JP2023038867A - Liquid masterbatch, resin molding material, and resin molding - Google Patents
Liquid masterbatch, resin molding material, and resin molding Download PDFInfo
- Publication number
- JP2023038867A JP2023038867A JP2021145811A JP2021145811A JP2023038867A JP 2023038867 A JP2023038867 A JP 2023038867A JP 2021145811 A JP2021145811 A JP 2021145811A JP 2021145811 A JP2021145811 A JP 2021145811A JP 2023038867 A JP2023038867 A JP 2023038867A
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- JP
- Japan
- Prior art keywords
- liquid
- resin
- fatty acid
- liquid masterbatch
- masterbatch
- 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.)
- Granted
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- 239000007788 liquid Substances 0.000 title claims abstract description 125
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 91
- 229920005989 resin Polymers 0.000 title claims abstract description 83
- 239000011347 resin Substances 0.000 title claims abstract description 83
- 238000000465 moulding Methods 0.000 title claims abstract description 36
- 239000012778 molding material Substances 0.000 title claims abstract description 28
- -1 polyethylene terephthalate Polymers 0.000 claims abstract description 69
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 61
- 239000000194 fatty acid Substances 0.000 claims abstract description 61
- 229930195729 fatty acid Natural products 0.000 claims abstract description 61
- 239000004094 surface-active agent Substances 0.000 claims abstract description 38
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000007787 solid Substances 0.000 claims abstract description 31
- 229920001707 polybutylene terephthalate Polymers 0.000 claims abstract description 19
- 229920000139 polyethylene terephthalate Polymers 0.000 claims abstract description 14
- 239000005020 polyethylene terephthalate Substances 0.000 claims abstract description 14
- 239000004431 polycarbonate resin Substances 0.000 claims abstract description 13
- 229920005668 polycarbonate resin Polymers 0.000 claims abstract description 13
- 239000004359 castor oil Substances 0.000 claims abstract description 11
- 235000019438 castor oil Nutrition 0.000 claims abstract description 11
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 11
- 239000000344 soap Substances 0.000 claims abstract description 10
- 239000000975 dye Substances 0.000 claims description 33
- 239000000049 pigment Substances 0.000 claims description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims description 22
- 238000003860 storage Methods 0.000 abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 abstract description 12
- 230000007774 longterm Effects 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 150000002314 glycerols Chemical class 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 12
- 239000008188 pellet Substances 0.000 description 12
- 238000004062 sedimentation Methods 0.000 description 12
- 239000000654 additive Substances 0.000 description 9
- 239000003086 colorant Substances 0.000 description 9
- 238000004898 kneading Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000015112 vegetable and seed oil Nutrition 0.000 description 6
- 239000008158 vegetable oil Substances 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 239000012141 concentrate Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000001815 facial effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 239000001023 inorganic pigment Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000011146 organic particle Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 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 2
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 2
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 235000019482 Palm oil Nutrition 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 229920001214 Polysorbate 60 Polymers 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000010775 animal oil Substances 0.000 description 2
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 2
- 150000004056 anthraquinones Chemical class 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000002216 antistatic agent Substances 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000000071 blow moulding Methods 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
- 150000004650 carbonic acid diesters Chemical class 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-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
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000008258 liquid foam Substances 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
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- UTOPWMOLSKOLTQ-UHFFFAOYSA-N octacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O UTOPWMOLSKOLTQ-UHFFFAOYSA-N 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 239000002540 palm oil Substances 0.000 description 2
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 2
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 235000013772 propylene glycol Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 229940037312 stearamide Drugs 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-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
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- CUNWUEBNSZSNRX-RKGWDQTMSA-N (2r,3r,4r,5s)-hexane-1,2,3,4,5,6-hexol;(z)-octadec-9-enoic acid Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O.CCCCCCCC\C=C/CCCCCCCC(O)=O CUNWUEBNSZSNRX-RKGWDQTMSA-N 0.000 description 1
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 description 1
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- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 description 1
- HCNHNBLSNVSJTJ-UHFFFAOYSA-N 1,1-Bis(4-hydroxyphenyl)ethane Chemical compound C=1C=C(O)C=CC=1C(C)C1=CC=C(O)C=C1 HCNHNBLSNVSJTJ-UHFFFAOYSA-N 0.000 description 1
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- FWLHAQYOFMQTHQ-UHFFFAOYSA-N 2-N-[8-[[8-(4-aminoanilino)-10-phenylphenazin-10-ium-2-yl]amino]-10-phenylphenazin-10-ium-2-yl]-8-N,10-diphenylphenazin-10-ium-2,8-diamine hydroxy-oxido-dioxochromium Chemical compound O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.O[Cr]([O-])(=O)=O.Nc1ccc(Nc2ccc3nc4ccc(Nc5ccc6nc7ccc(Nc8ccc9nc%10ccc(Nc%11ccccc%11)cc%10[n+](-c%10ccccc%10)c9c8)cc7[n+](-c7ccccc7)c6c5)cc4[n+](-c4ccccc4)c3c2)cc1 FWLHAQYOFMQTHQ-UHFFFAOYSA-N 0.000 description 1
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- KTMNDTPAJZKQPF-UHFFFAOYSA-N 2-tert-butyl-4-[1-(3-tert-butyl-4-hydroxyphenyl)propyl]phenol Chemical compound C=1C=C(O)C(C(C)(C)C)=CC=1C(CC)C1=CC=C(O)C(C(C)(C)C)=C1 KTMNDTPAJZKQPF-UHFFFAOYSA-N 0.000 description 1
- YMTYZTXUZLQUSF-UHFFFAOYSA-N 3,3'-Dimethylbisphenol A Chemical compound C1=C(O)C(C)=CC(C(C)(C)C=2C=C(C)C(O)=CC=2)=C1 YMTYZTXUZLQUSF-UHFFFAOYSA-N 0.000 description 1
- CKNCVRMXCLUOJI-UHFFFAOYSA-N 3,3'-dibromobisphenol A Chemical compound C=1C=C(O)C(Br)=CC=1C(C)(C)C1=CC=C(O)C(Br)=C1 CKNCVRMXCLUOJI-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
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 description 1
- RQCACQIALULDSK-UHFFFAOYSA-N 4-(4-hydroxyphenyl)sulfinylphenol Chemical compound C1=CC(O)=CC=C1S(=O)C1=CC=C(O)C=C1 RQCACQIALULDSK-UHFFFAOYSA-N 0.000 description 1
- RSSGMIIGVQRGDS-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)-phenylmethyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=CC=C1 RSSGMIIGVQRGDS-UHFFFAOYSA-N 0.000 description 1
- OVVCSFQRAXVPGT-UHFFFAOYSA-N 4-[1-(4-hydroxyphenyl)cyclopentyl]phenol Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCC1 OVVCSFQRAXVPGT-UHFFFAOYSA-N 0.000 description 1
- QHJPJZROUNGTRJ-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)octan-2-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)(CCCCCC)C1=CC=C(O)C=C1 QHJPJZROUNGTRJ-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
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Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は樹脂の液状マスターバッチ、樹脂成形材料、及び樹脂成形体に関する。 TECHNICAL FIELD The present invention relates to a resin liquid masterbatch, a resin molding material, and a resin molding.
近年、熱可塑性樹脂を用いた樹脂成形体は、成形加工が容易なことから容器、電気・電子部品、自動車部品など幅広い分野で利用されている。これら樹脂成形体は、使用用途に応じて機能性を高めるために添加剤を樹脂に混合する、また意匠性を高めるために顔料や染料によって樹脂を着色することが一般的に行われている。 BACKGROUND ART In recent years, resin molded articles using thermoplastic resins are used in a wide range of fields such as containers, electric/electronic parts, and automobile parts, because they are easy to mold. Generally, these resin moldings are mixed with additives in order to enhance their functionality according to their intended use, and are colored with pigments or dyes in order to enhance their design.
押出成形、射出成形、ブロー成形などの樹脂成形体の加工における添加剤の混合や、顔料や染料による着色は、あらかじめ高い濃度の添加剤濃縮物や着色剤濃縮物を作成し、成形直前に樹脂ペレットや樹脂粉により希釈する方法がとられる。こうした添加剤濃縮物や着色剤濃縮物の形態としては、樹脂と添加剤または顔染料を混練してペレット状にしたマスターバッチ、樹脂ペレット表面に顔染料を付着させたカラードペレット、金属石鹸と顔染料を混合してペースト状としたドライカラー、および添加剤または顔染料を油に分散させた液状マスターバッチ等が挙げられる。 Mixing of additives and coloring with pigments and dyes in the processing of resin moldings such as extrusion molding, injection molding, blow molding, etc., are performed by preparing high-concentration additive concentrates and colorant concentrates in advance, and adding resin immediately before molding. A method of dilution with pellets or resin powder is adopted. The forms of such additive concentrates and colorant concentrates include masterbatch pellets made by kneading resin and additives or facial dyes, colored pellets made by attaching facial dyes to the surface of resin pellets, metal soap and facial dyes, and so on. Examples include dry color pastes obtained by mixing dyes, and liquid masterbatches prepared by dispersing additives or facial dyes in oil.
なかでも、液状マスターバッチは、他の濃縮物と異なり、状態が液体であるため、樹脂ペレットや樹脂粉により希釈する際に、微量でも均一に混合され易く、混合が均一であることによる物性の向上や、透過色成形体の着色といった高度な分散が求められる用途に用いられてきた。 Among them, unlike other concentrates, the liquid masterbatch is in a liquid state, so when diluted with resin pellets or resin powder, even a small amount is easily mixed uniformly, and the physical properties due to uniform mixing are improved. It has been used for applications that require high degree of dispersion such as improvement and coloring of transmissive color moldings.
しかし、液状マスターバッチは、状態が（低粘度の）液体であるため、長期保管により添加剤、顔料、染料が液体底面に分離、沈降し易く、再使用する際は、再撹拌処理をする必要があった。 However, since the liquid masterbatch is a (low-viscosity) liquid, additives, pigments, and dyes tend to separate and settle to the bottom of the liquid during long-term storage, and must be re-stirred when reused. was there.
特許文献１は、顔料または染料と、脂肪族ジカルボン酸と二価アルコールを反応させて得られる液状ポリエステルを含むＡＢＳ樹脂用液状着色剤が記載されており、高温下における成形品の熱変形や、表面へのブリードがない成形品が得られる、とある。
しかし、前記のように液体であるため、長期保管により顔料、染料が沈降する。この沈降を防止するために液状マスターバッチへ分散剤を配合すると、複数ロット作製した成形品の表面に前記液状ポリエステル由来の液泡が発生することがあった。
Patent Document 1 describes a liquid colorant for ABS resin containing a liquid polyester obtained by reacting a pigment or dye with an aliphatic dicarboxylic acid and a dihydric alcohol. It states that a molded product without bleeding to the surface can be obtained.
However, since it is a liquid as described above, the pigments and dyes settle out during long-term storage. When a dispersant is added to the liquid masterbatch to prevent this sedimentation, liquid bubbles originating from the liquid polyester sometimes occur on the surface of molded articles produced in multiple lots.
また、特許文献２は、金属酸化物粒子と、可塑剤と、分散剤を含み、特定の成形体とした時のヘイズ差をパラメータとした金属酸化物粒子分散液が記載されており、液体の可塑剤として多価カルボン酸と多価アルコールの反応によって得られる脂肪酸ポリエステル樹脂、ポリアルキレングリコール樹脂、ポリエーテルエステル樹脂、及びアセチルクエン酸トリブチルより選択し、分散剤をリン酸エステル化合物とすることで、ナノサイズの金属酸化物粒子を用いた場合にも、物性の低下なく高分散な透明性の成形体が得られ、安定した分散液を作製できる、とある。 In addition, Patent Document 2 describes a metal oxide particle dispersion containing metal oxide particles, a plasticizer, and a dispersant, and using a haze difference as a parameter when forming a specific molded body. Fatty acid polyester resin obtained by reaction of polyhydric carboxylic acid and polyhydric alcohol as plasticizer, polyalkylene glycol resin, polyether ester resin, and tributyl acetylcitrate are selected, and dispersant is phosphoric acid ester compound. , that even when nano-sized metal oxide particles are used, a highly dispersed transparent molded article can be obtained without deterioration in physical properties, and a stable dispersion can be produced.
また、特許文献３は、樹脂と、ヨウ素価が９０以上の植物油脂を含有する液状着色剤とを混練し、樹脂あるいは液状着色剤のいずれかにフェルト自然沈降法が特定の値を示す界面活性剤を添加した樹脂着色用マスターバッチの製造方法であり、顔料の分散性が良好であり、色ムラなく良好に着色された樹脂着色用マスターバッチが得られる、とある。 Further, Patent Document 3 discloses kneading a resin and a liquid coloring agent containing a vegetable oil having an iodine value of 90 or more, and applying a felt natural sedimentation method to either the resin or the liquid coloring agent to exhibit a specific surfactant surface activity. It is a method for producing a resin-coloring masterbatch to which a coloring agent is added, and the dispersibility of the pigment is good, and a well-colored resin-coloring masterbatch without color unevenness can be obtained.
しかし、特許文献２はナノ粒子特有の課題解決の発明であり、分散液の沈降も、成形体を複数ロット作製した際の成形体表面の状態についても記載されていない。また特許文献３は液体着色剤作製後に樹脂と混練しているため液体着色剤における沈降についての視点はなく、また実施例ではホットプレートで薄膜を作製しているように、成形体における問題点についても触れられていない。 However, Patent Document 2 is an invention for solving problems peculiar to nanoparticles, and neither the sedimentation of the dispersion liquid nor the state of the surface of the molded body when a plurality of lots of molded bodies are produced is described. Further, in Patent Document 3, since the liquid coloring agent is kneaded with the resin after the liquid coloring agent is prepared, there is no point of view regarding sedimentation in the liquid coloring agent. has not been touched.
本発明は、長期保存において固体粒子が分離、沈降することのない保存安定性、および樹脂と混合し成形を行った際に、多数のロットの成形においても成形体表面に液泡が生じない成形性を備えた液状マスターバッチと、前記液状マスターバッチを用いた樹脂成形材料および成形体を提供する。
また、固体粒子を顔料および染料として着色用途に用いた際に、沈降による顔料または染料の偏りが生じることがない分散性の優れた液状マスターバッチを提供する。
The present invention provides storage stability in which solid particles do not separate or sediment during long-term storage, and moldability in which liquid bubbles do not occur on the surface of molded products even when molding is performed by mixing with a resin in a large number of lots. and a resin molding material and molded article using the liquid masterbatch.
Further, the present invention provides a liquid masterbatch excellent in dispersibility, which does not cause uneven distribution of pigments or dyes due to sedimentation when solid particles are used as pigments or dyes for coloring purposes.
本発明者らは、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、またはポリカーボネート樹脂の成形に用いられる液状マスターバッチであって、
前記液状マスターバッチは、常温で液状の脂肪酸エステル（Ａ）と、固体粒子（Ｂ）と、界面活性剤（Ｃ）を含み、前記脂肪酸エステル（Ａ）は、脂肪酸を有するジアセチルモノアシルグリセロール、および／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体を含み、前記界面活性剤（Ｃ）が、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも1つであることを特徴とする、液状マスターバッチであることにより、上記目的を達成できることを見出し、本発明を完成するに至った。
The present inventors have found a liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin,
The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C), wherein the fatty acid ester (A) is diacetyl monoacylglycerol having a fatty acid, and / or containing a diacetyl monoacylglycerol derivative having a fatty acid, wherein the surfactant (C) is at least one selected from fatty acid amide surfactants, metallic soaps, and hydrogenated castor oil The inventors have found that the above object can be achieved by being a liquid masterbatch, and have completed the present invention.
すなわち、本発明は、
（１）ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、またはポリカーボネート樹脂の成形に用いられる液状マスターバッチであって、
前記液状マスターバッチは、常温で液状の脂肪酸エステル（Ａ）と、固体粒子（Ｂ）と、界面活性剤（Ｃ）を含み、
前記脂肪酸エステル（Ａ）は、脂肪酸を有するジアセチルモノアシルグリセロール、および／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体を含み、前記界面活性剤（Ｃ）が、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも1つであることを特徴とする、液状マスターバッチ、
（２）前記液状マスターバッチ中の、前記界面活性剤（Ｃ）が、前記液状マスターバッチ１００重量部に対して、０．２～１５重量部であることを特徴とする（１）に記載の液状マスターバッチ、
（３）（１）または（２）に記載の液状マスターバッチであって、液状マスターバッチ中の、固体粒子が顔料または染料であることを特徴とする液状マスターバッチ、
（４）（１）～（３）のいずれかに記載の液状マスターバッチと、熱可塑性樹脂を含む樹脂成形材料、
（５）（１）～（３）のいずれかに記載の前記液状マスターバッチを含む樹脂成形体、
である。
（６）（４）に記載の樹脂成形材料を成形してなる樹脂成形体。
That is, the present invention
(1) A liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin,
The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C),
The fatty acid ester (A) contains a diacetylmonoacylglycerol having a fatty acid and/or a diacetylmonoacylglycerol derivative having a fatty acid, and the surfactant (C) is a fatty acid amide surfactant, a metal soap, and A liquid masterbatch, characterized in that it is at least one selected from hydrogenated castor oil,
(2) The surfactant (C) in the liquid masterbatch is 0.2 to 15 parts by weight with respect to 100 parts by weight of the liquid masterbatch. liquid masterbatch,
(3) The liquid masterbatch according to (1) or (2), wherein the solid particles in the liquid masterbatch are pigments or dyes;
(4) The liquid masterbatch according to any one of (1) to (3) and a resin molding material containing a thermoplastic resin,
(5) a resin molded body containing the liquid masterbatch according to any one of (1) to (3);
is.
(6) A resin molding obtained by molding the resin molding material according to (4).
本発明によれば、長期保存において固体粒子が分離、沈降することのない保存安定性、および樹脂と混合後に成形を行った際に、多数のロットの成形においても成形体表面に液泡が生じない成形性を備えた液状マスターバッチと、前記液状マスターバッチを用いた樹脂成形材料および成形体を提供できる。
また、固体粒子を顔料および染料として着色用途に用いた際に、沈降による顔料または染料の偏りが生じることがない分散性の優れた液状マスターバッチを提供できる。
According to the present invention, the solid particles do not separate or sediment during long-term storage, and when molding is performed after mixing with the resin, liquid bubbles do not occur on the surface of the molded product even when molding a large number of lots. It is possible to provide a liquid masterbatch having moldability, and a resin molding material and a molded article using the liquid masterbatch.
In addition, when the solid particles are used as pigments and dyes for coloring applications, it is possible to provide a liquid masterbatch with excellent dispersibility that does not cause bias in the pigments or dyes due to sedimentation.
以下、本発明を実施するための形態を詳細に説明する。なお、本実施形態は、本発明を実施するための一形態に過ぎず、本発明は本実施形態によって限定されるものではなく、本発明の要旨を逸脱しない範囲で種々の変更、実施の形態が可能である。また、本明細書中、数値範囲の説明における「ａ～ｂ」との表記は、特に断らない限り、ａ以上ｂ以下のことを表す。例えば、「１～５重量部」とは「１重量部以上５重量部以下」を意味する。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments for carrying out the present invention will be described in detail. It should be noted that the present embodiment is merely one form for carrying out the present invention, and the present invention is not limited by the present embodiment, and various modifications and embodiments can be made without departing from the gist of the present invention. is possible. Further, in this specification, the notation "a to b" in the description of numerical ranges means from a to b, unless otherwise specified. For example, "1 to 5 parts by weight" means "1 to 5 parts by weight".
本発明の液状マスターバッチは、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、またはポリカーボネート樹脂の成形に用いられる液状マスターバッチであって、常温で液状の脂肪酸エステル（Ａ）と、固体粒子（Ｂ）と、界面活性剤（Ｃ）を含み、前記脂肪酸エステルは、脂肪酸を有するジアセチルモノアシルグリセロールおよび／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体を含み、前記界面活性剤が、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも1つであることを特徴とする、液状マスターバッチである。 The liquid masterbatch of the present invention is a liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin, comprising a fatty acid ester (A) that is liquid at room temperature, solid particles (B), A surfactant (C) is included, wherein the fatty acid ester includes diacetyl monoacylglycerol having a fatty acid and/or a diacetyl monoacylglycerol derivative having a fatty acid, and the surfactant is a fatty acid amide-based surfactant or a metal soap. , and hydrogenated castor oil.
前記液状マスターバッチは、前記脂肪酸エステルと前記界面活性剤を併用することで、長期保存において固体粒子が沈降することのない保存安定性を備え、樹脂と混合後に複数ロットを成形した際に、成形体表面に液泡が生じない成形性を備えた液状マスターバッチを提供できる。
また、本発明の固体粒子が、顔料および染料である場合、沈降による顔料または染料の偏りが生じることがない分散性の優れた液状マスターバッチを提供できる。
By using the fatty acid ester and the surfactant together, the liquid masterbatch has storage stability in which solid particles do not settle during long-term storage, and when multiple lots are molded after mixing with the resin, molding It is possible to provide a liquid masterbatch having moldability that does not generate liquid bubbles on the body surface.
In addition, when the solid particles of the present invention are pigments and dyes, it is possible to provide a liquid masterbatch with excellent dispersibility that does not cause bias in the pigments or dyes due to sedimentation.
以下に、液状マスターバッチに含まれる組成物について記載する。 The compositions contained in the liquid masterbatch are described below.
[脂肪酸エステル]
本発明において、脂肪酸エステルは常温で液状であり、溶媒として用いられる。前記脂肪酸エステルとしては、脂肪酸を有するジアセチルモノアシルグリセロール、および／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体が用いられる。また、本発明において常温とは、２５℃を意味する。
[Fatty acid ester]
In the present invention, the fatty acid ester is liquid at room temperature and used as a solvent. As the fatty acid ester, a diacetylmonoacylglycerol having a fatty acid and/or a diacetylmonoacylglycerol derivative having a fatty acid is used. In the present invention, normal temperature means 25°C.
前記ジアセチルモノアシルグリセロールは、１価のアシル基と、２つのアセチル基を有する。
前記ジアセチルモノアシルグリセロールは、（ｉ）グリセロール、酢酸及びカルボキシル基を1つ有する脂肪酸とのエステル化反応、（ｉｉ）１つのエステル結合を有する脂肪酸アルキルエステルと、グリセロールまたは油脂等のトリグリセライドとをエステル交換反応したものを、アセチル化するなど公知の方法により得られるものであるが、その合成方法は特に限定されるものではない。
前記1価のアシル基の炭素数は、６～３６であることが好ましく、８～２４であることがより好ましい。
The diacetyl monoacylglycerol has a monovalent acyl group and two acetyl groups.
The diacetyl monoacylglycerol is obtained by (i) an esterification reaction with glycerol, acetic acid, and a fatty acid having one carboxyl group, and (ii) an esterification of a fatty acid alkyl ester having one ester bond with a triglyceride such as glycerol or oil. It can be obtained by a known method such as acetylation of an exchange-reacted product, but the synthesis method is not particularly limited.
The number of carbon atoms in the monovalent acyl group is preferably 6-36, more preferably 8-24.
前記ジアセチルモノアシルグリセロール誘導体は、２つのアセチル基、および脂肪酸の水酸基誘導体を有し、前記脂肪酸の水酸基誘導体は、水酸基を有する脂肪酸、若しくは水酸基を有する脂肪酸と１価のカルボキシル基を持つ脂肪酸とのエステルが挙げられる。前記水酸基を有する水酸基誘導体と、前記１価のカルボキシル基を持つ脂肪酸とのエステルを有する水酸基誘導体の、それぞれを有するジアセチルモノアシルグリセロール誘導体は、混合して用いることができる。
前記水酸基を有する脂肪酸の炭素数は、６～３６であることが好ましく、８～２４であることがより好ましい。
前記ジアセチルモノアシルグリセロール誘導体は、ヒマシ油と過剰のグリセロールを蒸留して得られたモノグリセリドを、酢酸とエステル化するなど、公知の方法により得られるものであるが、その合成方法は特に限定されるものではない。
The diacetyl monoacylglycerol derivative has two acetyl groups and a hydroxyl group derivative of a fatty acid, and the hydroxyl group derivative of the fatty acid is a fatty acid having a hydroxyl group, or a fatty acid having a hydroxyl group and a fatty acid having a monovalent carboxyl group. esters. The diacetylmonoacylglycerol derivative having each of the hydroxyl group derivative having a hydroxyl group and the hydroxyl group derivative having an ester with a fatty acid having a monovalent carboxyl group can be used in combination.
The fatty acid having a hydroxyl group preferably has 6 to 36 carbon atoms, more preferably 8 to 24 carbon atoms.
The diacetyl monoacylglycerol derivative can be obtained by a known method such as esterifying a monoglyceride obtained by distilling castor oil and excess glycerol with acetic acid, but the synthesis method is particularly limited. not a thing
前記脂肪酸エステルは、液状マスターバッチの溶媒として使用することにより、液状マスターバッチの長期保存において固体粒子が沈降することなく、また樹脂と液状マスターバッチを成形した際に成形体表面に液泡が生じない成形体を得ることができるが、本発明の効果を損なわない範囲で、植物油、ポリエチレングリコール、ポリプロピレングリコール、高級アルコール、流動パラフィン等の他の溶剤を加えてもよい。 By using the fatty acid ester as a solvent for the liquid masterbatch, solid particles do not settle during long-term storage of the liquid masterbatch, and liquid bubbles do not form on the surface of the molded body when the resin and the liquid masterbatch are molded. Although a molded article can be obtained, other solvents such as vegetable oil, polyethylene glycol, polypropylene glycol, higher alcohol, liquid paraffin, etc. may be added to the extent that the effects of the present invention are not impaired.
本発明において用いられる界面活性剤は、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも1つが用いられる。前記界面活性剤を使用することで、液状マスターバッチの長期保存において固体粒子が沈降することなく、また樹脂と液状マスターバッチを成形した際に成形体表面に液泡が生じない成形体を得ることができる。
前記界面活性剤は、液状マスターバッチ１００重量部に対して、０．２～１５重量部であることが好ましく、０．５～１０重量部であることがより好ましい。０．２重量部以上であることで、液状マスターバッチの長期保存時に固体粒子が沈降せず、１５重量部以下であることで、液泡の生じない優れた成形体を得られる。
The surfactant used in the present invention is at least one selected from fatty acid amide surfactants, metallic soaps, and hydrogenated castor oil. By using the above-mentioned surfactant, it is possible to obtain a molded product that does not allow solid particles to settle during long-term storage of the liquid masterbatch and that does not generate liquid bubbles on the surface of the molded product when the resin and the liquid masterbatch are molded. can.
The amount of the surfactant is preferably 0.2 to 15 parts by weight, more preferably 0.5 to 10 parts by weight, relative to 100 parts by weight of the liquid masterbatch. When the amount is 0.2 parts by weight or more, the solid particles do not settle during long-term storage of the liquid masterbatch, and when the amount is 15 parts by weight or less, an excellent molded article free from liquid bubbles can be obtained.
［脂肪酸アミド系界面活性剤］
前記脂肪酸アミド系界面活性剤は、ステアリン酸アマイド、オレイン酸アマイド、エルカ酸アマイド、エチレンビスステアリン酸アマイド、メチレンビスステアリン酸アマイド、エチレンビスオレイン酸アマイド、またはベヘニン酸アミドが好適であり、エチレンビスステアリン酸アマイドがより好ましい。
[Fatty acid amide surfactant]
The fatty acid amide surfactant is preferably stearamide, oleamide, erucamide, ethylene bis stearamide, methylene bis stear amide, ethylene bis oleamide, or behenamide. Stearamide is more preferred.
［金属石鹸］
前記金属石鹸は、脂肪酸のアルカリ金属塩のうち、脂肪酸がラウリン酸、ミリスチン酸、モンタン酸、ベヘン酸、パルミチン酸であるもの、アルカリ金属がマグネシウム、カルシウム、ナトリウム、カリウム、亜鉛、バリウム、アルミニウムであるものが好適であり、特にステアリン酸マグネシウムがより好ましい。
[Metallic soap]
Among the alkali metal salts of fatty acids, the metal soaps contain lauric acid, myristic acid, montanic acid, behenic acid, and palmitic acid as the fatty acids, and the alkali metals are magnesium, calcium, sodium, potassium, zinc, barium, and aluminum. Some are preferred, especially magnesium stearate.
［硬化ヒマシ油］
前記硬化ヒマシ油は、ヒマシ油を水素添加反応によって完全硬化して得られる１２－ヒドロキシステアリン酸のトリグリセリドであり、Ｋ－３ワックスやカワスターＣＲ（いずれも川研ファインケミカル社製）等の市販品が入手可能である。
[Hardened castor oil]
The hardened castor oil is a triglyceride of 12-hydroxystearic acid obtained by completely hardening castor oil by a hydrogenation reaction, and commercially available products such as K-3 wax and Kawastar CR (both manufactured by Kawaken Fine Chemicals Co., Ltd.) are available. Available.
本発明の液状マスターバッチは、本発明の効果を損なわず、また液状マスターバッチが膨潤しない範囲で、前記界面活性剤と併用してその他の界面活性剤を含むことができる。その他の界面界面活性剤としては、ソルビタン系界面活性剤、高級アルコール系界面活性剤またはアルキルフェノール系界面活性剤等のノニオン系界面活性剤、アニオン系界面活性剤、カチオン系界面活性剤、または両イオン性界面活性剤が挙げられる。 The liquid masterbatch of the present invention can contain other surfactants in combination with the above-mentioned surfactants, as long as the effects of the present invention are not impaired and the liquid masterbatch does not swell. Other surfactants include nonionic surfactants such as sorbitan surfactants, higher alcohol surfactants or alkylphenol surfactants, anionic surfactants, cationic surfactants, or amphoteric surfactants. surfactants.
前記ソルビタン系界面活性剤としては、例えばソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等を挙げることができ、具体例としてはソルビタンモノラウレート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタンジステアレート、ソルビタントリステアレート、ソルビタンモノオレエート、ソルビタントリオレエート、ソルビタンセスキオレエート、ポリオキシエチレンソルビタンモノラウレート、ポリオキシエチレンソルビタンモノパルミテート、ポリオキシエチレンソルビタンモノステアレート、ポリオキシエチレンソルビタントリステアレート、ポリオキシエチレンソルビタンモノオレエート、ポリオキシエチレンソルビタントリイソステアレート、等を挙げることができる。 Examples of the sorbitan-based surfactants include sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and specific examples include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, and sorbitan distearate. , sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate rate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, and the like.
［固体粒子］
本発明において用いられる固体粒子は特に限定されないが、本発明の脂肪酸エステルに不溶の顔料、染料、または樹脂改質剤として使用される固体粒子が含まれる。
[Solid particles]
The solid particles used in the present invention are not particularly limited, but include solid particles used as pigments, dyes, or resin modifiers that are insoluble in the fatty acid ester of the present invention.
前記顔料としては、無機顔料、及び有機顔料のいずれであってもよい。例えば、カーボンブラック、黒酸化鉄（四三酸化鉄）、黒酸化チタン、銅マンガンブラック、銅クロムブラック、及びコバルトブラック等の黒色無機顔料：シアニンブラック、及びアニリンブラックなどの黒色有機顔料：フタロシアニンブルー、フタロシアニングリーン等のフタロシアニン顔料：アゾイエローレーキ、アゾレーキレッド、モノアゾイエロー等のアゾ顔料：キナクリドン顔料、ペリレン顔料、キノフタロン顔料、アントラキノン顔料等の多環式顔料：群青、コバルト、弁柄、酸化チタン、ニッケルチタンイエロー、クロムチタンイエロー、銀粉、アルミ粉、ニッケル粉、パール顔料、金粉等の無機顔料などを含有してもよい。これら顔料は、１種または２種以上を用いることができる。 The pigment may be either an inorganic pigment or an organic pigment. For example, black inorganic pigments such as carbon black, black iron oxide (triiron tetraoxide), black titanium oxide, copper manganese black, copper chromium black, and cobalt black; black organic pigments such as cyanine black and aniline black; phthalocyanine blue , phthalocyanine pigments such as phthalocyanine green: azo pigments such as azo yellow lake, azo lake red, monoazo yellow; polycyclic pigments such as quinacridone pigments, perylene pigments, quinophthalone pigments, anthraquinone pigments: ultramarine blue, cobalt, red iron oxide, titanium oxide , nickel titanium yellow, chrome titanium yellow, silver powder, aluminum powder, nickel powder, pearl pigment, gold powder, and other inorganic pigments. These pigments can be used alone or in combination of two or more.
前記染料としては、ペリレン系染料、クマリン系染料、チオインジゴ系染料、アンスラキノン系染料、チオキサントン系染料、紺青等のフェロシアン化物、ペリノン系染料、キノリン系染料、キナクリドン系染料、ジオキサジン系染料、イソインドリノン系染料、およびフタロシアニン系染料などを含有してもよい。 Examples of the dyes include perylene-based dyes, coumarin-based dyes, thioindigo-based dyes, anthraquinone-based dyes, thioxanthone-based dyes, ferrocyanides such as Prussian blue, perinone-based dyes, quinoline-based dyes, quinacridone-based dyes, dioxazine-based dyes, iso Indolinone dyes, phthalocyanine dyes, and the like may be contained.
顔料および染料以外の固体粒子としては、無機粒子および有機粒子が上げられる。無機粒子の例としては、カオリン、ケイ酸アルミニウム、クレー、タルク、マイカ、シリカ、アルミナ、ケイ酸カルシウム、ベントナイト、ケイ酸マグネシウム、アスベスト、炭酸カルシウム、炭酸マグネシウム、炭酸バリウム、ドロマイト、硫酸カルシウム、硫酸バリウム、硫酸アルミニウム、ジルコニア、マグネシア、三酸化アンチモン、酸化チタン、珪藻土、酸化鉄、酸化亜鉛、水酸化マグネシウム、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、窒化アルミニウム、アンチモンドープ酸化錫、チタン酸バリウム、黒鉛、鉄粉、ガラス繊維等が挙げられる。有機粒子の例としては、澱粉、及びポリエチレン樹脂、ウレタン樹脂、メラミン樹脂、ポリスチレン樹脂、ポリ乳酸、また固体パラフィン等の粒子が挙げられる。 Solid particles other than pigments and dyes include inorganic particles and organic particles. Examples of inorganic particles include kaolin, aluminum silicate, clay, talc, mica, silica, alumina, calcium silicate, bentonite, magnesium silicate, asbestos, calcium carbonate, magnesium carbonate, barium carbonate, dolomite, calcium sulfate, sulfuric acid. Barium, aluminum sulfate, zirconia, magnesia, antimony trioxide, titanium oxide, diatomaceous earth, iron oxide, zinc oxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, aluminum nitride, antimony dope Tin oxide, barium titanate, graphite, iron powder, glass fiber and the like can be mentioned. Examples of organic particles include particles of starch, polyethylene resin, urethane resin, melamine resin, polystyrene resin, polylactic acid, solid paraffin, and the like.
前記無機粒子および有機粒子には、酸化防止剤、紫外線吸収剤、ヒンダードアミン系耐候安定剤、若しくは帯電防止剤等の各種安定剤、または難燃剤、若しくはアンチブロッキング剤等のプラスチック添加剤のうち、前記脂肪酸エステルに不溶な粒子、も含まれる。 For the inorganic particles and organic particles, among various stabilizers such as antioxidants, ultraviolet absorbers, hindered amine weather stabilizers, or antistatic agents, or plastic additives such as flame retardants or antiblocking agents, Also included are particles that are insoluble in fatty acid esters.
本発明において用いられる固体粒子は、液状マスターバッチ１００重量部に対して、０．０１～４０重量部であることが好ましく、０．０５～３０重量部であることがより好ましい。０．０１重量部未満であると、十分な物性向上または着色を得られず、４０重量部より大きいと長期保存時にも固体粒子が沈降する。 The solid particles used in the present invention are preferably 0.01 to 40 parts by weight, more preferably 0.05 to 30 parts by weight, per 100 parts by weight of the liquid masterbatch. If the amount is less than 0.01 part by weight, sufficient improvement in physical properties or coloration cannot be obtained, and if the amount is more than 40 parts by weight, the solid particles will sediment even during long-term storage.
前記固体粒子は１種を単独で使用することができ、又は２種以上を併用することができる。固体粒子を２種以上を併用する場合、液状マスターバッチ１００重量部に対する全固体粒子の重量部の合計値が、前記固体粒子の重量部の範囲となることが好ましい。 The solid particles may be used singly or in combination of two or more. When two or more kinds of solid particles are used in combination, it is preferable that the total weight part of all the solid particles per 100 parts by weight of the liquid masterbatch is in the range of the weight parts of the solid particles.
本発明の液状マスターバッチは、増粘剤を含むことができる。増粘剤としては、例えば、リン酸エステルの塩、微粒子シリカ、硬化性の植物油、硬化性動物油脂などが挙げられ、これらは１種もしくは２種以上用いることができる。 The liquid masterbatch of the present invention can contain a thickening agent. Examples of thickeners include salts of phosphate esters, fine particle silica, curable vegetable oils, curable animal oils and fats, and the like, and one or more of these can be used.
前記微粒子シリカは、親水性微粒子シリカと疎水性微粒子シリカがあり、親水性シリカの好ましい市販品としては、ＡＥＲＯＳＩＬ－３００、ＡＥＲＯＳＩＬ－３８０（日本アエロジル社製）等が挙げられ、また、疎水性シリカの好ましい市販品としては、ＡＥＲＯＳＩＬ－９７４Ｄ、ＡＥＲＯＳＩＬ－９７２（日本アエロジル社製）、サイロホービック２００、サイロホービック３２６（富士サイリシア社製）等が挙げられる。 The particulate silica includes hydrophilic particulate silica and hydrophobic particulate silica. Preferred commercial products of hydrophilic silica include AEROSIL-300 and AEROSIL-380 (manufactured by Nippon Aerosil Co., Ltd.). Preferable commercially available products include AEROSIL-974D, AEROSIL-972 (manufactured by Nippon Aerosil Co., Ltd.), Cyrophobic 200, Cyrophobic 326 (manufactured by Fuji Silysia Co., Ltd.) and the like.
前記硬化性の植物油としては、融点が３０度以上の硬化性の植物油や動物油が挙げられ、植物油としては、硬化菜種油、硬化大豆油、硬化パーム油、硬化ヤシ油、硬化米油、または硬化ホホバ油が挙げられ、硬化動物油脂としては、硬化牛脂、硬化豚脂、または硬化馬油が挙げられる。 Examples of the curable vegetable oils include curable vegetable oils and animal oils having a melting point of 30 degrees or higher. Vegetable oils include hydrogenated rapeseed oil, hydrogenated soybean oil, hydrogenated palm oil, hydrogenated palm oil, hydrogenated rice oil, and hydrogenated jojoba. Oils include hardened animal fats and oils, including hardened beef tallow, hardened lard, or hardened horse oil.
前記増粘剤は、液状マスターバッチ１００重量部に対して、０．１～３０重量部であることが好ましく、０．５～２０重量部であることがより好ましい。 The thickener is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the liquid masterbatch.
［液状マスターバッチの製造方法］
本発明における液状マスターバッチの製造方法は、特に限定されるものではなく、例えば、液状の脂肪酸エステル（Ａ）、固体粒子（Ｂ）と、界面活性剤（Ｃ）、更に必要に応じて各種添加剤とを加え、ヘンシェルミキサーやタンブラー、ディスパー等で混合し、ミキサー、ビーズミル、及びペイントシェーカーを用いて分散することで、液状マスターバッチを得ることができる。分散装置は、上記以外にもニーダー、ロールミル、ボールミル、サンドミル等、任意の装置を使用することができる。
[Method for producing liquid masterbatch]
The method for producing the liquid masterbatch in the present invention is not particularly limited. agent, mixed with a Henschel mixer, a tumbler, a disper, etc., and dispersed using a mixer, a bead mill, and a paint shaker to obtain a liquid masterbatch. As the dispersing device, any device such as a kneader, a roll mill, a ball mill, a sand mill, etc. can be used in addition to the above.
［樹脂成形材料］
本発明の樹脂成形材料は、前記液状マスターバッチと熱可塑性樹脂を含有する成形体を形成するための樹脂成形材料である。樹脂成形材料は、例えば、熱可塑性樹脂ペレットと液状マスターバッチの混合物、あるいはあらかじめ熱可塑性樹脂と液状マスターバッチを混練したペレット状、粉末状、顆粒状あるいはビーズ状等の混練物があげられる。
[Resin molding material]
The resin molding material of the present invention is a resin molding material for forming a molded article containing the liquid masterbatch and a thermoplastic resin. The resin molding material may be, for example, a mixture of thermoplastic resin pellets and liquid masterbatch, or a kneaded material obtained by kneading thermoplastic resin and liquid masterbatch in advance in the form of pellets, powder, granules or beads.
前記樹脂成形材料は、液状マスターバッチと熱可塑性樹脂の混合物を、そのまま溶融混練させて樹脂成形材料とし、成形体を成形することができ、またあらかじめペレット状等とした樹脂成形材料をさらに熱可塑性樹脂と溶融混練して希釈し、成形体を成形することもできる。 The resin molding material can be obtained by melting and kneading a mixture of a liquid masterbatch and a thermoplastic resin as it is to obtain a resin molding material to mold a molded body, and pre-pelletized resin molding material can be further made thermoplastic. It can also be melt-kneaded with a resin, diluted, and formed into a molded product.
［熱可塑性樹脂］
本発明の樹脂成形材料または成形体に含有される熱可塑性樹脂は、液状マスターバッチにより着色される成形体の主材となる樹脂であって、ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、またはポリカーボネート樹脂が好適に使用される。
[Thermoplastic resin]
The thermoplastic resin contained in the resin molding material or molded article of the present invention is a resin that is the main material of the molded article colored by the liquid masterbatch, and is polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin. preferably used.
［ポリエチレンテレフタレート樹脂］
前記ポリエチレンテレフタレートは、テレフタル酸とエチレングリコールを主成分とするものである。
前記ポリエチレンテレフタレートは、特性を損なわない範囲で、テレフタル酸以外の酸成分として、例えば、イソフタル酸、５－ナトリウムスルホイソフタル酸、２，６－ナフタレンジカルボン酸、４，４’－ジフェニルジカルボン酸、ジフェニルスルホンジカルボン酸等の芳香族ジカルボン酸；トリメリット酸、ピロメリット酸等の芳香族多価カルボン酸及びその酸無水物；シュウ酸、コハク酸、アジピン酸、セバシン酸、アゼライン酸、デカンジカルボン酸等の脂肪族ジカルボン酸が共重合されてもよい。
また、前記ポリエチレンテレフタレートは、特性を損なわない範囲で、エチレングリコール以外のアルコール成分として、例えば、プロピレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、２，３－ブタンジオール、ジエチレングリコール、１，５－ペンタンジオール、ネオペンチルグリコール、トリエチレングリコール、ポリエチレングリコール等の脂肪族ジオール；トリメチロールプロパン、ペンタエリスリトール等の脂肪族多価アルコール；１，４－シクロヘキサンジメタノール、１，４－シクロヘキサンジエタノール等の脂環族ジオール；ビスフェノールＡやビスフェノールＳのエチレンオキシド付加体等の芳香族ジオール；４－ヒドロキシ安息香酸、ε－カプロラクトン等のヒドロキシカルボン酸が共重合されてもよい。
[Polyethylene terephthalate resin]
The polyethylene terephthalate is mainly composed of terephthalic acid and ethylene glycol.
The polyethylene terephthalate contains acid components other than terephthalic acid, such as isophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, diphenyl Aromatic dicarboxylic acids such as sulfonedicarboxylic acid; Aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid and their acid anhydrides; Oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, decanedicarboxylic acid of aliphatic dicarboxylic acids may be copolymerized.
In addition, the polyethylene terephthalate may contain alcohol components other than ethylene glycol, such as propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, Aliphatic diols such as 3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, 1,5-pentanediol, neopentyl glycol, triethylene glycol, polyethylene glycol; trimethylolpropane, pentaerythritol Alicyclic diols such as 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol; Aromatic diols such as ethylene oxide adducts of bisphenol A and bisphenol S; 4-hydroxybenzoic acid, Hydroxycarboxylic acids such as ε-caprolactone may be copolymerized.
［ポリブチレンテレフタレート樹脂］
前記ポリブチレンテレフタレート樹脂は、テレフタル酸あるいはそのエステル形成性誘導体と１，４－ブタンジオールあるいはそのエステル形成性誘導体とを主成分とするものである。
前記ポリブチレンテレフタレート樹脂は、特性を損なわない範囲で、他の共重合成分を含んでもよい。これら重合体および共重合体の好ましい例としては、ポリブチレンテレフタレート、ポリブチレン（テレフタレート／イソフタレート）、ポリブチレン（テレフタレート／アジペート）、ポリブチレン（テレフタレート／セバケート）、ポリブチレン（テレフタレート／デカンジカルボキシレート）、ポリブチレン（テレフタレート／ナフタレート）、ポリ（ブチレン／エチレン）テレフタレート等が挙げられ、単独で用いても２種以上を併用してもよい。
[Polybutylene terephthalate resin]
The polybutylene terephthalate resin is mainly composed of terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative.
The polybutylene terephthalate resin may contain other copolymer components as long as the properties are not impaired. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate/isophthalate), polybutylene (terephthalate/adipate), polybutylene (terephthalate/sebacate), polybutylene (terephthalate/decanedicarboxylate), polybutylene (terephthalate/naphthalate), poly(butylene/ethylene) terephthalate, and the like, and may be used alone or in combination of two or more.
［ポリカーボネート樹脂］
前記ポリカーボネート樹脂は、芳香族ジヒドロキシ化合物と、ホスゲン或いは炭酸ジエステル等のカーボネート前駆体とを反応させることにより容易に製造される。反応は公知の反応、例えば、ホスゲンを用いる場合は界面法により、また炭酸ジエステルを用いる場合は溶融状で反応させるエステル交換法により得ることができる。
[Polycarbonate resin]
The polycarbonate resin is easily produced by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or carbonic acid diester. The reaction can be obtained by a known reaction, for example, an interfacial method when phosgene is used, and an ester exchange method in which the reaction is performed in a molten state when a carbonic acid diester is used.
上記芳香族ジヒドロキシ化合物としては、例えば、２，２－ビス（４－ヒドロキシフェニル）プロパン（ビスフェノールＡ）、ビス（４－ヒドロキシフェニル）メタン、１，１－ビス（４－ヒドロキシフェニル）エタン、２，２－ビス（４－ヒドロキシフェニル）ブタン、２，２－ビス（４－ヒドロキシフェニル）オクタン、ビス（４－ヒドロキシフェニル）フェニルメタン、２，２－ビス（４－ヒドロキシ－３－メチルフェニル）プロパン、１，１－ビス（４－ヒドロキシ－３－ｔ－ブチルフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３－ブロモフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジブロモフェニル）プロパン、２，２－ビス（４－ヒドロキシ－３，５－ジクロロフェニル）プロパン等のビス（ヒドロキシアリール）アルカン類、１，１－ビス（４－ヒドロキシフェニル）シクロペンタン、１，１－ビス（４－ヒドロキシフェニル）シクロヘキサン等のビス（ヒドロキシアリール）シクロアルカン類４，４´－ジヒドロキシジフェニルエーテル、４，４´－ジヒドロキシ－３，３´－ジメチルジフェニルエーテル等のジヒドロキシジアリールエーテル類、４，４´－ジヒドロキシジフェニルスルフィド、４，４´－ジヒドロキシ－３，３´－ジメチルジフェニルスルフィドのようなジヒドロキシジアリールスルフィド類、４，４´－ジヒドロキシジフェニルスルホキシド、４，４´－ジヒドロキシ－３，３´－ジメチルジフェニルスルホキシド等のジヒドロキシジアリールスルホキシド類、４，４´－ジヒドロキシジフェニルスルホン、４，４´－ジヒドロキシ－３，３´－ジメチルジフェニルスルホン等のジヒドロキシジアリールスルホン類等が挙げられる。これらは単独または２種以上混合して使用される。これらの他にピペラジン、ジピペリジルハイドロキノン、レゾルシン、４，４´－ジヒドロキシジフェニル類を混合して使用してもよい。更に、フロログルシン等の多官能性化合物を併用した分岐を有する芳香族ポリカーボネート樹脂を使用することも出来る。 Examples of the aromatic dihydroxy compound include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2 , 2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl) Propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3, bis(hydroxyaryl)alkanes such as 5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclopentane, 1, bis(hydroxyaryl)cycloalkanes such as 1-bis(4-hydroxyphenyl)cyclohexane; dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether; ,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide and other dihydroxydiaryl sulfides, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 dihydroxydiarylsulfoxides such as '-dimethyldiphenylsulfoxide; and dihydroxydiarylsulfones such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone. These are used singly or in combination of two or more. In addition to these, piperazine, dipiperidylhydroquinone, resorcinol, and 4,4'-dihydroxydiphenyls may be mixed and used. Furthermore, a branched aromatic polycarbonate resin in which a polyfunctional compound such as phloroglucin is used in combination can also be used.
前記芳香族ジヒドロキシ化合物と反応させるカーボネート前駆体としては、例えば、ホスゲン、ジフェニルカーボネート、ジトリルカーボネート等のジアリールカーボネート類、ジメチルカーボネート、ジエチルカーボネート等のジアルキルカーボネート類等が挙げられる。 Examples of carbonate precursors to be reacted with the aromatic dihydroxy compound include phosgene, diphenyl carbonate, diaryl carbonates such as ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.
前記樹脂成形材料における熱可塑性樹脂と液状マスターバッチの混合比は、熱可塑性樹脂１００重量部に対して、液状マスターバッチ中の液状の脂肪酸エステルが０．０５～１０重量部となるよう混合することが好ましく、０．１～５重量部であることがより好ましい。１０重量部より大きいと、脂肪酸エステルが成形した際に成形体表面に液泡が発生することがあり、また混合時に使用する混合機内で材料が空転するおそれがある。０．０５重量部未満であると十分な物性向上または着色を得られない。 The mixing ratio of the thermoplastic resin and the liquid masterbatch in the resin molding material is such that the liquid fatty acid ester in the liquid masterbatch is 0.05 to 10 parts by weight per 100 parts by weight of the thermoplastic resin. is preferred, and 0.1 to 5 parts by weight is more preferred. If the amount is more than 10 parts by weight, liquid bubbles may form on the surface of the molded body when the fatty acid ester is molded, and the material may idle in the mixer used during mixing. If it is less than 0.05 parts by weight, sufficient improvement in physical properties or coloration cannot be obtained.
前記樹脂成形材料は、本発明の効果を損なわない範囲で、他の界面活性剤、酸化防止剤、紫外線吸収剤、ヒンダードアミン系耐候安定剤、帯電防止剤等各種安定剤、難燃剤、アンチブロッキング剤の添加剤を加えてもよい。また、前記添加剤は、あらかじめ熱可塑性樹脂に練り込んだマスターバッチとして添加してもよい。 The resin molding material may contain other surfactants, antioxidants, ultraviolet absorbers, hindered amine weather stabilizers, various stabilizers such as antistatic agents, flame retardants, and antiblocking agents, as long as they do not impair the effects of the present invention. additives may be added. Moreover, the additive may be added as a masterbatch that is kneaded into the thermoplastic resin in advance.
［成形体］
本発明の成形体は、前記液状マスターバッチと前記熱可塑性樹脂を含有する樹脂成形材料より形成してなる。
本発明の成形体は、前記液状マスターバッチと前記熱可塑性樹脂が含まれているものであればよく、その形成方法は具体的には、例えば、（ａ）液状マスターバッチと、熱可塑性樹脂のペレット等を混合の上、溶融混練して樹脂成形材料として、成形体を得る方法、（ｂ）液状マスターバッチと熱可塑性樹脂をあらかじめ溶融混練してペレット状のマスターバッチとした樹脂成形材料を用い、さらに熱可塑性樹脂のペレット等と一緒に溶融混練して成形体を得る方法、（ｃ）液状マスターバッチと、熱可塑性樹脂を溶融混練してペレット等にした樹脂成形材料を、そのまま溶融混練して成形体を得る方法、などが挙げられる。
[Molded body]
The molded article of the present invention is formed from a resin molding material containing the liquid masterbatch and the thermoplastic resin.
The molded article of the present invention may contain the liquid masterbatch and the thermoplastic resin, and the method for forming the molded article is specifically, for example, (a) the liquid masterbatch and the thermoplastic resin A method of obtaining a molded body as a resin molding material by mixing pellets or the like and melt-kneading them. , a method of obtaining a molded body by further melt-kneading together with thermoplastic resin pellets, etc., (c) melt-kneading the liquid masterbatch and the resin molding material made into pellets by melt-kneading the thermoplastic resin as they are. and a method of obtaining a molded body.
前記成形体に含まれる液状マスターバッチの含有量は、成形体１００重量部に対して、液状マスターバッチ中の液状の脂肪酸エステルが０．０５～１０重量部となるよう混合することが好ましく、０．１～５重量部であることがより好ましい。１０重量部より大きいと、液状マスターバッチの溶媒により白化が発生することがあり、また成形機の押出スクリュー内で材料が空転するおそれがある。０．０５重量部未満であると十分な物性向上または着色を得られない。 The content of the liquid masterbatch contained in the molded body is preferably 0.05 to 10 parts by weight of the liquid fatty acid ester in the liquid masterbatch with respect to 100 parts by weight of the molded body. .1 to 5 parts by weight is more preferred. If the amount is more than 10 parts by weight, whitening may occur due to the solvent of the liquid masterbatch, and the material may slip inside the extrusion screw of the molding machine. If it is less than 0.05 parts by weight, sufficient improvement in physical properties or coloration cannot be obtained.
液状マスターバッチを用いて成形体を得る成形方法は、特に限定されず、射出成形、ブロー成形、押出成形、フィルム成形、圧縮成形などの公知の方法を用いることができる。 A molding method for obtaining a molded article using a liquid masterbatch is not particularly limited, and known methods such as injection molding, blow molding, extrusion molding, film molding, and compression molding can be used.
成形体は、熱可塑性樹脂と液状マスターバッチの混合物であればよく、成形の際に成形機のホッパーへ熱可塑性樹脂を投入し、既知のポンプ等を用いて液状マスターバッチを添加して混合の上、溶融混練して成形体を得てもよく、また、あらかじめペレット状、粉末状、顆粒状あるいはビーズ状とした樹脂成形材料を成形機に投入してもよい。 The molded body may be a mixture of a thermoplastic resin and a liquid masterbatch. When molding, the thermoplastic resin is put into a hopper of a molding machine, and the liquid masterbatch is added using a known pump or the like to mix. In addition, a molding may be obtained by melt-kneading, or a resin molding material which has been made into pellets, powder, granules or beads in advance may be put into a molding machine.
以下に実施例および比較例を示して本発明を更に具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例および比較例中の部は重量部を、％は重量％を表す。 EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to these. In the examples and comparative examples, "parts" means parts by weight, and "%" means "% by weight".
実施例と比較例に使用した各材料を表１に、また液状マスターバッチの組成を表２および表３に示す。 Table 1 shows the materials used in Examples and Comparative Examples, and Tables 2 and 3 show the compositions of liquid masterbatches.
＜液状マスターバッチの作製＞
実施例１～１５および比較例１～１２について、表２および表３に記載の配合に従い材料を混合攪拌した後、ペイントシェーカーにて、２時間分散し、液状マスターバッチを作製した。なお、表２および表３の数値は重量％を示す。
<Production of liquid masterbatch>
For Examples 1 to 15 and Comparative Examples 1 to 12, the materials were mixed and stirred according to the formulations shown in Tables 2 and 3, and then dispersed for 2 hours using a paint shaker to prepare a liquid masterbatch. Incidentally, the numerical values in Tables 2 and 3 indicate % by weight.
＜樹脂成形材料および成形体の作製＞
表２および表３に記載の熱可塑性樹脂のペレット１００重量部に対し、得られた液状マスターバッチ０．２重量部を計量後に混合して樹脂成形材料を作製した。
熱可塑性樹脂は下記のものを使用した。
ポリエチレンテレフタレート樹脂（ＰＥＴ）： ＰＩＦＧ８（株式会社ベルポリエステルプロダクツ製）
ポリカーボネート樹脂（ＰＣ）：ユーピロンＳ－１０００（三菱エンジニアリングプラスチックス株式会社製）
ポリブチレンテレフタレート樹脂（ＰＢＴ）：ノバデュラン５０２０（三菱エンジニアリングプラスチックス株式会社製）
実施例１～１５および比較例１～１２で使用した樹脂を、表２および表３に記載する。
<Preparation of Resin Molding Material and Molded Body>
0.2 parts by weight of the obtained liquid masterbatch was weighed and mixed with 100 parts by weight of the thermoplastic resin pellets shown in Tables 2 and 3 to prepare a resin molding material.
The following thermoplastic resins were used.
Polyethylene terephthalate resin (PET): PIFG8 (manufactured by Bell Polyester Products Co., Ltd.)
Polycarbonate resin (PC): Iupilon S-1000 (Mitsubishi Engineering-Plastics Co., Ltd.)
Polybutylene terephthalate resin (PBT): NOVADURAN 5020 (Mitsubishi Engineering-Plastics Co., Ltd.)
The resins used in Examples 1-15 and Comparative Examples 1-12 are listed in Tables 2 and 3.
さらに、前記樹脂成形材料をインジェクションブロー成形機（日精エー・エス・ビー株式会社製、型番：ＡＳＢ－１２Ｎ、スクリュー径：４４ｍｍ）のホッパーへ投入後、以下の成形温度、および金型温度１５～２０℃の条件によりボトル状の成形体を作製した。
・ポリエチレンテレフタレート樹脂：２９０℃
・ポリブチレンテレフタレート樹脂：２６０℃
・ポリカーボネート樹脂：２９０℃
作成した成形体は、高さ１６０ｍｍ、直径６１ｍｍ、肉厚０．５ｍｍであった。
Furthermore, after the resin molding material is put into the hopper of an injection blow molding machine (manufactured by Nissei ASB Co., Ltd., model number: ASB-12N, screw diameter: 44 mm), the following molding temperature and mold temperature 15 ~ A bottle-shaped molding was produced under the condition of 20°C.
・Polyethylene terephthalate resin: 290°C
・Polybutylene terephthalate resin: 260°C
・Polycarbonate resin: 290°C
The formed body had a height of 160 mm, a diameter of 61 mm and a thickness of 0.5 mm.
実施例１～１５および比較例１～１２の液状マスターバッチの沈降性評価と、成形体の液泡評価を行った。また顔料・染料を含有する実施例１～４、実施例６～１５、および比較例１～１２の成形体については、併せて着色性評価を行った。評価結果を、表４および表５に記載する。総合評価は、評価を行ったうち、すべての評価が○のものを良品とした。 The sedimentation properties of the liquid masterbatches of Examples 1 to 15 and Comparative Examples 1 to 12 were evaluated, and the molded bodies were evaluated for liquid foam. The molded articles of Examples 1 to 4, Examples 6 to 15, and Comparative Examples 1 to 12 containing pigments and dyes were also evaluated for colorability. Evaluation results are shown in Tables 4 and 5. As for the comprehensive evaluation, those with all evaluations of ◯ were regarded as non-defective products.
＜沈降性評価＞
前記液状マスターバッチを、作成後、ガラス瓶に保管し７日放置後の沈降状態を目視により確認して沈降性を評価した。沈降性について、○：沈降が見られない、×：沈降が見られる、の２段階で評価した。
<Evaluation of sedimentation>
After the liquid masterbatch was prepared, it was stored in a glass bottle and left for 7 days. The sedimentation property was evaluated on a two-grade scale of ◯: no sedimentation observed and x: sedimentation observed.
＜液泡評価＞
前記ボトル状の成形体を５０ショット作成し、すべての成形体の表面を観察して、直径１ｍｍ以上の液泡の有無を評価した。液泡の評価は、○：すべての成形体で表面に液泡が見られない、×：１個以上の成形体で表面に液泡が見られる、の２段階で評価した。
<Liquid foam evaluation>
50 shots of the bottle-shaped moldings were prepared, and the surfaces of all the moldings were observed to evaluate the presence or absence of liquid bubbles having a diameter of 1 mm or more. Evaluation of liquid bubbles was made according to two grades: ○: No liquid bubbles were observed on the surface of all molded articles, and ×: Liquid bubbles were observed on the surface of one or more molded articles.
＜着色性評価＞
前記成形体を用いて、成形体表面の着色性を評価した。着色性の評価は、○：成形体表面が均一に着色している、×：成形体表面の一部に他と色と異なる色むらが見られる、の２段階で評価した。
<Colorability evaluation>
Using the molded article, the colorability of the surface of the molded article was evaluated. Colorability was evaluated on a two-grade scale: ○: the surface of the molded article was uniformly colored;
すなわち、本発明は、
（１）ポリエチレンテレフタレート樹脂、ポリブチレンテレフタレート樹脂、またはポリカーボネート樹脂の成形に用いられる液状マスターバッチであって、
前記液状マスターバッチは、常温で液状の脂肪酸エステル（Ａ）と、固体粒子（Ｂ）と、界面活性剤（Ｃ）を含み、
前記脂肪酸エステル（Ａ）は、脂肪酸を有するジアセチルモノアシルグリセロール、および／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体を含み、前記界面活性剤（Ｃ）が、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも１つであり、前記固体粒子（Ｂ）は顔料、または染料から選択される少なくとも１つであり、前記脂肪酸を有するジアセチルモノアシルグリセロールおよび／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体が、前記液状マスターバッチ１００重量部に対して、６６．０～９６．０重量部含み、前記界面活性剤（Ｃ）が、前記液状マスターバッチ１００重量部に対して、０．２～１５重量部含み、前記固体粒子（Ｂ）が、液状マスターバッチ１００重量部に対して０．０１～４０重量部含む、ことを特徴とする、液状マスターバッチ、
（２）（１）に記載の液状マスターバッチと、熱可塑性樹脂を含む樹脂成形材料、
（３）（１）に記載の液状マスターバッチを含む樹脂成形体、
（４）（２）に記載の樹脂成形材料を成形してなる樹脂成形体、
である。
That is, the present invention
(1) A liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin,
The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C),
The fatty acid ester (A) contains a diacetylmonoacylglycerol having a fatty acid and/or a diacetylmonoacylglycerol derivative having a fatty acid, and the surfactant (C) is a fatty acid amide surfactant, a metal soap, and It is at least one selected from hydrogenated castor oil, the solid particles (B) are at least one selected from pigments or dyes, and the diacetyl monoacylglycerol having the fatty acid and / or fatty acid The diacetyl monoacylglycerol derivative having 66.0 to 96.0 parts by weight with respect to 100 parts by weight of the liquid masterbatch, and the surfactant (C) with respect to 100 parts by weight of the liquid masterbatch, A liquid masterbatch comprising 0.2 to 15 parts by weight, and containing 0.01 to 40 parts by weight of the solid particles (B) with respect to 100 parts by weight of the liquid masterbatch ,
(2) The liquid masterbatch according to (1) and a resin molding material containing a thermoplastic resin,
(3) A resin molding containing the liquid masterbatch according to (1),
(4) a resin molded body obtained by molding the resin molding material according to (2);
is.
Claims (6)
前記液状マスターバッチは、常温で液状の脂肪酸エステル（Ａ）と、固体粒子（Ｂ）と、界面活性剤（Ｃ）を含み、
前記脂肪酸エステル（Ａ）は、脂肪酸を有するジアセチルモノアシルグリセロール、および／または脂肪酸を有するジアセチルモノアシルグリセロール誘導体を含み、
前記界面活性剤（Ｃ）が、脂肪酸アミド系界面活性剤、金属石鹸、および硬化ヒマシ油の中から選択される少なくとも1つであることを特徴とする、液状マスターバッチ。 A liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin,
The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C),
The fatty acid ester (A) contains a diacetyl monoacylglycerol with fatty acid and/or a diacetyl monoacylglycerol derivative with fatty acid,
The liquid masterbatch, wherein the surfactant (C) is at least one selected from fatty acid amide surfactants, metallic soaps, and hydrogenated castor oil.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002053742A (en) * | 2000-08-07 | 2002-02-19 | Riken Vitamin Co Ltd | Plasticizer for pet-based resin, and pet-based resin composition |
| JP2020200364A (en) * | 2019-06-06 | 2020-12-17 | 東洋インキＳｃホールディングス株式会社 | Liquid master batch composition, thermoplastic resin composition and molded article |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002053742A (en) * | 2000-08-07 | 2002-02-19 | Riken Vitamin Co Ltd | Plasticizer for pet-based resin, and pet-based resin composition |
| JP2020200364A (en) * | 2019-06-06 | 2020-12-17 | 東洋インキＳｃホールディングス株式会社 | Liquid master batch composition, thermoplastic resin composition and molded article |
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