JP2008094932A - Titanium dioxide-containing polyester composition and its manufacturing method - Google Patents
Titanium dioxide-containing polyester composition and its manufacturing method Download PDFInfo
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- JP2008094932A JP2008094932A JP2006277387A JP2006277387A JP2008094932A JP 2008094932 A JP2008094932 A JP 2008094932A JP 2006277387 A JP2006277387 A JP 2006277387A JP 2006277387 A JP2006277387 A JP 2006277387A JP 2008094932 A JP2008094932 A JP 2008094932A
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- Prior art keywords
- titanium dioxide
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- polyester composition
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 322
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 153
- 229920000728 polyester Polymers 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title claims description 26
- 239000002245 particle Substances 0.000 claims abstract description 64
- 239000011362 coarse particle Substances 0.000 claims abstract description 31
- 239000002002 slurry Substances 0.000 claims description 48
- 229920000642 polymer Polymers 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000002612 dispersion medium Substances 0.000 claims description 14
- 150000002894 organic compounds Chemical group 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 7
- 150000002009 diols Chemical class 0.000 claims description 6
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 230000032050 esterification Effects 0.000 claims description 2
- 238000000034 method Methods 0.000 description 23
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 22
- YZTJKOLMWJNVFH-UHFFFAOYSA-N 2-sulfobenzene-1,3-dicarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1S(O)(=O)=O YZTJKOLMWJNVFH-UHFFFAOYSA-N 0.000 description 12
- 238000001914 filtration Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 230000006866 deterioration Effects 0.000 description 9
- 229920001225 polyester resin Polymers 0.000 description 9
- 239000004645 polyester resin Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000010298 pulverizing process Methods 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- -1 diphenyl ester Chemical class 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000004576 sand Substances 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052787 antimony Inorganic materials 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000009987 spinning Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 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 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GYUVMLBYMPKZAZ-UHFFFAOYSA-N dimethyl naphthalene-2,6-dicarboxylate Chemical compound C1=C(C(=O)OC)C=CC2=CC(C(=O)OC)=CC=C21 GYUVMLBYMPKZAZ-UHFFFAOYSA-N 0.000 description 2
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 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
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 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
- 238000005464 sample preparation method Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000006059 cover glass Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- WYIBAMPRACRCOM-UHFFFAOYSA-N dimethyl naphthalene-2,7-dicarboxylate Chemical compound C1=CC(C(=O)OC)=CC2=CC(C(=O)OC)=CC=C21 WYIBAMPRACRCOM-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229940014772 dimethyl sebacate Drugs 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000010101 extrusion blow moulding Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- LJJFYAPFNPSEFD-UHFFFAOYSA-N hexane-1,6-diol;2-(2-hydroxypropoxy)propan-1-ol Chemical compound OCCCCCCO.CC(O)COC(C)CO LJJFYAPFNPSEFD-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 1
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000010333 wet classification Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は二酸化チタン含有ポリエステル組成物及びその製造方法に関し、更に詳しくは、該組成物中の二酸化チタンの分散性並びに二酸化チタンポリエステル組成物の色相が改善されたポリエステル組成物及びその製造方法に関する。 The present invention relates to a titanium dioxide-containing polyester composition and a method for producing the same, and more particularly to a polyester composition having improved dispersibility of titanium dioxide in the composition and the hue of the titanium dioxide polyester composition and a method for producing the same.
一般にポリエステル樹脂に二酸化チタン等の微粒子を含有させて、得られる成型品の表面に凹凸を付与し、表面の滑り性や、反射・屈折光等を制御することが行われている。
しかしながら、二酸化チタン含有ポリエステル組成物を製造する際には、二酸化チタンの表面活性によってポリエステル樹脂が分解し、その分子量が低下するといった問題が発生することがある。また、二酸化チタンの粗大粒子が混入することにより成型時のフィルター詰まり、紡糸時の単糸切れ等の製造時の問題、色相斑、不透明性斑又は布帛の風合斑、染斑等の製品としての問題が発生すると共に、製品の成型または製糸工程設備の金属部が磨耗する等の工程上での問題点も発生しており、その解決手段として各種の提案がなされている。
In general, polyester resin is made to contain fine particles such as titanium dioxide to give unevenness to the surface of the resulting molded product, thereby controlling the slipperiness of the surface, reflected / refracted light, and the like.
However, when a titanium dioxide-containing polyester composition is produced, there may be a problem that the polyester resin is decomposed by the surface activity of titanium dioxide and its molecular weight is lowered. In addition, as titanium dioxide coarse particles are mixed, products such as filter clogging during molding, production problems such as single yarn breakage during spinning, hue spots, opaque spots, fabric texture spots, dyed spots, etc. In addition to the above problems, there are also problems in processes such as product molding or wear of metal parts of the yarn making process equipment, and various proposals have been made as means for solving the problems.
例えば、粗大粒子を除去する方法として、ポリエステル製造時に二酸化チタンを添加する際に、あらかじめ該二酸化チタンに対して粉砕、分級等の操作を行って粗大粒子を除去し、スラリー状あるいは液状にして添加する方法（例えば特許文献１参照。）や、製造後のポリエステルに二酸化チタンを添加し、溶融混練する場合には単軸あるいは多軸溶融混練押出機を用いてポリエステルポリマー及び二酸化チタンに剪断応力を加えて溶融混練を行う方法（例えば特許文献２参照。）、ベント付き押出機を用いてポリエステルポリマーに平均粒径０．０１〜５μｍの範囲にある無機粒子を、水及び／又は沸点２００℃以下の有機化合物のスラリーとして添加する方法（例えば特許文献３参照。）などが提案されている。 For example, as a method of removing coarse particles, when adding titanium dioxide at the time of polyester production, the coarse particles are removed in advance by subjecting the titanium dioxide to operations such as pulverization and classification, and added in a slurry or liquid form. (For example, refer to Patent Document 1) or when adding titanium dioxide to the polyester after production and melt-kneading, a shear stress is applied to the polyester polymer and titanium dioxide using a single-screw or multi-screw melt-kneading extruder. In addition, a method of performing melt-kneading (see, for example, Patent Document 2), an inorganic particle having an average particle size of 0.01 to 5 μm is added to a polyester polymer using a vented extruder, water and / or a boiling point of 200 ° C. or less. A method of adding the organic compound as a slurry (see, for example, Patent Document 3) has been proposed.
しかしながら、あらかじめ粗大粒子を除去する方法では、粉砕・分級操作に多大な費用や作業時間がかかる。更に、たとえこれらの除去作業を行っても、ポリエステル製造系に二酸化チタンを添加する際に、あるいは添加終了後にポリエステルポリマー内にて二酸化チタンが再凝集し、製品ポリエステル中での粗大粒子の生成を防止することは困難である。 However, in the method of removing coarse particles in advance, a large cost and work time are required for the pulverization / classification operation. Furthermore, even if these removal operations are performed, titanium dioxide is re-agglomerated in the polyester polymer when titanium dioxide is added to the polyester production system or after the addition is completed, and coarse particles are produced in the product polyester. It is difficult to prevent.
一方、単軸又は多軸の溶融混練押出機を用いて溶融混練する方法では、粉末中に存在する粗大粒子を単軸又は多軸押出機内で完全に粉砕するあるいは完全に混練することは非常に難しい。また、ポリエステルポリマー中に二酸化チタンを均一に分散させるために剪断応力をかけすぎると、ポリエステルポリマーの固有粘度が著しく低下する、更にあらかじめ粗大粒子を除去する方法と同様に、ポリマーと微粒子を混練押出機に供給する場合には混練工程中に二酸化チタンの再凝集を避けるのが困難である。その結果、製造工程中に生じた粗大粒子を除去することができず、満足する製品を得ることができなかった。 On the other hand, in the method of melt-kneading using a single-screw or multi-screw melt-kneading extruder, it is very difficult to completely pulverize or completely knead coarse particles present in the powder in the single-screw or multi-screw extruder. difficult. If too much shear stress is applied to uniformly disperse the titanium dioxide in the polyester polymer, the intrinsic viscosity of the polyester polymer will be significantly reduced, and the polymer and fine particles will be kneaded and extruded in the same way as coarse particles are removed beforehand. When supplying to the machine, it is difficult to avoid reaggregation of titanium dioxide during the kneading process. As a result, coarse particles generated during the production process could not be removed, and a satisfactory product could not be obtained.
このような問題に鑑み、上記の問題を解決し、ポリエステルの耐熱性を維持しつつ、二酸化チタンの分散性に優れ、金属磨耗が低減された、二酸化チタン含有ポリエステル組成物およびその製造法を提供するべく、特定の表面処理を施した二酸化チタンを含有するポリエステル組成物およびその製造方法を本発明者らは先に提案した（例えば特許文献４、５参照。）。しかしながら本発明においては、ポリエステル樹脂中の分散性の安定性の面ではばらつきがあり、必ずしも十分とは言えないことが分かった。そこで本発明者らは二酸化チタンの再設計し、二酸化チタンの再凝集を抑制し、分散性が更に向上された、二酸化チタン含有ポリエステル組成物およびその製造方法を先に提案した（例えば特許文献６参照。）。しかしながら、同発明においては、ポリエステルの色相、特に黄色味が強く出るという欠点があり、必ずしも十分とは言えないことが分かった。 In view of these problems, a titanium dioxide-containing polyester composition that solves the above-described problems and has excellent dispersibility of titanium dioxide and reduced metal wear while maintaining the heat resistance of polyester and a method for producing the same are provided. Therefore, the present inventors previously proposed a polyester composition containing titanium dioxide subjected to a specific surface treatment and a method for producing the same (see, for example, Patent Documents 4 and 5). However, in the present invention, it has been found that there is a variation in terms of stability of dispersibility in the polyester resin, which is not necessarily sufficient. Accordingly, the present inventors have previously proposed a titanium dioxide-containing polyester composition and a method for producing the same, by redesigning titanium dioxide, suppressing reaggregation of titanium dioxide, and further improving dispersibility (for example, Patent Document 6). reference.). However, in the present invention, it has been found that there is a drawback that the hue of polyester, particularly yellowishness, is strong, and it is not necessarily sufficient.
原因を考察したところ、二酸化チタン中に含有するＰ２Ｏ５，Ｋ２Ｏ及びＳｂが二酸化チタン添加後のポリエステル組成物の色相を悪化させているためではないかと我々は考えた。そこで、二酸化チタンを新規設計することにより、二酸化チタンの分散性を維持したままポリエステルの色相を改善させることを発見し、本発明に至った。すなわち、本発明の第１の目的は、新規に物性を設計した二酸化チタンを含有することで、色相が改善されたポリエステル組成物を提供することにある。本発明の第２の目的は、上記の二酸化チタン含有ポリエステル組成物の製造方法を提供することにある。 When the cause was considered, we thought that P 2 O 5 , K 2 O and Sb contained in titanium dioxide deteriorated the hue of the polyester composition after addition of titanium dioxide. Then, it discovered that the hue of polyester was improved by maintaining the dispersibility of titanium dioxide by designing titanium dioxide newly, and it came to this invention. That is, the first object of the present invention is to provide a polyester composition having improved hue by containing titanium dioxide having a newly designed physical property. The second object of the present invention is to provide a method for producing the above-mentioned titanium dioxide-containing polyester composition.
すなわち本発明は、下記（ａ）〜（ｊ）の各要件を同時に満足する二酸化チタンをポリエステル組成物全重量を基準として０．０１重量％以上７０重量％以下含有する二酸化チタン含有ポリエステル組成物である。
（ａ）平均粒子径が０．１〜０．５μｍの範囲にあること。
（ｂ）粒子径が３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下であること。
（ｃ）粒子径が４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること。
（ｄ）Ｐ２Ｏ５を二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲で含有すること。
（ｅ）Ｋ２Ｏを二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲で含有すること。
（ｆ）強熱減量率が０．４重量％以下であること。
（ｇ）結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であること。
（ｈ）結晶子サイズが１０〜１５０ｎｍの範囲にあること。
（ｉ）実質的にＦｅを含有しないこと。
（ｊ）Ｓｂ元素を二酸化チタンの全重量を基準として５０ｐｐｍ以下の範囲で含有すること。
That is, the present invention is a titanium dioxide-containing polyester composition containing 0.01% by weight or more and 70% by weight or less of titanium dioxide that simultaneously satisfies the following requirements (a) to (j): is there.
(A) The average particle diameter is in the range of 0.1 to 0.5 μm.
(B) Coarse particles having a particle diameter of 3 μm or more are 5000 particles / 0.4 mg or less.
(C) The number of coarse particles having a particle diameter of 4 μm or more is 1500 particles / 0.4 mg or less.
(D) P 2 O 5 in that it contains in the range of 0.10 to 0.30 weight percent based on the total weight of titanium dioxide.
(E) containing K 2 O in the range of 0.01 to 0.15% by weight based on the total weight of titanium dioxide.
(F) The ignition loss rate is 0.4% by weight or less.
(G) The value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less.
(H) The crystallite size is in the range of 10 to 150 nm.
(I) It does not contain Fe substantially.
(J) Containing Sb element in the range of 50 ppm or less based on the total weight of titanium dioxide.
本発明によれば、本発明による二酸化チタン含有ポリエステル組成物は、熱劣化が無く、ポリエステル組成物中においても成型品や繊維等に加工しても二酸化チタンが再凝集することなく高度の分散性を保ち、ポリエステル成型設備における金属の磨耗を低減し、更に色相の良好なポリエステル組成物を得ることができる。 According to the present invention, the titanium dioxide-containing polyester composition according to the present invention is not thermally deteriorated and has high dispersibility without being re-aggregated even when the polyester composition is processed into a molded article or fiber. Thus, it is possible to reduce the metal wear in the polyester molding equipment and to obtain a polyester composition having a good hue.
本発明の第一は特定の特性を有する二酸化チタンを、ポリエステル組成物全重量を基準として０．０１〜７０重量％含有する二酸化チタン含有ポリエステル組成物である。 The first of the present invention is a titanium dioxide-containing polyester composition containing 0.01 to 70% by weight of titanium dioxide having specific characteristics based on the total weight of the polyester composition.
本発明で使用される二酸化チタンは、その平均粒径が０．１〜０．５μｍの範囲にあり、３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下、且つ４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であり、更にＰ２Ｏ５量が二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲にあり、かつＫ２Ｏ量が二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲にあることが必要である。平均粒径が０．５μｍを超えると二酸化チタンの粗大粒子が増加する上、分散性が悪化し、成型時のフィルター詰まりや紡糸時の断糸が多発する。また、平均粒径が０．１μｍ未満であると、二酸化チタンの比表面積が大きくなるため、二酸化チタン単位重量あたりの表面活性が高くなりすぎて、ポリマーを劣化させたり、二酸化チタン粒子同士の凝集を促進するので好ましくない。また、粒子径が３μｍを超える粗大粒子が５０００個／０．４ｍｇを超えるか、４μｍを超える粗大粒子が１５００個／０．４ｍｇを超えるか、更にＰ２Ｏ５量が二酸化チタンの全重量を基準として０．１０重量％未満であるか、又はＫ２Ｏ量が０．０１重量％未満であると、二酸化チタン含有ポリエステル組成物中の粒子分散性が著しく劣るようになり、製糸工程におけるパック圧の上昇や、製糸・製膜その他成形工程においてフィルター寿命を著しく短くしたり、製糸・成形設備に対する金属磨耗が著しく悪化してしまう。一方、Ｐ２Ｏ５量が二酸化チタンの全重量を基準として０．３０重量％を超えるか、Ｋ２Ｏ量が０．１５重量％を超える場合には、二酸化チタン含有ポリエステル組成物の分子量の低下、組成物の色相悪化が発現することがある。詳細な理由は不明であるが、一つの原因としてアルカリ金属であるカリウムからなるＫ２Ｏがポリエステル組成物の分解を促進し、分子量の低下並びに色相の悪化を引き起こすと考えることができる。 The titanium dioxide used in the present invention has an average particle size in the range of 0.1 to 0.5 μm, 5000 / 0.4 mg or less coarse particles of 3 μm or more, and 1500 coarse particles of 4 μm or more. /0.4 mg or less, the amount of P 2 O 5 is in the range of 0.10 to 0.30% by weight based on the total weight of titanium dioxide, and the amount of K 2 O is based on the total weight of titanium dioxide. As a range from 0.01 to 0.15% by weight. When the average particle size exceeds 0.5 μm, coarse particles of titanium dioxide increase, dispersibility deteriorates, and filter clogging during molding and yarn breakage during spinning occur frequently. In addition, when the average particle size is less than 0.1 μm, the specific surface area of titanium dioxide increases, so that the surface activity per unit weight of titanium dioxide becomes too high, causing deterioration of the polymer or aggregation of titanium dioxide particles. This is not preferable. Further, the number of coarse particles exceeding 3 μm exceeds 5000 particles / 0.4 mg, the amount of coarse particles exceeding 4 μm exceeds 1500 particles / 0.4 mg, and the amount of P 2 O 5 is the total weight of titanium dioxide. When the amount is less than 0.10% by weight or the amount of K 2 O is less than 0.01% by weight, the particle dispersibility in the titanium dioxide-containing polyester composition becomes extremely inferior, and the pack in the yarn making process The filter life is significantly shortened in the pressure increase, the yarn making / film forming and other forming processes, and the metal wear on the yarn forming / forming equipment is remarkably deteriorated. On the other hand, when the amount of P 2 O 5 exceeds 0.30% by weight based on the total weight of titanium dioxide or the amount of K 2 O exceeds 0.15% by weight, the molecular weight of the titanium dioxide-containing polyester composition Reduction and deterioration of the hue of the composition may occur. Although the detailed reason is unknown, it can be considered that K 2 O composed of potassium, which is an alkali metal, promotes the decomposition of the polyester composition as one cause, causing a decrease in molecular weight and a deterioration in hue.
本発明において使用する二酸化チタンはその強熱減量が０．４重量％以下であることが必要である。該強熱減量が０．４重量％を超えると、得られる二酸化チタン含有ポリエステル組成物の熱安定性が著しく低下する。即ち、該組成物を溶融押出した際の固有粘度の変化が大きくなり、特に二酸化チタンの配合量が多い場合にポリエステル組成物の熱安定性の低下が著しい。 The titanium dioxide used in the present invention must have a loss on ignition of 0.4% by weight or less. When the ignition loss exceeds 0.4% by weight, the thermal stability of the resulting titanium dioxide-containing polyester composition is significantly lowered. That is, the change in intrinsic viscosity when the composition is melt-extruded becomes large, and particularly when the amount of titanium dioxide is large, the thermal stability of the polyester composition is remarkably lowered.
本発明において使用する二酸化チタンは、結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であることが必要である。該値が９×１０−３を超える場合には、二酸化チタンの硬さが増し、成形・紡糸設備に対する金属磨耗が著しく悪化する。 The titanium dioxide used in the present invention needs to have a value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less. When the value exceeds 9 × 10 −3 , the hardness of titanium dioxide increases and the metal wear on the forming / spinning equipment is significantly deteriorated.
本発明において使用する二酸化チタンは、結晶子サイズが１０〜１５０ｎｍの範囲にある必要がある。該結晶子サイズが１０ｎｍ未満であると、解砕処理により粒子が微細化されすぎており、必要となる平均粒子径の維持が困難である。一方、１５０ｎｍを越える場合には解砕処理が困難で、処理に多大な時間を要する。 The titanium dioxide used in the present invention needs to have a crystallite size in the range of 10 to 150 nm. If the crystallite size is less than 10 nm, the particles are too fined by the crushing treatment, and it is difficult to maintain the required average particle size. On the other hand, when it exceeds 150 nm, the crushing process is difficult, and the process takes a lot of time.
また、本発明において、使用する二酸化チタンは実質的にＦｅを含有しないことが必要である。該Ｆｅを含有する場合には成形・製糸設備に対する金属磨耗が著しくなり、色相も悪化する。Ｆｅは密度が高く、その粒子表面が硬いので、金属磨耗が著しくなるものと考えられる。実質的に含有しないとは絶対的に含有していない事とは異なり、通常当業者がＦｅの含有の定性分析・定量分析に用いる測定機器を用いても検知できない事を表す。 In the present invention, it is necessary that the titanium dioxide used contains substantially no Fe. When Fe is contained, metal wear on the forming / spinning equipment becomes remarkable, and the hue deteriorates. Fe has a high density and its particle surface is hard, so it is considered that metal wear becomes remarkable. The fact that it is not substantially contained means that it cannot be detected even if a person skilled in the art normally uses a measuring instrument used for qualitative analysis / quantitative analysis of Fe content.
本発明においては、使用する二酸化チタンはＳｂ元素の含有量が二酸化チタンの全重量を基準として５０ｐｐｍ以下である必要がある。５０ｐｐｍを超えて含有する場合は、ポリエステル組成物の分子量の低下、組成物の色相悪化が発現することがある。Ｓｂ化合物はポリエステルの重合触媒として一般的に使用されているが、同時に分解活性も有しているため、ポリエステル組成物の分解を促進し、分子量の低下並びに色相の悪化（特に黄色味の増加）を引き起こすと考えることができる。このために二酸化チタン中のＳｂ元素含有量を減らす事は、分子量の低下及び色相悪化の抑制のために有効であると考えられる。 In the present invention, the titanium dioxide used must have an Sb element content of 50 ppm or less based on the total weight of titanium dioxide. When it contains exceeding 50 ppm, the fall of the molecular weight of a polyester composition and the hue deterioration of a composition may express. The Sb compound is generally used as a polymerization catalyst for polyester, but also has decomposition activity at the same time, so it promotes the decomposition of the polyester composition, lowers the molecular weight as well as the hue (especially increases the yellowness). Can be thought of as causing For this reason, it is considered that reducing the Sb element content in titanium dioxide is effective for reducing molecular weight and suppressing hue deterioration.
これらの要件の中で好ましくは平均粒径が０．２〜０．３５μｍであること、３μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること、Ｋ２Ｏ量が０．０２〜０．０８重量％であること、強熱減量率が０．２５重量％以下であること、ルチル／アナターゼ比が１．０×１０−３以下、より好ましくは０．５×１０−３以下であること、の少なくともいずれか１つの項目を満たすことであり、より好ましくは複数の項目を満たすことである。 Among these requirements, the average particle diameter is preferably 0.2 to 0.35 μm, the coarse particles of 3 μm or more are 1500 particles / 0.4 mg or less, and the K 2 O amount is 0.02 to 0. 0.08 wt%, ignition loss ratio is 0.25 wt% or less, rutile / anatase ratio is 1.0 × 10 −3 or less, more preferably 0.5 × 10 −3 or less. Satisfying at least one of the items, more preferably satisfying a plurality of items.
また本発明において二酸化チタン含有量がポリエステル組成物全重量を基準として０．０１重量％未満であるとポリエステル組成物としての色相の改善効果が発現しないことがあり、７０重量％を超えると含有量が多すぎて、ポリエステル中での分散性が悪化することがある。好ましくは０．１重量％〜６０重量％である。 In the present invention, if the titanium dioxide content is less than 0.01% by weight based on the total weight of the polyester composition, the hue improving effect as the polyester composition may not be exhibited. In some cases, the dispersibility in the polyester may deteriorate. Preferably it is 0.1 weight%-60 weight%.
本発明において、二酸化チタンを含有させるポリエステル組成物を構成するポリエステルとは、ジカルボン酸及び／又はそのエステル形成性誘導体並びにジオールとから合成される線状飽和ポリエステルであって、汎用樹脂としてその物性を損なわない範囲で目的に応じて他の成分が共重合されていても良い。 In the present invention, the polyester constituting the polyester composition containing titanium dioxide is a linear saturated polyester synthesized from dicarboxylic acid and / or an ester-forming derivative thereof and a diol, and has physical properties as a general-purpose resin. Other components may be copolymerized depending on the purpose as long as they are not impaired.
本発明の別の１つは、上記の二酸化チタンと、水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物である分散媒とからなる二酸化チタンスラリーである。そのスラリーは二酸化チタンがスラリーの全重量を基準として２０〜７０重量％含有し、該スラリーの粘度が常温で１００ｍＰａ・ｓ以下であることを特徴とする。スラリー濃度が２０重量％未満では、ポリエステル製造時に所定量の二酸化チタンを添加するために多量のスラリーを供給せねばならず、スラリーの分散媒によりポリエステル製造装置の内温低下に伴う固有粘度、ジエチレングリコールその他の副生物の含有量ばらつきが大きくなる他、経済的にも好ましくない。７０重量％を超えるとスラリーの粘度を１００ｍＰａ・ｓ以下に保つことが困難になり、スラリーの流動性が悪化して送液配管中での二酸化チタンの沈降、配管閉塞を誘起したり、ポリエステル組成物中での均一分散が困難になり、好ましくない。 Another one of the present invention is a titanium dioxide slurry comprising the above titanium dioxide and water and / or a dispersion medium which is an organic compound having a boiling point in the range of 50 to 240 ° C. The slurry is characterized in that titanium dioxide contains 20 to 70% by weight based on the total weight of the slurry, and the viscosity of the slurry is 100 mPa · s or less at room temperature. If the slurry concentration is less than 20% by weight, a large amount of slurry must be supplied in order to add a predetermined amount of titanium dioxide at the time of producing the polyester, and the inherent viscosity accompanying the decrease in the internal temperature of the polyester production apparatus due to the dispersion medium of the slurry, diethylene glycol The content variation of other by-products becomes large, and it is not preferable economically. When it exceeds 70% by weight, it becomes difficult to keep the viscosity of the slurry at 100 mPa · s or less, and the fluidity of the slurry is deteriorated to induce sedimentation of titanium dioxide in the liquid feeding pipe, blockage of the pipe, polyester composition Uniform dispersion in the material becomes difficult, which is not preferable.
ここで、水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物としては、水、メタノール、エタノール、エチレングリコール若しくは１，４−ブタンジオール等のアルコール類、ベンゼン、トルエン若しくはキシレン等の芳香族有機化合物、テトラヒドロフラン、１，３−ジオキソラン若しくは２−メチル−１，３−ジオキソラン等のエーテル類、その他エステル類、ケトン類又はアミン類等を挙げることができるが、特に制限されるものではない。しかし、スラリーとして添加した後、後に行う分散媒の除去の容易性から、水、エチレングリコール、１，４−ブタンジオール又はテトラヒドロフランを用いることが好ましく、ハンドリング性、安全性、コストの観点から水が最も好ましい。該スラリーの分散媒は一種を用いても、二種以上の混合分散媒を用いても構わない。 Here, water and / or organic compounds having a boiling point in the range of 50 to 240 ° C. include water, alcohols such as methanol, ethanol, ethylene glycol, and 1,4-butanediol, and aromatics such as benzene, toluene, and xylene. Group ether compounds, ethers such as tetrahydrofuran, 1,3-dioxolane or 2-methyl-1,3-dioxolane, and other esters, ketones or amines, but are not particularly limited. . However, it is preferable to use water, ethylene glycol, 1,4-butanediol or tetrahydrofuran from the viewpoint of ease of removal of the dispersion medium to be performed later after addition as a slurry, and water from the viewpoint of handling properties, safety, and cost. Most preferred. One kind of the dispersion medium of the slurry may be used, or two or more kinds of mixed dispersion mediums may be used.
分散媒として用いる有機化合物の沸点が５０〜２４０℃の範囲を外れると、分散媒が揮発しやすいため、スラリー中の二酸化チタンの濃度を一定保つのが困難であったり、ポリエステル組成物を製造する工程内で用いる際に分散媒を後で除去するのが困難になるため好ましくない。この点は又後述する。 When the boiling point of the organic compound used as the dispersion medium is outside the range of 50 to 240 ° C., the dispersion medium is likely to volatilize, so that it is difficult to keep the concentration of titanium dioxide in the slurry constant, or a polyester composition is produced. Since it becomes difficult to remove a dispersion medium later when using it in a process, it is not preferable. This point will also be described later.
更に、二酸化チタンが均一に分散しているスラリーを得るために、本発明の目的を奏する範囲内であれば各種の添加剤を用いてもよく、該添加剤としては、ポリスチレンスルホン酸ソーダ、カルボキシメチルセルロース若しくはポリビニルアルコール等の保護剤、水酸化ナトリウム若しくはヘキサメタリン酸ナトリウム等のナトリウム塩、テトラメチルアンモニウムクロライド若しくはテトラエチルアンモニウムヒドロキサイド等のオニウム化合物、ドデシルベンゼンスルホン酸ナトリウム若しくはラウリル硫酸ナトリウム等のアニオン系界面活性剤又はポリエチレングリコールモノステアレート等のノニオン系界面活性剤等を挙げることができる。 Furthermore, in order to obtain a slurry in which titanium dioxide is uniformly dispersed, various additives may be used as long as the purpose of the present invention is achieved. Examples of the additive include polystyrene sulfonate, carboxy Protective agents such as methylcellulose or polyvinyl alcohol, sodium salts such as sodium hydroxide or sodium hexametaphosphate, onium compounds such as tetramethylammonium chloride or tetraethylammonium hydroxide, anionic surfactants such as sodium dodecylbenzenesulfonate or sodium lauryl sulfate And nonionic surfactants such as polyethylene glycol monostearate.
本発明において、上述のように二酸化チタンを含有させるポリエステル組成物を構成するポリエステルとは、ジカルボン酸及び／又はそのエステル形成性誘導体並びにジオールとから合成される線状飽和ポリエステルであって、汎用樹脂としての物性を失わない範囲で目的に応じて他の成分が共重合されていてもよい。 In the present invention, the polyester constituting the polyester composition containing titanium dioxide as described above is a linear saturated polyester synthesized from dicarboxylic acid and / or its ester-forming derivative and diol, and is a general-purpose resin. Other components may be copolymerized depending on the purpose as long as the physical properties are not lost.
ジカルボン酸及び／又はそのエステル形成性誘導体として、テレフタル酸、２，６−ナフタレンジカルボン酸、２，７−ナフタレンジカルボン酸、イソフタル酸、１，４−シクロヘキシルジカルボン酸、アジピン酸、セバシン酸、フタル酸、無水フタル酸、５−リチウムスルホイソフタル酸、５−ナトリウムスルホイソフタル酸、５−カリウムスルホイソフタル酸、５−テトラメチルホスホニウムスルホイソフタル酸、５−テトラエチルホスホニウムスルホイソフタル酸、５−テトラプロピルホスホニウムスルホイソフタル酸、５−テトラブチルホスホニウムスルホイソフタル酸、テレフタル酸ジメチル、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、イソフタル酸ジメチル、１，４−シクロヘキサンジカルボン酸ジメチル、アジピン酸ジメチル、セバシン酸ジメチル、フタル酸ジメチル、５−リチウムスルホイソフタル酸ジメチル、５−ナトリウムスルホイソフタル酸ジメチル、５−カリウムスルホイソフタル酸ジメチル、５−テトラメチルホスホニウムスルホイソフタル酸ジメチル、５−テトラエチルホスホニウムスルホイソフタル酸ジメチル、５−テトラプロピルホスホニウムスルホイソフタル酸ジメチル又は５−テトラブチルホスホニウムスルホイソフタル酸ジメチル等を挙げることができる。またエステル形成性誘導体としては、上記のようなジメチルエステルその他の低級アルキルエステル以外に、ジフェニルエステル、酸塩化物、酸臭化物を用いても良い。これらの中でも特に、テレフタル酸、２，６−ナフタレンジカルボン酸、テレフタル酸ジメチル又は２，６−ナフタレンジカルボン酸ジメチルを用いることが好ましい。 Dicarboxylic acids and / or ester-forming derivatives thereof include terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, isophthalic acid, 1,4-cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, phthalic acid Phthalic anhydride, 5-lithium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, 5-tetramethylphosphonium sulfoisophthalic acid, 5-tetraethylphosphonium sulfoisophthalic acid, 5-tetrapropylphosphonium sulfoisophthalic acid Acid, 5-tetrabutylphosphonium sulfoisophthalic acid, dimethyl terephthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, dimethyl isophthalate, 1,4-cyclohexa Dimethyl dicarboxylate, dimethyl adipate, dimethyl sebacate, dimethyl phthalate, dimethyl 5-lithium sulfoisophthalate, dimethyl 5-sodium sulfoisophthalate, dimethyl 5-potassium sulfoisophthalate, dimethyl 5-tetramethylphosphonium sulfoisophthalate, Examples thereof include dimethyl 5-tetraethylphosphonium sulfoisophthalate, dimethyl 5-tetrapropylphosphonium sulfoisophthalate, and dimethyl 5-tetrabutylphosphonium sulfoisophthalate. In addition to the dimethyl ester and other lower alkyl esters as described above, diphenyl ester, acid chloride, and acid bromide may be used as the ester-forming derivative. Among these, it is particularly preferable to use terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, or dimethyl 2,6-naphthalenedicarboxylate.
また、ジオールとして、エチレングリコール、１，４−ブタンジオール、ジエチレングリコール、トリメチレングリコール、１，２−プロピレングリコール、２，２−ジメチル−１，３−プロパンジオール（ネオペンチレングリコール）、ジプロピレングリコール、１，６−ヘキサンジオール、１，４−ヘキサンジメタノール、ジメチロールプロピオン酸、ポリ（エチレンオキシド）グリコール又はポリ（テトラメチレンオキシド）グリコール等を挙げることができ、特にエチレングリコール、トリメチレングリコール又は１，４−ブタンジオールを用いることが好ましい。
これらのジカルボン酸及び／又はそのエステル形成性誘導体並びにジオールはそれぞれ１種ずつを単独で用いても、２種以上を併用してもどちらでもよい。
Further, as the diol, ethylene glycol, 1,4-butanediol, diethylene glycol, trimethylene glycol, 1,2-propylene glycol, 2,2-dimethyl-1,3-propanediol (neopentylene glycol), dipropylene glycol 1,6-hexanediol, 1,4-hexanedimethanol, dimethylolpropionic acid, poly (ethylene oxide) glycol or poly (tetramethylene oxide) glycol, and the like, particularly ethylene glycol, trimethylene glycol or 1 1,4-butanediol is preferably used.
Each of these dicarboxylic acids and / or ester-forming derivatives thereof and diols may be used alone or in combination of two or more.
尚本発明における該ポリエステルには、トリメリット酸、トリメシン酸、無水トリメリット酸、ピロメリット酸若しくはトリメリット酸モノカリウム塩などの多価カルボン酸、グリセリン、ジメチロールエチルスルホン酸ナトリウム若しくはジメチロールプロピオン酸カリウム等の多価ヒドロキシ化合物又はｐ−ヒドロキシ安息香酸等のヒドロキシカルボン酸を、本発明の目的を達成する範囲内であれば共重合してもよい。 In the present invention, the polyester includes trimellitic acid, trimesic acid, trimellitic anhydride, pyromellitic acid or trimellitic acid monopotassium salt, glycerin, dimethylol ethyl sulfonate sodium or dimethylol propion. Polyhydric hydroxy compounds such as potassium acid or hydroxycarboxylic acids such as p-hydroxybenzoic acid may be copolymerized as long as the object of the present invention is achieved.
本発明のポリエステル組成物には通常ポリエステルの製造時に通常用いられるリチウム、ナトリウム、カルシウム、マグネシウム、マンガン、亜鉛、アンチモン、ゲルマニウム若しくはチタン等の金属化合物触媒、着色防止剤としてのリン化合物又はその他のポリエステルの改質に用いられる不活性粒子や有機化合物等を本発明の目的を奏する範囲内で含んでいてもよい。 The polyester composition of the present invention is usually a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium or titanium, which is usually used in the production of polyester, a phosphorus compound as an anti-coloring agent or other polyester. An inert particle, an organic compound, or the like used for the modification of the resin may be included within the range that achieves the object of the present invention.
本発明のポリエステル組成物には通常ポリエステルの製造時に通常用いられるリチウム、ナトリウム、カルシウム、マグネシウム、マンガン、亜鉛、アンチモン、ゲルマニウム若しくはチタン等の金属化合物触媒、着色防止剤としてのリン化合物又はその他のポリエステルの改質に用いられる不活性粒子や有機化合物等を本発明の目的を奏する範囲内で含んでいてもよい。 The polyester composition of the present invention is usually a metal compound catalyst such as lithium, sodium, calcium, magnesium, manganese, zinc, antimony, germanium or titanium, which is usually used in the production of polyester, a phosphorus compound as an anti-coloring agent or other polyester. An inert particle, an organic compound, or the like used for the modification of the resin may be included within the range that achieves the object of the present invention.
本発明における二酸化チタン含有ポリエステル組成物の製造としては、ジカルボン酸及び／又はそのエステル形成性誘導体と、ジオールとをエステル化及び／又はエステル交換反応させ、次いで重縮合反応を行ってポリエステルポリマーを製造する際に、エステル化及び／又はエステル交換反応終了後から重合反応完結前の任意の段階で、下記（ａ’）〜（ｊ’）の各要件を同時に満足する二酸化チタンを、二酸化チタンの含有量が該二酸化チタン含有ポリエステル組成物の全重量を基準として０．０１重量％以上７０重量％以下になるように添加することにより製造することができる。該二酸化チタンは、上述した該二酸化チタンをそのまま粉体状で添加しても良いし、該二酸化チタンと、水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物である分散媒からなるスラリーを用いて添加しても良いが、取り扱いが容易な事、反応機内への分散が容易な点から該スラリーを用いて添加することが好ましい。添加する手法としては通常の器の形状の反応機で重合反応を行う場合には反応の完結前までにその反応器に投入すればよいし、エクストルーダーのような混練機中で重合反応を行う際には機内で反応が開始する前に投入すればよい。
（ａ’）平均粒子径が０．１〜０．５μｍの範囲にあること。
（ｂ’）粒子径が３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下であること。
（ｃ’）粒子径が４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること。
（ｄ’）Ｐ２Ｏ５を二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲で含有すること。
（ｅ’）Ｋ２Ｏを二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲で含有すること。
（ｆ’）強熱減量率が０．４重量％以下であること。
（ｇ’）結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であること。
（ｈ’）結晶子サイズが１０〜１５０ｎｍの範囲にあること。
（ｉ’）実質的にＦｅを含有しないこと。
（ｊ’）Ｓｂを二酸化チタンの全重量を基準として、５０ｐｐｍ以下であること。
In the production of the polyester composition containing titanium dioxide in the present invention, a polyester polymer is produced by esterifying and / or transesterifying a dicarboxylic acid and / or an ester-forming derivative thereof and a diol, followed by a polycondensation reaction. In this case, the titanium dioxide containing titanium dioxide that simultaneously satisfies the following requirements (a ′) to (j ′) at any stage after completion of the esterification and / or transesterification reaction and before completion of the polymerization reaction: It can manufacture by adding so that the quantity may be 0.01 to 70 weight% on the basis of the total weight of this titanium dioxide containing polyester composition. The titanium dioxide may be added in the form of powder as described above, or comprises titanium and a dispersion medium that is water and / or an organic compound having a boiling point in the range of 50 to 240 ° C. Although it may be added using a slurry, it is preferable to add using the slurry from the viewpoint of easy handling and easy dispersion in the reactor. As a method of addition, when a polymerization reaction is carried out in a reactor having a normal vessel shape, it may be introduced into the reactor before the completion of the reaction, or the polymerization reaction is carried out in a kneader such as an extruder. In some cases, it may be added before the reaction starts in the machine.
(A ′) The average particle diameter is in the range of 0.1 to 0.5 μm.
(B ′) Coarse particles having a particle diameter of 3 μm or more are 5000 particles / 0.4 mg or less.
(C ′) Coarse particles having a particle diameter of 4 μm or more are 1500 particles / 0.4 mg or less.
(D ′) P 2 O 5 is contained in the range of 0.10 to 0.30% by weight based on the total weight of titanium dioxide.
(E ′) containing K 2 O in a range of 0.01 to 0.15% by weight based on the total weight of titanium dioxide.
(F ′) The ignition loss rate is 0.4% by weight or less.
(G ′) The value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less.
(H ′) The crystallite size is in the range of 10 to 150 nm.
(I ′) substantially not containing Fe.
(J ′) Sb is 50 ppm or less based on the total weight of titanium dioxide.
また上述の二酸化チタンを、水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物を分散媒とするスラリー状態で添加する場合に、分散媒の沸点が５０℃未満だと室温での蒸発散逸が激しく、スラリー濃度の変化や気化した蒸気により作業環境を悪化させるため好ましくない。分散媒の沸点が２４０℃を越えると分散媒を気化させて反応器からの脱気することが困難となる。ここで分散媒の気化を促進させるため、反応器の温度を上げるとポリエステル樹脂の劣化を促進するため、好ましくない。特にポリエステル樹脂組成物の全重量を基準として二酸化チタンを５〜７０重量％含有しているポリエステル樹脂組成物、すなわち比較的高濃度の二酸化チタン含有ポリエステル樹脂、いわゆるマスターバッチと称するポリエステル樹脂を製造する際には、押出機へ供給されたポリエステル樹脂へ二酸化チタンを添加する時、ノズルを通じて二酸化チタンスラリーの水スラリーを液体状態で添加する方法等が好適に実施される。 In addition, when the above-mentioned titanium dioxide is added in a slurry state using water and / or an organic compound having a boiling point in the range of 50 to 240 ° C. as a dispersion medium, if the boiling point of the dispersion medium is less than 50 ° C., evaporation at room temperature is performed. Dissipation is severe, and the working environment is deteriorated by changes in slurry concentration and vaporized vapor. When the boiling point of the dispersion medium exceeds 240 ° C., it is difficult to vaporize the dispersion medium and degas from the reactor. Here, in order to promote the vaporization of the dispersion medium, it is not preferable to raise the temperature of the reactor because it promotes the deterioration of the polyester resin. In particular, a polyester resin composition containing 5 to 70% by weight of titanium dioxide based on the total weight of the polyester resin composition, that is, a polyester resin containing a relatively high concentration of titanium dioxide-containing polyester resin, a so-called masterbatch is produced. In this case, when adding titanium dioxide to the polyester resin supplied to the extruder, a method of adding an aqueous slurry of titanium dioxide slurry in a liquid state through a nozzle is preferably performed.
二酸化チタンと水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物とのスラリーは単独で用いても、二種類以上を混合して用いてもよく、これらは常法に従って調製することができる。例えば一例を挙げると、上述の範囲の重量になるように二酸化チタン並びに水及び／又は有機化合物を計量する。次に水及び／又は有機化合物に対して二酸化チタンを投入し、高速回転可能な撹拌機にて激しく撹拌を行うことによりスラリーを製造することができる。また、スラリー濃度については、特に制限されないが、計量のハンドリング性等を考慮し、スラリーの全重量を基準として、二酸化チタンの重量が２０〜７０重量％程度に設定すればよい。 A slurry of titanium dioxide and water and / or an organic compound having a boiling point in the range of 50 to 240 ° C. may be used alone or in combination of two or more, and these may be prepared according to conventional methods. it can. For example, titanium dioxide and water and / or organic compounds are weighed so that the weight is in the above range. Next, a slurry can be manufactured by throwing titanium dioxide into water and / or an organic compound and stirring vigorously with a stirrer capable of high-speed rotation. Further, the slurry concentration is not particularly limited, but the weight of titanium dioxide may be set to about 20 to 70% by weight on the basis of the total weight of the slurry in consideration of the handleability of measurement.
さらにスラリー調製後に二酸化チタンの粉砕処理等を行うことも好ましい。即ち、二酸化チタン粒子を水及び／又は沸点５０〜２４０℃の範囲にある有機化合物とのスラリーとした後、粉砕又は解砕し、更に分級処理を加えても良いし、逆に、分級処理後に粉砕又は解砕しても良い。また乾式で粉砕又は解砕し、更に分級処理を加えるか、粉砕又は解砕単独の処理を行うか、分級処理単独の処理を行った後、水及び／又は沸点が５０〜２４０℃の範囲にある有機化合物とのスラリーとしてもよい。あるいは、乾式と湿式とを適宜組み合わせても良く、例えば、乾式で粉砕した粒子をスラリー化した後、湿式にて分級処理を行う、乾式にて解砕及び／又は分級処理を行った後に湿式にて粉砕処理を行う等の方法を任意に採用すればよい。 Furthermore, it is also preferable to carry out a pulverization treatment of titanium dioxide after slurry preparation. That is, after the titanium dioxide particles are made into a slurry with water and / or an organic compound having a boiling point in the range of 50 to 240 ° C., they may be crushed or crushed and further subjected to a classification treatment. You may grind | pulverize or crush. Moreover, after pulverizing or crushing in a dry process, further classifying treatment is performed, processing of crushing or crushing alone is performed, or processing of classification processing is performed alone, water and / or boiling point is in the range of 50 to 240 ° C. A slurry with a certain organic compound may be used. Alternatively, dry and wet may be combined as appropriate. For example, after pulverizing dry particles, slurrying is performed, and then wet classification is performed. After dry crushing and / or classification, wet processing is performed. A method such as pulverization may be arbitrarily employed.
本発明におけるポリエステルの製造方法においては、エステル交換反応又はエステル化反応、その後の重縮合反応については、通常のポリエステルの製造方法の条件をそのまま採用すること又は二酸化チタンの変更に伴う条件設定を適宜行うことで製造することができる。従って溶融重縮合の後、必要に応じて結晶化、固相重合、後処理の工程を採用しても良い。なお本発明におけるポリエステル組成物とは、これら溶融重縮合、固相重合又はその後に必要に応じて行う各種添加剤の添加工程を実質的に終了した段階のポリエステル組成物を指し、繊維、フィルム、シート、ボトル若しくはその他の射出成形法、押し出し成形法、ブロー成形法により得られる各種の最終成形品、又はこれらの最終成形品の前駆体となる成形品については含まれないものと考える。 In the polyester production method of the present invention, for the transesterification reaction or esterification reaction, and the subsequent polycondensation reaction, the conditions of the normal polyester production method are employed as they are, or the condition settings accompanying changes in titanium dioxide are appropriately selected. It can be manufactured by doing. Therefore, after the melt polycondensation, crystallization, solid phase polymerization, and post-treatment steps may be employed as necessary. In addition, the polyester composition in the present invention refers to a polyester composition at the stage of substantially completing the melt polycondensation, solid phase polymerization, or the process of adding various additives as necessary thereafter, fibers, films, Sheets, bottles or other types of final molded products obtained by injection molding, extrusion molding, or blow molding, or molded products that are precursors of these final molded products are not considered to be included.
上述した製造方法を採用することによって、二酸化チタン含有ポリエステル組成物を製造する際の、該二酸化チタンの分散、再凝集、熱劣化による品質低下、色相悪化等の問題を解消し、作業性も改善することができる。 By adopting the manufacturing method described above, problems such as dispersion, re-aggregation, quality deterioration due to thermal degradation, hue deterioration, etc., when titanium dioxide-containing polyester compositions are produced, and workability are also improved. can do.
以下、実施例を挙げて本発明を更に具体的に説明するが、本発明はこれにより何等限定を受けるものではない。尚、実施例中における各特性の測定は以下の方法で行った。また本発明の特徴である上述の（ａ）〜（ｊ）、又は（ａ’）〜（ｊ’）の特性を満たす二酸化チタンとしては堺化学（株）製「ＳＡ−１」（商品名）を購入して、或いはこれを上述のような手法にて粉砕、解砕、分級して用いた。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further more concretely, this invention does not receive any limitation by this. In addition, the measurement of each characteristic in an Example was performed with the following method. In addition, as titanium dioxide satisfying the above-mentioned characteristics (a) to (j) or (a ′) to (j ′), which is a feature of the present invention, “SA-1” (trade name) manufactured by Sakai Chemical Co., Ltd. Or was used after being pulverized, crushed and classified by the method described above.
（１）強熱減量率：
試料の二酸化チタン２ｇを精秤し、磁性ルツボ中にいれ、電気炉（９００〜９５０℃）で２時間強熱した。冷却後精秤して求めた重量を全強熱減量とした。また、同一の二酸化チタン試料２ｇを精秤し、１０５〜１１０℃の温度にて３時間乾燥させて、その乾燥後の重量を乾燥後重量とした。下記数式（Ｉ）より強熱減量を求め、下記数式（ＩＩ）より強熱減量率を求めた。
（強熱減量）＝（乾燥後重量）−（全強熱減量） （Ｉ）
（強熱減量率）＝（強熱減量）／２（ｇ）×１００ （ＩＩ）
(1) Loss on ignition:
A sample of titanium dioxide (2 g) was precisely weighed, placed in a magnetic crucible, and ignited in an electric furnace (900 to 950 ° C.) for 2 hours. The weight obtained by precise weighing after cooling was defined as the total ignition loss. Moreover, 2 g of the same titanium dioxide sample was precisely weighed and dried at a temperature of 105 to 110 ° C. for 3 hours, and the weight after drying was defined as the weight after drying. The ignition loss was calculated | required from the following numerical formula (I), and the ignition loss rate was calculated | required from the following numerical formula (II).
(Loss on ignition) = (Weight after drying)-(Total loss on ignition) (I)
(Ignition loss rate) = (Ignition loss) / 2 (g) × 100 (II)
（２）二酸化チタンの平均粒径：
（２）−１試料調製方法：
購入してきた二酸化チタンから上述のような手法により二酸化チタンスラリーを調製した。次に五十嵐機械社製サンドグラインダー（８ガロン容）に解砕用メディアとして東芝バロディーニ製「ＥＧＢ−２００ＭＭ」（商品名）を充填し、スラリー流量を所定の流量で一定量になるように供給し、２回の粉砕処理を行った。その際に平均粒径が大きい水準は解砕用メディアの充填量を少なくすることによって調製した。また粗大粒子量は粉砕処理時のスラリー流量を増減し、滞留時間を変えることにより調製した。そのスラリーを流量１３０Ｌ／ｈで日本ポール製「ポールフィルターＲ１Ｆ０６０」（公称目開き６μｍ）又はポールフィルターＲ１Ｆ１００（公称目開き１０μｍ）を用いて濾過を行い、調製した。
(2) Average particle diameter of titanium dioxide:
(2) -1 Sample preparation method:
A titanium dioxide slurry was prepared from the purchased titanium dioxide by the method described above. Next, the sand grinder (8 gallons) made by Igarashi Machinery Co., Ltd. is filled with “EGB-200MM” (trade name) manufactured by Toshiba Barodini as a crushing medium, and the slurry flow rate is supplied at a predetermined flow rate so as to be a constant amount. Two pulverization processes were performed. In this case, a level having a large average particle diameter was prepared by reducing the filling amount of the crushing media. The amount of coarse particles was adjusted by increasing or decreasing the slurry flow rate during pulverization and changing the residence time. The slurry was prepared by filtering at a flow rate of 130 L / h using “Pole Filter R1F060” (nominal aperture 6 μm) or Pole Filter R1F100 (nominal aperture 10 μm) manufactured by Nippon Pole.
（２）−２測定方法：
島津製作所製「ＣＰ−５０型Ｃｅｎｔｒｉｆｕｇａｌ Ｐａｒｔｉｃｌｅ Ｓｉｚｅ Ａｎａｌｙｚｅｒ」を用いて測定した。次いで、この測定器によって得られる遠心沈降曲線をもとに算出した各粒径の粒子とその存在量とのｃｕｍｕｌａｔｉｖｅ曲線から、５０ｍａｓｓ ｐｅｒｃｅｎｔに相当する粒径を読み取り、この値を上記平均粒径とした（参照「粒度測定技術」、２４２〜２４７頁、日刊工業新聞社、１９７５年発行。）。
(2) -2 Measuring method:
This was measured using “CP-50 Centrifugal Particle Size Analyzer” manufactured by Shimadzu Corporation. Next, the particle size corresponding to 50 mass percent is read from the cumulative curve of the particles of each particle size calculated based on the centrifugal sedimentation curve obtained by this measuring instrument and the abundance thereof, and this value is taken as the average particle size. (Reference “Particle Size Measurement Technology”, pages 242-247, published by Nikkan Kogyo Shimbun, 1975).
（３）結晶子サイズ：
二酸化チタンのＸ線回折の２θ＝２４．５°〜２６．０°にあたる結晶（１０１）面の回折ピークを２つのガウス関数でフィッティングし、その２つの合成関数から、ピーク位置、半値幅を求めて、Ｓｈｅｒｒｅｒの式から結晶子のサイズを求めた。
(3) Crystallite size:
The diffraction peak of the crystal (101) plane corresponding to 2θ = 24.5 ° to 26.0 ° of X-ray diffraction of titanium dioxide is fitted with two Gaussian functions, and the peak position and half-value width are obtained from the two composite functions. Thus, the size of the crystallite was obtained from the Serrer equation.
（４）スラリー中の粗大粒子：
（４）−１試料調製方法：
上述の（２）−１の項参照。
（４）−２測定方法：
コールター・エレクトロニクス社製「コールターマルチサイザーＴＡ−II型」を用いて測定される粒子体積分布を球相当径に換算して求めた。
(4) Coarse particles in the slurry:
(4) -1 Sample preparation method:
See the section (2) -1 above.
(4) -2 Measuring method:
The particle volume distribution measured using “Coulter Multisizer TA-II type” manufactured by Coulter Electronics was converted into a sphere equivalent diameter.
（５）スラリーの粘度測定：
調製した二酸化チタンスラリーを定法に従いＢ型粘度計にて測定した。
(5) Viscosity measurement of slurry:
The prepared titanium dioxide slurry was measured with a B-type viscometer according to a conventional method.
（６）固有粘度（［η］）：
１，１，２，２−テトラクロルエタン４０重量部とフェノール６０重量部の混合溶媒中に試料を溶解して定法に従って３５℃にて測定した。
(6) Intrinsic viscosity ([η]):
A sample was dissolved in a mixed solvent of 40 parts by weight of 1,1,2,2-tetrachloroethane and 60 parts by weight of phenol and measured at 35 ° C. according to a conventional method.
（７）ポリエステル組成物の濾過昇圧：
ポリエステル組成物中の二酸化チタン粗大粒子を評価するため、下記のように濾過昇圧速度を評価した。小型１軸スクリュータイプ押出機の溶融ポリマー出側にポリマー定量供給装置を取り付け、更にその出側に内径６４ｍｍφの２４００メッシュ金網フィルターを２枚重ねて装着した。次いで、溶融ポリマーの温度を２９０℃一定となるようにコントロールし、ポリマー流量が３３．３ｇ／ｍｉｎの速度となるようにポリマーを１０時間連続して濾過する。この時のフィルター入側の圧力上昇値の平均値をもって、濾過圧力上昇速度（濾過昇圧）とした。尚、評価は以下の判定基準に従い、特級及び１級のみが実用に供することができる。
特級：濾過圧力上昇速度が、０．５ＭＰａ／ｈ以下である。
１級：濾過圧力上昇速度が、０．５ＭＰａ／ｈを超え〜１．０ＭＰａ／ｈ以下である。
２級：濾過圧力上昇速度が、１．０ＭＰａ／ｈを超え〜２．０ＭＰａ／ｈ未満である。
３級：濾過圧力上昇速度が、２．０ＭＰａ／ｈ以上である。
(7) Filtration pressure increase of the polyester composition:
In order to evaluate the titanium dioxide coarse particles in the polyester composition, the filtration pressure increase rate was evaluated as follows. A polymer quantitative supply device was attached to the molten polymer outlet side of a small single screw type extruder, and two 2400 mesh wire mesh filters with an inner diameter of 64 mmφ were attached to the outlet side. Next, the temperature of the molten polymer is controlled to be constant at 290 ° C., and the polymer is continuously filtered for 10 hours so that the polymer flow rate is 33.3 g / min. The average value of the pressure increase values on the filter entrance side at this time was defined as the filtration pressure increase rate (filtration pressure increase). In addition, according to the following judgment criteria, only a special grade and a 1st grade can use for evaluation.
Special grade: Filtration pressure increase rate is 0.5 MPa / h or less.
First grade: Filtration pressure increase rate is more than 0.5 MPa / h and not more than 1.0 MPa / h.
Second grade: Filtration pressure increase rate is more than 1.0 MPa / h to less than 2.0 MPa / h.
Third grade: Filtration pressure increase rate is 2.0 MPa / h or more.
（８）ポリエステル組成物中の二酸化チタン分散性：
ポリマー５０ｍｇを２枚のカバーグラス間にはさんで２８０℃で溶融プレスし、急冷したのち、位相差顕微鏡を用いて観察し、画像解析装置「ルーゼックス５００」で顕微鏡像内の最大長が５．０μｍ以上の粒子数をカウントした。尚、評価は下記の判定基準に従い、特級及び１級のみが実用に供される。
特級：５．０μｍをこえる粒子が全く見当らない。
１級：５．０μｍをこえる粒子数が５個／ｍｍ２未満である。
２級：５．０μｍをこえる粒子数が５〜１０個／ｍｍ２である。
３級：５．０μｍをこえる粒子数が１０個／ｍｍ２を超える。
(8) Dispersibility of titanium dioxide in the polyester composition:
50 mg of polymer was melt-pressed between two cover glasses at 280 ° C., quenched, observed using a phase-contrast microscope, and the maximum length in the microscopic image was 5. The number of particles of 0 μm or more was counted. In addition, according to the following judgment criteria, only a special grade and 1st grade are used for evaluation.
Special grade: No particles exceeding 5.0 μm are found.
First grade: The number of particles exceeding 5.0 μm is less than 5 particles / mm 2 .
Second grade: The number of particles exceeding 5.0 μm is 5 to 10 particles / mm 2 .
Third grade: The number of particles exceeding 5.0 μm exceeds 10 particles / mm 2 .
（９）ポリエステル組成物の色相：
ポリエステル組成物の濾過昇圧評価時の吐出ポリマーをプレート上にサンプリングし、１４０℃×２ｈｒの条件にて結晶化させた後、ミノルタ社製カラーマシン「ＣＲ−５０」を用いて測定し、Ｈｕｎｔｅｒ図の色度図法によりＬａｂ表示で色相を得て、Ｌ−ｂを計算した。尚、熱劣化の評価は以下の判定基準に従って行い、評価は［Ｌ−ｂ値］及び［ｂ値］の２段階での評価を実施した。両方の評価共に特級及び１級のみが実用に供される。
［Ｌ−ｂ値］
特級：（Ｌ−ｂ）値が６８以上である。
１級：（Ｌ−ｂ）値が６３以上６８未満である。
２級：（Ｌ−ｂ）値が５８以上６３未満である。
３級：（Ｌ−ｂ）値が５８未満である。
［ｂ値］
特級：ｂ値が２．０以下である。
１級：ｂ値が２．０以上２．３未満である。
２級：ｂ値が２．３以上２．５未満である。
３級：ｂ値が２．５以上である。
(9) Hue of the polyester composition:
The polymer discharged during the filtration pressure increase evaluation of the polyester composition was sampled on a plate and crystallized under the conditions of 140 ° C. × 2 hr, then measured using a Minolta color machine “CR-50”. The hue was obtained in the Lab display by the chromaticity diagram of, and L−b was calculated. The evaluation of thermal degradation was performed according to the following criteria, and the evaluation was performed in two stages of [Lb value] and [b value]. In both evaluations, only the special grade and the first grade are put to practical use.
[Lb value]
Special grade: (L−b) value is 68 or more.
First grade: (Lb) value is 63 or more and less than 68.
Second grade: (Lb) value is 58 or more and less than 63.
Third grade: (Lb) value is less than 58.
[B value]
Special grade: b value is 2.0 or less.
First grade: b value is 2.0 or more and less than 2.3.
Second grade: b value is 2.3 or more and less than 2.5.
Third grade: b value is 2.5 or more.
（１０）チタン、Ｆｅ、Ｐ２Ｏ５、Ｋ２Ｏ、Ｓｂの含有量の測定：
対応する元素を蛍光Ｘ線（リガク電機工業（株）社製ＺＳＸ１００ｅ）を用いて測定を行った。
(10) Measurement of content of titanium, Fe, P 2 O 5 , K 2 O, Sb:
The corresponding element was measured using fluorescent X-rays (ZSX100e manufactured by Rigaku Electric Industry Co., Ltd.).
（１１）ルチル／アナターゼ比
リガク電機工業（株）社製「ＲＩＧＡＫＵ ＲＩＮＴ ＴＴＲ(III)」を用いて測定を行った。
(11) Rutile / anatase ratio Measurement was performed using "RIGAKU RINT TTR (III)" manufactured by Rigaku Electric Industry Co., Ltd.
［実施例１］
表１に示す二酸化チタンを２００ｋｇ、エチレングリコールを８００ｋｇを混合し、１．２ｍｍビーズを３０Ｌ投入した五十嵐機械製サンドグラインダーで２００Ｌ／ｈで分散させ、二酸化チタンスラリーを得た。得られたスラリーの粘度を表２に示す。なおこの条件でサンドグラインダー処理を行っても、処理前後において二酸化チタンの平均粒径、粗大粒子量の値の変化はなかった。
[Example 1]
200 kg of titanium dioxide and 800 kg of ethylene glycol shown in Table 1 were mixed and dispersed at 200 L / h with a sand grinder manufactured by Igarashi Machinery Co., Ltd. into which 30 L of 1.2 mm beads were added to obtain a titanium dioxide slurry. The viscosity of the obtained slurry is shown in Table 2. Even when the sand grinder treatment was performed under these conditions, the average particle diameter and the coarse particle amount of titanium dioxide did not change before and after the treatment.
次にジメチルテレフタレート１００重量部とエチレングリコール７０重量部とを用い、酢酸マンガン・４水和物０．０３８重量部を触媒として常法に従ってエステル交換反応により生成したオリゴマーに、リン酸トリメチル０．０２５重量部を添加し、１５分間反応させてから三酸化アンチモン０．０４５重量部を添加し、更に表１に示す特性を有する二酸化チタンを、二酸化チタンの含有量が二酸化チタン含有ポリエステル組成物の２．５重量％になるように、上述の二酸化チタンスラリーを用いて添加した。その後、内温を２５０℃から２９０℃に昇温して１３３Ｐａ以下の減圧下で３時間重縮合反応させて、[η]が０．６４ｄＬ／ｇの二酸化チタン含有ポリエステル組成物を得た。定法により製糸を行った。評価結果を表２に示す。 Next, using 100 parts by weight of dimethyl terephthalate and 70 parts by weight of ethylene glycol, 0.038 parts by weight of manganese acetate tetrahydrate as a catalyst was added to an oligomer produced by a transesterification reaction according to a conventional method, and 0.025 of trimethyl phosphate was added. After adding 15 parts by weight and reacting for 15 minutes, 0.045 part by weight of antimony trioxide was added, and titanium dioxide having the characteristics shown in Table 1 was added. It added using the above-mentioned titanium dioxide slurry so that it might become 0.5 weight%. Thereafter, the internal temperature was raised from 250 ° C. to 290 ° C. and a polycondensation reaction was performed for 3 hours under a reduced pressure of 133 Pa or less to obtain a titanium dioxide-containing polyester composition having an [η] of 0.64 dL / g. Yarn production was performed by a conventional method. The evaluation results are shown in Table 2.
［実施例２］
実施例１において、添加する二酸化チタンの物性を表１に記載した通りのものと変更すること以外は同様の操作を行い、二酸化チタンスラリーを用いて二酸化チタン含有ポリエステル組成物を製造し、さらに製糸を行った。評価結果を表２に示す。
[Example 2]
In Example 1, the same operation was performed except that the physical properties of titanium dioxide to be added were changed to those shown in Table 1, to produce a titanium dioxide-containing polyester composition using a titanium dioxide slurry, and further to yarn production Went. The evaluation results are shown in Table 2.
[実施例３および比較例１〜８]
表１に示す二酸化チタンを６００ｋｇ、水を４００ｋｇを混合し、１．２ｍｍビーズを３０Ｌ投入した五十嵐機械製サンドグラインダーで２００Ｌ／ｈで分散させた二酸化チタンスラリーを得た。得られたスラリーの粘度を表２に示す。なおこの条件でサンドグラインダー処理を行っても、処理前後において二酸化チタンの平均粒径、粗大粒子量の値の変化はなかった。
[Example 3 and Comparative Examples 1-8]
600 kg of titanium dioxide and 400 kg of water shown in Table 1 were mixed, and a titanium dioxide slurry dispersed at 200 L / h was obtained with a sand grinder manufactured by Igarashi Machine, in which 30 L of 1.2 mm beads were added. The viscosity of the obtained slurry is shown in Table 2. Even when the sand grinder treatment was performed under these conditions, the average particle diameter and the coarse particle amount of titanium dioxide did not change before and after the treatment.
チップ投入口を１箇所、スラリー添加ノズルを１箇所、常圧ベントをスラリー添加ノズルの前後に各１箇所及び真空ベントを２箇所設けた神戸製鋼製二軸押出機ＫＴＸ−７３に、二酸化チタンを含まない固有粘度０．６５ｄＬ／ｇのポリエステルチップ４０ｋｇ／ｈと表１にそれぞれ示した二酸化チタンの６０％水スラリーを４５ｋｇ／ｈの速度にて供給した。水分を開放ベント（常圧ベント）より排出しながら、真空ベントにより押出機内部を１３３Ｐａ以下に保ち、スクリュー回転数２５０ｒｐｍでポリエステルと二酸化チタンとを混練し、二酸化チタン含有量４０％のポリエステル組成物を得た。さらに実施例１と同様の手法により製糸を行った。結果を表２に示す。 Titanium dioxide was added to a Kobe Steel twin screw extruder KTX-73 with one tip inlet, one slurry addition nozzle, one atmospheric pressure vent before and after the slurry addition nozzle, and two vacuum vents. A polyester chip having an intrinsic viscosity of 0.65 dL / g not containing 40 kg / h and a titanium dioxide 60% water slurry shown in Table 1 were fed at a rate of 45 kg / h. While discharging moisture from an open vent (normal pressure vent), the inside of the extruder is kept at 133 Pa or less by a vacuum vent, and polyester and titanium dioxide are kneaded at a screw rotation speed of 250 rpm, and a polyester composition having a titanium dioxide content of 40%. Got. Further, yarn production was performed in the same manner as in Example 1. The results are shown in Table 2.
本発明によれば、色相の良好な二酸化チタン含有ポリエステル組成物を得ることができる。該ポリエステル組成物は、熱劣化がなく組成物中においても成形品や繊維等に加工しても、二酸化チタンが再凝集することなく高度の分散性を保ち、その結果得られるポリエステル組成物の成形品や繊維は不透明性の斑が少ない。一方ポリエステル成形設備における金属の摩耗を低減することができ、長時間の使用に耐えうるので工業的な意義は大きい。 According to the present invention, a titanium dioxide-containing polyester composition having a good hue can be obtained. The polyester composition has no thermal deterioration and maintains high dispersibility without re-aggregation of titanium dioxide even when processed into a molded product or fiber in the composition, and the resulting polyester composition is molded. Goods and fibers have few opaque spots. On the other hand, metal wear in polyester molding equipment can be reduced, and it can withstand long-term use, so it has great industrial significance.
Claims (4)
（ａ）平均粒子径が０．１〜０．５μｍの範囲にあること。
（ｂ）粒子径が３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下であること。
（ｃ）粒子径が４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること。
（ｄ）Ｐ２Ｏ５を二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲で含有すること。
（ｅ）Ｋ２Ｏを二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲で含有すること。
（ｆ）強熱減量率が０．４重量％以下であること。
（ｇ）結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であること。
（ｈ）結晶子サイズが１０〜１５０ｎｍの範囲にあること。
（ｉ）実質的にＦｅを含有しないこと。
（ｊ）Ｓｂ元素を二酸化チタンの全重量を基準として５０ｐｐｍ以下の範囲で含有すること。 A titanium dioxide-containing polyester composition containing 0.01 to 70% by weight of titanium dioxide that simultaneously satisfies the following requirements (a) to (j) based on the total weight of the polyester composition.
(A) The average particle diameter is in the range of 0.1 to 0.5 μm.
(B) Coarse particles having a particle diameter of 3 μm or more are 5000 particles / 0.4 mg or less.
(C) The number of coarse particles having a particle diameter of 4 μm or more is 1500 particles / 0.4 mg or less.
(D) P 2 O 5 in that it contains in the range of 0.10 to 0.30 weight percent based on the total weight of titanium dioxide.
(E) containing K 2 O in the range of 0.01 to 0.15% by weight based on the total weight of titanium dioxide.
(F) The ignition loss rate is 0.4% by weight or less.
(G) The value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less.
(H) The crystallite size is in the range of 10 to 150 nm.
(I) It does not contain Fe substantially.
(J) Containing Sb element in the range of 50 ppm or less based on the total weight of titanium dioxide.
（ａ）平均粒子径が０．１〜０．５μｍの範囲にあること。
（ｂ）粒子径が３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下であること。
（ｃ）粒子径が４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること。
（ｄ）Ｐ２Ｏ５を二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲で含有すること。
（ｅ）Ｋ２Ｏを二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲で含有すること。
（ｆ）強熱減量率が０．４重量％以下であること。
（ｇ）結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であること。
（ｈ）結晶子サイズが１０〜１５０ｎｍの範囲にあること。
（ｉ）実質的にＦｅを含有しないこと。
（ｊ）Ｓｂ元素を二酸化チタンの全重量を基準として５０ｐｐｍ以下の範囲で含有すること。 A slurry comprising titanium dioxide that simultaneously satisfies the following requirements (a) to (j) and water and / or a dispersion medium that is an organic compound having a boiling point in the range of 50 to 240 ° C. The titanium dioxide slurry is contained in an amount of 20 to 70% by weight based on the total weight, and the viscosity of the slurry at room temperature is 100 mPa · s or less.
(A) The average particle diameter is in the range of 0.1 to 0.5 μm.
(B) Coarse particles having a particle diameter of 3 μm or more are 5000 particles / 0.4 mg or less.
(C) The number of coarse particles having a particle diameter of 4 μm or more is 1500 particles / 0.4 mg or less.
(D) P 2 O 5 in that it contains in the range of 0.10 to 0.30 weight percent based on the total weight of titanium dioxide.
(E) containing K 2 O in the range of 0.01 to 0.15% by weight based on the total weight of titanium dioxide.
(F) The ignition loss rate is 0.4% by weight or less.
(G) The value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less.
(H) The crystallite size is in the range of 10 to 150 nm.
(I) It does not contain Fe substantially.
(J) Containing Sb element in the range of 50 ppm or less based on the total weight of titanium dioxide.
（ａ’）平均粒子径が０．１〜０．５μｍの範囲にあること。
（ｂ’）粒子径が３μｍ以上の粗大粒子が５０００個／０．４ｍｇ以下であること。
（ｃ’）粒子径が４μｍ以上の粗大粒子が１５００個／０．４ｍｇ以下であること。
（ｄ’）Ｐ２Ｏ５を二酸化チタンの全重量を基準として０．１０〜０．３０重量％の範囲で含有すること。
（ｅ’）Ｋ２Ｏを二酸化チタンの全重量を基準として０．０１〜０．１５重量％の範囲で含有すること。
（ｆ’）強熱減量率が０．４重量％以下であること。
（ｇ’）結晶形態がルチル型である二酸化チタンの重量をアナターゼ型である二酸化チタンの重量で除した値が９×１０−３以下であること。
（ｈ’）結晶子サイズが１０〜１５０ｎｍの範囲にあること。
（ｉ’）実質的にＦｅを含有しないこと。
（ｊ’）Ｓｂ元素を二酸化チタンの全重量を基準として５０ｐｐｍ以下の範囲で含有すること。 In the method for producing a titanium dioxide-containing polyester composition, a dicarboxylic acid and / or an ester-forming derivative thereof and a diol are esterified and / or transesterified and then subjected to a polycondensation reaction to produce a polyester polymer. The total weight of the titanium dioxide-containing polyester composition containing titanium dioxide that simultaneously satisfies the following requirements (a ′) to (j ′) at any stage after completion of the esterification and / or transesterification reaction and before completion of the polycondensation reaction: A method for producing a titanium dioxide-containing polyester composition, comprising adding 0.01% by weight or more and 70% by weight or less based on the weight.
(A ′) The average particle diameter is in the range of 0.1 to 0.5 μm.
(B ′) Coarse particles having a particle diameter of 3 μm or more are 5000 particles / 0.4 mg or less.
(C ′) Coarse particles having a particle diameter of 4 μm or more are 1500 particles / 0.4 mg or less.
(D ′) P 2 O 5 is contained in the range of 0.10 to 0.30% by weight based on the total weight of titanium dioxide.
(E ′) containing K 2 O in a range of 0.01 to 0.15% by weight based on the total weight of titanium dioxide.
(F ′) The ignition loss rate is 0.4% by weight or less.
(G ′) The value obtained by dividing the weight of titanium dioxide whose crystal form is rutile type by the weight of titanium dioxide which is anatase type is 9 × 10 −3 or less.
(H ′) The crystallite size is in the range of 10 to 150 nm.
(I ′) substantially not containing Fe.
(J ′) The Sb element is contained in a range of 50 ppm or less based on the total weight of titanium dioxide.
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| CN115490455A (en) * | 2022-10-09 | 2022-12-20 | 临沂海螺新材料科技有限公司 | Low-doping-amount enhanced cement grinding aid and preparation method thereof |
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| JPH11217492A (en) * | 1998-02-03 | 1999-08-10 | Nippon Ester Co Ltd | Polyester resin composition for fiber |
| JP2005042218A (en) * | 2003-07-23 | 2005-02-17 | Toray Ind Inc | Superfine polyester multifilament |
| JP2006002067A (en) * | 2004-06-18 | 2006-01-05 | Teijin Fibers Ltd | Titanium dioxide-containing polyester composition and method for producing the same |
| JP2006176629A (en) * | 2004-12-22 | 2006-07-06 | Teijin Fibers Ltd | Polyester composition and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11217492A (en) * | 1998-02-03 | 1999-08-10 | Nippon Ester Co Ltd | Polyester resin composition for fiber |
| JP2005042218A (en) * | 2003-07-23 | 2005-02-17 | Toray Ind Inc | Superfine polyester multifilament |
| JP2006002067A (en) * | 2004-06-18 | 2006-01-05 | Teijin Fibers Ltd | Titanium dioxide-containing polyester composition and method for producing the same |
| JP2006176629A (en) * | 2004-12-22 | 2006-07-06 | Teijin Fibers Ltd | Polyester composition and method for producing the same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115490455A (en) * | 2022-10-09 | 2022-12-20 | 临沂海螺新材料科技有限公司 | Low-doping-amount enhanced cement grinding aid and preparation method thereof |
| CN115490455B (en) * | 2022-10-09 | 2023-08-18 | 临沂海螺新材料科技有限公司 | Low-doping-amount enhanced cement grinding aid and preparation method thereof |
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