ-t-ブチル-6-(3,5-ジ-t-ブチル-4-ヒドロキシベンゾイルオキシ)-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ブチル-6-(3,5-ジ-t-ブチル-4-ヒドロキシベンゾイルオキシ)-12-メチル-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10-ジメチル-4,8-ジ-t-ブチル-6-[3-(3-メチル-4-ヒドロキシ-5-t-ブチルフェニル)プロポキシ]-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ブチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロポキシ]-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,10-ジエチル-4,8-ジ-t-ブチル-6-[3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロポキシ]-12H-ジベンゾ[d,g][1,3,2]ジオキサホスホシン、2,4,8,10-テトラ-t-ブチル-6-[2,2-ジメチル-3-(3-t-ブチル-4-ヒドロキシ-5-メチルフェニル)プロポキシ]-ジベンゾ[d,f][1,3,2]ジオキサホスフェピンなどを挙げることができる。これらはいずれも入手容易である。上記ホスファイト系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Also, for example, 2,4,8,10-tetra-t-butyl-6-[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propoxy]dibenzo[d,f][1,3 , 2] dioxaphosphepine [commercially available as "Sumilizer GP" (manufactured by Sumitomo Chemical Co., Ltd.). ], 2,10-dimethyl-4,8-di-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g] [1,3,2]dioxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]dibenzo [d,f][1,3,2]dioxaphosphepin, 2,4,8,10-tetra-t-pentyl-6-[3-(3,5-di-t-butyl-4- hydroxyphenyl)propoxy]-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,10-dimethyl-4,8-di-t-butyl-6-[3 -(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,4,8,10-tetra -t-pentyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-12-methyl-12H-dibenzo[d,g][1,3,2]di Oxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy]-dibenzo[d,f][ 1,3,2]dioxaphosphepine, 2,10-dimethyl-4,8-di-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy)-12H- Dibenzo[d,g][1,3,2]dioxaphosphosine, 2,4,8,10-tetra-t-butyl-6-(3,5-di-t-butyl-4-hydroxybenzoyloxy )-12-methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,10-dimethyl-4,8-di-t-butyl-6-[3-(3- methyl-4-hydroxy-5-t-butylphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,4,8,10-tetra-t-butyl- 6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]dioxaphosphosine, 2,10-diethyl- 4,8-di-t-butyl-6-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propoxy]-12H-dibenzo[d,g][1,3,2]di Oxaphosphosine, 2,4,8,10-tetra-t-butyl-6-[2,2-dimethyl-3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-dibenzo[ d,f][1,3,2]dioxaphosphepin and the like can be mentioned. All of these are readily available. The above phosphite compounds can be used alone or in combination of two or more.
ホスホナイト系化合物としては、テトラキス(2,4-ジ-tert-ブチルフェニル)-4,4’-ビフェニレンジホスホナイト、テトラキス(2,4-ジ-tert-ブチルフェニル)-4,3’-ビフェニレンジホスホナイト、テトラキス(2,4-ジ-tert-ブチルフェニル)-3,3’-ビフェニレンジホスホナイト、テトラキス(2,6-ジ-tert-ブチルフェニル)-4,4’-ビフェニレンジホスホナイト、テトラキス(2,6-ジ-tert-ブチルフェニル)-4,3’-ビフェニレンジホスホナイト、テトラキス(2,6-ジ-tert-ブチルフェニル)-3,3’-ビフェニレンジホスホナイト、ビス(2,4-ジ-tert-ブチルフェニル)-4-フェニル-フェニルホスホナイト、ビス(2,4-ジ-tert-ブチルフェニル)-3-フェニル-フェニルホスホナイト、ビス(2,6-ジ-n-ブチルフェニル)-3-フェニル-フェニルホスホナイト、ビス(2,6-ジ-tert-ブチルフェニル)-4-フェニル-フェニルホスホナイト、ビス(2,6-ジ-tert-ブチルフェニル)-3-フェニル-フェニルホスホナイト等が挙げられる。テトラキス(ジ-tert-ブチルフェニル)-ビフェニレンジホスホナイト、ビス(ジ-tert-ブチルフェニル)-フェニル-フェニルホスホナイトが好ましく、テトラキス(2,4-ジ-tert-ブチルフェニル)-ビフェニレンジホスホナイト、ビス(2,4-ジ-tert-ブチルフェニル)-フェニル-フェニルホスホナイトがより好ましい。かかるホスホナイト系化合物は上記アルキル基が2以上置換したアリール基を有するホスファイト系化合物との併用可能であり好ましい。ホスホナイト系化合物としてはテトラキス(2,4-ジ-tert-ブチルフェニル)-ビフェニレンジホスホナイトが好ましく、該ホスホナイトを主成分とする安定剤は、Sandostab P-EPQ(商標、Clariant社製)およびIrgafos P-EPQ(商標、CIBA SPECIALTY CHEMICALS社製)として市販されておりいずれも利用できる。上記ホスホナイト系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Phosphonite compounds include tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite, tetrakis(2,4-di-tert-butylphenyl)-4,3'-biphenyl diphosphonite, tetrakis(2,4-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-4,4'-biphenylenediphosphonite night, tetrakis(2,6-di-tert-butylphenyl)-4,3'-biphenylenediphosphonite, tetrakis(2,6-di-tert-butylphenyl)-3,3'-biphenylenediphosphonite, bis(2,4-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, bis(2,4-di-tert-butylphenyl)-3-phenyl-phenylphosphonite, bis(2,6- Di-n-butylphenyl)-3-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl)-4-phenyl-phenylphosphonite, Bis(2,6-di-tert-butylphenyl) )-3-phenyl-phenylphosphonite and the like. Tetrakis(di-tert-butylphenyl)-biphenylenediphosphonite, bis(di-tert-butylphenyl)-phenyl-phenylphosphonite are preferred, and tetrakis(2,4-di-tert-butylphenyl)-biphenylenediphosphonite Night, bis(2,4-di-tert-butylphenyl)-phenyl-phenylphosphonite is more preferred. Such a phosphonite-based compound can be used in combination with a phosphite-based compound having an aryl group substituted with two or more alkyl groups, and is therefore preferable. Tetrakis (2,4-di-tert-butylphenyl)-biphenylene diphosphonite is preferable as the phosphonite compound, and the stabilizer containing the phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant) and Irgafos. It is commercially available as P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and any of them can be used. The above phosphonite compounds can be used alone or in combination of two or more.
チオエーテル系化合物の具体例として、ジラウリルチオジプロピオネート、ジトリデシルチオジプロピオネート、ジミリスチルチオジプロピオネート、ジステアリルチオジプロピオネート、ペンタエリスリトール-テトラキス(3-ラウリルチオプロピオネート)、ペンタエリスリトール-テトラキス(3-ドデシルチオプロピオネート)、ペンタエリスリトール-テトラキス(3-オクタデシルチオプロピオネート)、ペンタエリスリトールテトラキス(3-ミリスチルチオプロピオネート)、ペンタエリスリトール-テトラキス(3-ステアリルチオプロピオネート)等が挙げられる。上記チオエーテル系化合物は、単独でまたは2種以上を組み合わせて使用することができる。 Specific examples of thioether compounds include dilaurylthiodipropionate, ditridecylthiodipropionate, dimyristylthiodipropionate, distearylthiodipropionate, pentaerythritol-tetrakis(3-laurylthiopropionate), Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3-stearylthio propionate) and the like. The above thioether compounds can be used alone or in combination of two or more.
酸化防止剤の含有量は、A成分100重量部に対し、0.01~2重量部が好ましく、より好ましくは0.03~1重量部、さらに好ましくは0.05~0.5重量部である。酸化防止剤の含有量が0.01重量部より少ない場合は酸化防止効果が不足し、成形加工時の色相や流動性が不安定になるだけでなく、耐加水分解性も悪化する場合がある。また、かかる含有量が2重量部よりも多い場合、酸化防止剤由来の反応成分などがかえって耐加水分解性を悪化させてしまう場合がある。 The content of the antioxidant is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, and still more preferably 0.05 to 0.5 parts by weight with respect to 100 parts by weight of component A. be. When the content of the antioxidant is less than 0.01 parts by weight, the antioxidant effect is insufficient, and not only the hue and fluidity during molding become unstable, but also the hydrolysis resistance may deteriorate. . On the other hand, if the content is more than 2 parts by weight, the reactive components derived from the antioxidant may rather deteriorate the hydrolysis resistance.
また、前記ヒンダードフェノール系化合物とホスファイト系化合物、ホスホナイト系化合物、チオエーテル系化合物のいずれか2種類以上を組み合わせて使用することが好ましい。ヒンダードフェノール系化合物とホスファイト系化合物、ホスホナイト系化合物、チオエーテル系化合物のいずれか2種類以上を組み合わせて使用することで、安定剤としての相乗効果が発揮され、より成形加工時の色相、流動性の安定化、耐加水分解性の向上に効果がある。 Further, it is preferable to use a combination of two or more of the hindered phenol-based compound, the phosphite-based compound, the phosphonite-based compound, and the thioether-based compound. By using a combination of two or more types of hindered phenol-based compounds and phosphite-based compounds, phosphonite-based compounds, and thioether-based compounds, a synergistic effect as a stabilizer is exhibited, resulting in better color and fluidity during molding. It is effective in stabilizing properties and improving hydrolysis resistance.
<離型剤>
本発明の樹脂組成物は離型剤を含むことができる。離型剤として具体的には、脂肪酸、脂肪酸金属塩、オキシ脂肪酸、パラフィン、低分子量のポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミド、脂肪族ケトン、脂肪酸部分鹸化エステル、脂肪酸低級アルコールエステル、脂肪酸多価アルコールエステル、脂肪酸ポリグリコールエステルおよび変性シリコーン等を挙げることができる。これらを配合することで機械特性、成形性、耐熱性に優れた成形品を得ることができる。
<Release agent>
The resin composition of the present invention can contain a release agent. Specific examples of release agents include fatty acids, fatty acid metal salts, oxyfatty acids, paraffins, low-molecular-weight polyolefins, fatty acid amides, alkylenebis fatty acid amides, aliphatic ketones, fatty acid partially saponified esters, fatty acid lower alcohol esters, and fatty acid polyvalents. Examples include alcohol esters, fatty acid polyglycol esters and modified silicones. By blending these, a molded article having excellent mechanical properties, moldability and heat resistance can be obtained.
脂肪酸としては炭素数6~40のものが好ましく、具体的には、オレイン酸、ステアリン酸、ラウリン酸、ヒドロキシステアリン酸、ベヘン酸、アラキドン酸、リノール酸、リノレン酸、リシノール酸、パルミチン酸、モンタン酸およびこれらの混合物等が挙げられる。脂肪酸金属塩としては炭素数6~40の脂肪酸のアルカリ(土類)金属塩が好ましく、具体的にはステアリン酸カルシウム、モンタン酸ナトリウム、モンタン酸カルシウム等が挙げられる。 Fatty acids preferably have 6 to 40 carbon atoms, and specific examples include oleic acid, stearic acid, lauric acid, hydroxystearic acid, behenic acid, arachidonic acid, linoleic acid, linolenic acid, ricinoleic acid, palmitic acid, and montan. Acids and mixtures thereof and the like. The fatty acid metal salt is preferably an alkali (earth) metal salt of a fatty acid having 6 to 40 carbon atoms, and specific examples include calcium stearate, sodium montanate, calcium montanate and the like.
オキシ脂肪酸としては1,2-オキシステリン酸等が挙げられる。パラフィンとしては炭素数18以上のものが好ましく、流動パラフィン、天然パラフィン、マイクロクリスタリンワックス、ペトロラクタム等が挙げられる。 Oxy fatty acids include 1,2-oxysteric acid and the like. As the paraffin, those having 18 or more carbon atoms are preferable, and examples thereof include liquid paraffin, natural paraffin, microcrystalline wax, and petrolactam.
低分子量のポリオレフィンとしては例えば分子量5000以下のものが好ましく、具体的にはポリエチレンワックス、マレイン酸変性ポリエチレンワックス、酸化タイプポリエチレンワックス、塩素化ポリエチレンワックス、ポリプロピレンワックス等が挙げられる。 Low-molecular-weight polyolefins preferably have a molecular weight of 5,000 or less, and specific examples include polyethylene wax, maleic acid-modified polyethylene wax, oxidized-type polyethylene wax, chlorinated polyethylene wax, and polypropylene wax.
脂肪酸アミドとしては炭素数6以上のものが好ましく、具体的にはオレイン酸アミド、エルカ酸アミド、ベヘン酸アミド等が挙げられる。 As the fatty acid amide, those having 6 or more carbon atoms are preferable, and specific examples include oleic acid amide, erucic acid amide, and behenic acid amide.
アルキレンビス脂肪酸アミドとしては炭素数6以上のものが好ましく、具体的にはメチレンビスステアリン酸アミド、エチレンビスステアリン酸アミド、N,N-ビス(2-ヒドロキシエチル)ステアリン酸アミド等が挙げられる。 The alkylenebis fatty acid amide preferably has 6 or more carbon atoms, and specific examples include methylenebisstearic acid amide, ethylenebisstearic acid amide, N,N-bis(2-hydroxyethyl)stearic acid amide and the like.
脂肪族ケトンとしては炭素数6以上のものが好ましく、高級脂肪族ケトン等が挙げられる。 As the aliphatic ketone, those having 6 or more carbon atoms are preferable, and examples thereof include higher aliphatic ketones.
脂肪酸部分鹸化エステルとしてはモンタン酸部分鹸化エステル等が挙げられる。脂肪酸低級アルコールエステルとしてはステアリン酸エステル、オレイン酸エステル、リノール酸エステル、リノレン酸エステル、アジピン酸エステル、ベヘン酸エステル、アラキドン酸エステル、モンタン酸エステル、イソステアリン酸エステル等が挙げられる。 Partially saponified fatty acid esters include partially saponified montanic acid esters. Examples of fatty acid lower alcohol esters include stearates, oleates, linoleates, linolenates, adipates, behenates, arachidonates, montanates and isostearates.
脂肪酸多価アルコールエステルとしては、グリセロールトリステアレート、グリセロールジステアレート、グリセロールモノステアレート、ペンタエリスルトールテトラステアレート、ペンタエリスルトールトリステアレート、ペンタエリスルトールジミリステート、ペンタエリスルトールモノステアレート、ペンタエリスルトールアジペートステアレート、ソルビタンモノベヘネート等が挙げられる。脂肪酸ポリグリコールエステルとしてはポリエチレングリコール脂肪酸エステル、ポリトリメチレングリコール脂肪酸エステル、ポリプロピレングリコール脂肪酸エステル等が挙げられる。 Examples of fatty acid polyhydric alcohol esters include glycerol tristearate, glycerol distearate, glycerol monostearate, pentaerythritol tetrastearate, pentaerythritol tristearate, pentaerythritol dimilystate, and pentaerythritol. Toll monostearate, pentaerythritol adipate stearate, sorbitan monobehenate and the like. Examples of fatty acid polyglycol esters include polyethylene glycol fatty acid esters, polytrimethylene glycol fatty acid esters, polypropylene glycol fatty acid esters, and the like.
変性シリコーンとしてはポリエーテル変性シリコーン、高級脂肪酸アルコキシ変性シリコーン、高級脂肪酸含有シリコーン、高級脂肪酸エステル変性シリコーン、メタクリル変性シリコーン、フッ素変性シリコーン等が挙げられる。 Modified silicones include polyether-modified silicones, higher fatty acid alkoxy-modified silicones, higher fatty acid-containing silicones, higher fatty acid ester-modified silicones, methacryl-modified silicones, and fluorine-modified silicones.
そのうち脂肪酸、脂肪酸金属塩、オキシ脂肪酸、脂肪酸エステル、脂肪酸部分鹸化エステル、パラフィン、低分子量ポリオレフィン、脂肪酸アミド、アルキレンビス脂肪酸アミドが好ましく、脂肪酸部分鹸化エステル、アルキレンビス脂肪酸アミドがより好ましい。なかでもモンタン酸エステル、モンタン酸部分鹸化エステル、ポリエチレンワックス、酸価ポリエチレンワックス、ソルビタン脂肪酸エステル、エルカ酸アミド、エチレンビスステアリン酸アミドが好ましく、特にモンタン酸部分鹸化エステル、エチレンビスステアリン酸アミドが好ましい。 Of these, fatty acids, fatty acid metal salts, oxyfatty acids, fatty acid esters, partially saponified fatty acid esters, paraffins, low molecular weight polyolefins, fatty acid amides, and alkylenebis fatty acid amides are preferred, and partially saponified fatty acid esters and alkylenebis fatty acid amides are more preferred. Among them, montanic acid ester, partially saponified montanic acid ester, polyethylene wax, acid value polyethylene wax, sorbitan fatty acid ester, erucic acid amide, and ethylenebisstearic acid amide are preferred, and partially saponified montanic acid ester and ethylenebisstearic acid amide are particularly preferred. .
離型剤は、1種類で用いても良いし2種以上を組み合わせて用いても良い。離型剤の含有量は、A成分100重量部に対し、好ましくは0.01~3重量部、より好ましくは0.03~2重量部である。 The release agent may be used alone or in combination of two or more. The content of the release agent is preferably 0.01 to 3 parts by weight, more preferably 0.03 to 2 parts by weight, per 100 parts by weight of component A.
<樹脂組成物の製造方法>
本発明の樹脂組成物を製造するには、任意の方法が採用される。例えば各成分、並びに任意に他の成分を予備混合し、その後溶融混練し、ペレット化する方法を挙げることができる。予備混合の手段としては、ナウターミキサー、V型ブレンダー、ヘンシェルミキサー、メカノケミカル装置、押出混合機などを挙げることができる。予備混合においては場合により押出造粒器やブリケッティングマシーンなどにより造粒を行うこともできる。予備混合後、ベント式二軸押出機に代表される溶融混練機で溶融混練、およびペレタイザー等の機器によりペレット化する。溶融混練機としては他にバンバリーミキサー、混練ロール、恒熱撹拌容器などを挙げることができるが、ベント式ニ軸押出機が好ましい。他に、各成分、並びに任意に他の成分を予備混合することなく、それぞれ独立に二軸押出機に代表される溶融混練機に供給する方法も取ることもできる。
<Method for producing resin composition>
Any method may be employed to produce the resin composition of the present invention. For example, a method of premixing each component and optionally other components, followed by melt-kneading and pelletizing can be mentioned. Means for premixing include a Nauta mixer, a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, and the like. In the pre-mixing, granulation can be performed by an extrusion granulator, a briquetting machine, or the like. After pre-mixing, the mixture is melt-kneaded by a melt-kneader typified by a vented twin-screw extruder, and pelletized by a device such as a pelletizer. Other examples of the melt-kneader include a Banbury mixer, a kneading roll, a constant temperature stirring vessel and the like, but a vented twin-screw extruder is preferred. Alternatively, each component and, optionally, other components may be supplied independently to a melt-kneader typified by a twin-screw extruder without being premixed.
<成形体について>
本発明の樹脂組成物からなる成形体は、上記の如く製造されたペレットを成形して得ることができる。好適には、射出成形、押出成形により得られる。射出成形においては、通常の成形方法だけでなく、射出圧縮成形、射出プレス成形、ガスアシスト射出成形、発泡成形(超臨界流体を注入する方法を含む)、インサート成形、インモールドコーティング成形、断熱金型成形、急速加熱冷却金型成形、二色成形、多色成形、サンドイッチ成形、および超高速射出成形等を挙げることができる。また成形はコールドランナー方式およびホットランナー方式のいずれも選択することができる。成形体は、開口部となる口部、胴部および底部を有する容器形状であり、容器中央部の肉厚が0.5~2mmであり、かつ波長450nmにおける光線透過率が55%以上である成形体であることが好ましい。押出成形においては、各種異形押出成形品、シート、フィルムなどの形で使用することもできる。またシート、フィルムの成形にはインフレーション法や、カレンダー法、キャスティング法なども使用可能である。さらに、シート形状の成形体を真空成形やプレス成形により特定形状を付与した成形体とし使用することも可能である。
<About the compact>
A molded article made of the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, heat insulation metal Mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, ultra-high speed injection molding and the like can be mentioned. For molding, either cold runner method or hot runner method can be selected. The molded body has a container shape having a mouth portion serving as an opening, a body portion and a bottom portion. Molded bodies are preferred. In extrusion molding, it can also be used in the form of various profile extrusion moldings, sheets, films, and the like. In addition, the inflation method, calender method, casting method, and the like can be used for forming sheets and films. Furthermore, it is also possible to use the sheet-shaped molded body as a molded body that has been given a specific shape by vacuum forming or press molding.
以下、実施例により本発明を実施する形態を説明するが、本発明はこれらに限定されるものではない。また、諸物性の評価は以下の方法により実施した。 [EXAMPLES] Hereafter, although the form which implements this invention is demonstrated by an Example, this invention is not limited to these. Moreover, evaluation of various physical properties was carried out by the following methods.
[樹脂組成物の評価]
(1)透明性
下記の方法で得られたペレットを140℃で7時間乾燥した後に、射出成形機(東芝機械(株)製 EC130SXII―4Y)によりシリンダー温度310℃、金型温度90℃の条件にて長さ25mm、幅50mm、厚み1mmの試験片を成形し、日本分光(株)製紫外可視分光光度計V-560により450nmの波長における光線透過率を測定した。光線透過率は55%以上であることが必要である。
(2)ガラス転移温度
下記の方法で得られたペレットを使用して、示差走査熱量計(TAインスツルメント・ジャパン(株)製:DSC-2910)により昇温速度20℃/minの条件でガラス転移温度(Tg)を測定した。
ガラス転移温度は140℃以上であることが必要である。
[Evaluation of Resin Composition]
(1) Transparency After drying the pellets obtained by the following method at 140 ° C. for 7 hours, an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) was used with a cylinder temperature of 310 ° C. and a mold temperature of 90 ° C. A test piece having a length of 25 mm, a width of 50 mm, and a thickness of 1 mm was molded with a UV-visible spectrophotometer V-560 manufactured by JASCO Corporation, and the light transmittance at a wavelength of 450 nm was measured. The light transmittance should be 55% or more.
(2) Glass transition temperature Using pellets obtained by the following method, a differential scanning calorimeter (manufactured by TA Instruments Japan Co., Ltd.: DSC-2910) was used at a temperature increase rate of 20 ° C. / min. The glass transition temperature (Tg) was measured.
The glass transition temperature should be 140° C. or higher.
[実施例1-7、比較例1-2]
表1で示した含有量に従って、A成分およびB成分を第1供給口より別々に二軸押出機に供給し310℃の温度にて溶融混練押出してペレット化した。ここで第1供給口とは根元の供給口のことである。二軸押出機は、径30mmΦのベント式二軸押出機((株)日本製鋼所製:TEX30α-31.5BW-2V)を使用した。
本発明の実施例および比較例には、以下の材料を使用した。
[Example 1-7, Comparative Example 1-2]
According to the contents shown in Table 1, the A component and the B component were supplied separately from the first supply port to a twin-screw extruder and melt-kneaded and extruded at a temperature of 310° C. to form pellets. Here, the first supply port is the root supply port. The twin-screw extruder used was a vented twin-screw extruder with a diameter of 30 mmΦ (manufactured by Japan Steel Works, Ltd.: TEX30α-31.5BW-2V).
The following materials were used in the examples and comparative examples of the present invention.
(A成分)
A-I:製造例Iで得られたポリエチレンナフタレート樹脂
<製造例I>
ナフタレンジカルボン酸ジメチルエステル100重量部およびエチレングリコール51重量部を、酢酸コバルト四水和物0.003重量部(0.012mmol)、酢酸カルシウム一水和物0.014重量部(0.08mmol)および酢酸マンガン四水和物0.044重量部(0.0205mmol)をエステル交換触媒として用い、常法によりエステル交換反応させ、非晶性二酸化ゲルマニウムのエチレングリコール1%溶液1.5重量部(0.14mmol)を添加したのちに、トリメチルフォスフェート0.0057重量部(0.41mmol)を添加しエステル交換反応を終了せしめた。次いで温度227℃、真空度0.5Torrの条件にて8時間固相重合を行い固有粘度が0.60dl/gのポリエチレンナフタレート樹脂を得た。
(A component)
AI: Polyethylene naphthalate resin obtained in Production Example I <Production Example I>
100 parts by weight of naphthalenedicarboxylic acid dimethyl ester and 51 parts by weight of ethylene glycol, 0.003 parts by weight (0.012 mmol) of cobalt acetate tetrahydrate, 0.014 parts by weight (0.08 mmol) of calcium acetate monohydrate and Using 0.044 parts by weight (0.0205 mmol) of manganese acetate tetrahydrate as a transesterification catalyst, transesterification was carried out by a conventional method, and 1.5 parts by weight (0.0205 mmol) of ethylene glycol 1% solution of amorphous germanium dioxide was obtained. 14 mmol) was added, and then 0.0057 parts by weight (0.41 mmol) of trimethyl phosphate was added to terminate the transesterification reaction. Solid phase polymerization was then carried out for 8 hours at a temperature of 227° C. and a degree of vacuum of 0.5 Torr to obtain a polyethylene naphthalate resin having an intrinsic viscosity of 0.60 dl/g.
(B成分)
B-I:SHPPジャパン合同会社製 ULTEM1010(商品名)
(B component)
B-I: ULTEM1010 (trade name) manufactured by SHPP Japan LLC
<実施例1~7>
本請求の範囲内にある組成物であるため、透明性、耐熱性に優れた成形体を得ることができた。
<Examples 1 to 7>
Since the composition is within the scope of the claims, a molded article having excellent transparency and heat resistance could be obtained.
<比較例1>
B成分の含有量が下限未満であるため、耐熱性が改善されなかった。
<比較例2>
B成分の含有量が上限を超えるため、透明性に劣る結果であった。
<Comparative Example 1>
Since the content of component B was less than the lower limit, heat resistance was not improved.
<Comparative Example 2>
Since the content of component B exceeded the upper limit, the result was poor transparency.
Claims (3)
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