JP4634082B2 - Polyester composition, production method thereof and fiber - Google Patents
Polyester composition, production method thereof and fiber Download PDFInfo
- Publication number
- JP4634082B2 JP4634082B2 JP2004202727A JP2004202727A JP4634082B2 JP 4634082 B2 JP4634082 B2 JP 4634082B2 JP 2004202727 A JP2004202727 A JP 2004202727A JP 2004202727 A JP2004202727 A JP 2004202727A JP 4634082 B2 JP4634082 B2 JP 4634082B2
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- JP
- Japan
- Prior art keywords
- polyester
- polyester composition
- mass
- color adjusting
- color
- 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.)
- Expired - Fee Related
Links
- 229920000728 polyester Polymers 0.000 title claims description 143
- 239000000203 mixture Substances 0.000 title claims description 66
- 239000000835 fiber Substances 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000002245 particle Substances 0.000 claims description 47
- 239000000975 dye Substances 0.000 claims description 41
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 38
- 125000003118 aryl group Chemical group 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- -1 polyethylene terephthalate Polymers 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 24
- 150000003609 titanium compounds Chemical class 0.000 claims description 23
- 238000000862 absorption spectrum Methods 0.000 claims description 20
- 230000031700 light absorption Effects 0.000 claims description 20
- 238000006068 polycondensation reaction Methods 0.000 claims description 20
- 238000002835 absorbance Methods 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 230000007423 decrease Effects 0.000 claims description 10
- 230000005484 gravity Effects 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 8
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 8
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 7
- 239000001506 calcium phosphate Substances 0.000 claims description 7
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 7
- 239000000049 pigment Substances 0.000 claims description 7
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000002074 melt spinning Methods 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000000378 calcium silicate Substances 0.000 claims description 4
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 4
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229910000391 tricalcium phosphate Inorganic materials 0.000 claims description 4
- 235000019731 tricalcium phosphate Nutrition 0.000 claims description 4
- 229940078499 tricalcium phosphate Drugs 0.000 claims description 4
- 238000004040 coloring Methods 0.000 claims description 3
- 229910052622 kaolinite Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims 1
- 235000012241 calcium silicate Nutrition 0.000 claims 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 11
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 10
- 229910052719 titanium Inorganic materials 0.000 description 10
- 239000010936 titanium Substances 0.000 description 10
- 229910052787 antimony Inorganic materials 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- 229910052732 germanium Inorganic materials 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 229910000389 calcium phosphate Inorganic materials 0.000 description 3
- 235000011010 calcium phosphates Nutrition 0.000 description 3
- 150000001869 cobalt compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005886 esterification reaction Methods 0.000 description 3
- 150000002148 esters Chemical group 0.000 description 3
- 239000006224 matting agent Substances 0.000 description 3
- 208000016261 weight loss Diseases 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002291 germanium compounds Chemical class 0.000 description 2
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 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
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 229920000874 polytetramethylene terephthalate Polymers 0.000 description 2
- 229920002215 polytrimethylene terephthalate Polymers 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
- 238000004451 qualitative analysis Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 238000005809 transesterification reaction Methods 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
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- OCQDPIXQTSYZJL-UHFFFAOYSA-N 1,4-bis(butylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NCCCC)=CC=C2NCCCC OCQDPIXQTSYZJL-UHFFFAOYSA-N 0.000 description 1
- QOSTVEDABRQTSU-UHFFFAOYSA-N 1,4-bis(methylamino)anthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(NC)=CC=C2NC QOSTVEDABRQTSU-UHFFFAOYSA-N 0.000 description 1
- ZKIVUFFTMWIBCO-UHFFFAOYSA-N 1,5-bis(4-methylanilino)anthracene-9,10-dione Chemical compound C1=CC(C)=CC=C1NC1=CC=CC2=C1C(=O)C1=CC=CC(NC=3C=CC(C)=CC=3)=C1C2=O ZKIVUFFTMWIBCO-UHFFFAOYSA-N 0.000 description 1
- BWQIGAJDKXZJTG-UHFFFAOYSA-N 1-(cyclohexylamino)anthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C(=O)C2=C1NC1CCCCC1 BWQIGAJDKXZJTG-UHFFFAOYSA-N 0.000 description 1
- GBAJQXFGDKEDBM-UHFFFAOYSA-N 1-(methylamino)-4-(3-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=CC(C)=C1 GBAJQXFGDKEDBM-UHFFFAOYSA-N 0.000 description 1
- ITYXXSSJBOAGAR-UHFFFAOYSA-N 1-(methylamino)-4-(4-methylanilino)anthracene-9,10-dione Chemical compound C1=2C(=O)C3=CC=CC=C3C(=O)C=2C(NC)=CC=C1NC1=CC=C(C)C=C1 ITYXXSSJBOAGAR-UHFFFAOYSA-N 0.000 description 1
- NIDFGXDXQKPZMA-UHFFFAOYSA-N 14h-benz[4,5]isoquino[2,1-a]perimidin-14-one Chemical compound C1=CC(N2C(=O)C=3C4=C(C2=N2)C=CC=C4C=CC=3)=C3C2=CC=CC3=C1 NIDFGXDXQKPZMA-UHFFFAOYSA-N 0.000 description 1
- ZPSZXWVBMOMXED-UHFFFAOYSA-N 2-(2-bromo-5-chlorophenyl)acetic acid Chemical compound OC(=O)CC1=CC(Cl)=CC=C1Br ZPSZXWVBMOMXED-UHFFFAOYSA-N 0.000 description 1
- UBZVRROHBDDCQY-UHFFFAOYSA-N 20749-68-2 Chemical compound C1=CC(N2C(=O)C3=C(C(=C(Cl)C(Cl)=C3C2=N2)Cl)Cl)=C3C2=CC=CC3=C1 UBZVRROHBDDCQY-UHFFFAOYSA-N 0.000 description 1
- DZNJMLVCIZGWSC-UHFFFAOYSA-N 3',6'-bis(diethylamino)spiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C2=CC=CC=C2C21C1=CC=C(N(CC)CC)C=C1OC1=CC(N(CC)CC)=CC=C21 DZNJMLVCIZGWSC-UHFFFAOYSA-N 0.000 description 1
- XBIUWALDKXACEA-UHFFFAOYSA-N 3-[bis(2,4-dioxopentan-3-yl)alumanyl]pentane-2,4-dione Chemical compound CC(=O)C(C(C)=O)[Al](C(C(C)=O)C(C)=O)C(C(C)=O)C(C)=O XBIUWALDKXACEA-UHFFFAOYSA-N 0.000 description 1
- AMPCGOAFZFKBGH-UHFFFAOYSA-N 4-[[4-(dimethylamino)phenyl]-(4-methyliminocyclohexa-2,5-dien-1-ylidene)methyl]-n,n-dimethylaniline Chemical compound C1=CC(=NC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 AMPCGOAFZFKBGH-UHFFFAOYSA-N 0.000 description 1
- NMZURKQNORVXSV-UHFFFAOYSA-N 6-methyl-2-phenylquinoline Chemical compound C1=CC2=CC(C)=CC=C2N=C1C1=CC=CC=C1 NMZURKQNORVXSV-UHFFFAOYSA-N 0.000 description 1
- VJUKWPOWHJITTP-UHFFFAOYSA-N 81-39-0 Chemical compound C1=CC(C)=CC=C1NC1=CC=C2C3=C1C(=O)C1=CC=CC=C1C3=CC(=O)N2C VJUKWPOWHJITTP-UHFFFAOYSA-N 0.000 description 1
- NDSXSCFKIAPKJG-UHFFFAOYSA-N CC(C)O[Ti] Chemical compound CC(C)O[Ti] NDSXSCFKIAPKJG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- HLNMYBZPLZNJPZ-UHFFFAOYSA-N N-cyclohexylcyclohexanamine 7-hydroxy-8-[(4-phenyldiazenylphenyl)diazenyl]naphthalene-1,3-disulfonic acid Chemical compound C1CCC(CC1)NC1CCCCC1.Oc1ccc2cc(cc(c2c1N=Nc1ccc(cc1)N=Nc1ccccc1)S(O)(=O)=O)S(O)(=O)=O HLNMYBZPLZNJPZ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPGIHFRTRXVWOY-UHFFFAOYSA-N Oil red O Chemical compound Cc1ccc(C)c(c1)N=Nc1cc(C)c(cc1C)N=Nc1c(O)ccc2ccccc12 NPGIHFRTRXVWOY-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- LIPOUNRJVLNBCD-UHFFFAOYSA-N acetyl dihydrogen phosphate Chemical class CC(=O)OP(O)(O)=O LIPOUNRJVLNBCD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 description 1
- 229940067460 calcium acetate monohydrate Drugs 0.000 description 1
- 229910000394 calcium triphosphate Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- NHXXLZBKTKNTEF-UHFFFAOYSA-N chembl1997306 Chemical compound CC1=CC=CC(N=NC=2C(=CC(=CC=2)N=NC=2C3=CC=CC=C3C=CC=2O)C)=C1 NHXXLZBKTKNTEF-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000986 disperse dye Substances 0.000 description 1
- SVTDYSXXLJYUTM-UHFFFAOYSA-N disperse red 9 Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2NC SVTDYSXXLJYUTM-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 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 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RFWLACFDYFIVMC-UHFFFAOYSA-D pentacalcium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O RFWLACFDYFIVMC-UHFFFAOYSA-D 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- RCTGMCJBQGBLKT-PAMTUDGESA-N scarlet red Chemical compound CC1=CC=CC=C1\N=N\C(C=C1C)=CC=C1\N=N\C1=C(O)C=CC2=CC=CC=C12 RCTGMCJBQGBLKT-PAMTUDGESA-N 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229940033816 solvent red 27 Drugs 0.000 description 1
- LJFWQNJLLOFIJK-UHFFFAOYSA-N solvent violet 13 Chemical compound C1=CC(C)=CC=C1NC1=CC=C(O)C2=C1C(=O)C1=CC=CC=C1C2=O LJFWQNJLLOFIJK-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
- Artificial Filaments (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明はポリエステル組成物、その製造方法および繊維に関する。さらに詳しくは、真比重５．０以上の金属元素、特にアンチモン、ゲルマニウムの含有量が極めて少なく、色相に優れ、繊維製造時の成形性に優れているという性能を有し、鮮明性、染色時に深色染色性が発現されるポリエステル組成物その製造方法および繊維に関する。 The present invention relates to a polyester composition, a method for producing the same, and a fiber. More specifically, the content of metal elements having a true specific gravity of 5.0 or more, particularly antimony and germanium, is extremely small, has excellent properties of hue, and excellent moldability during fiber production. The present invention relates to a polyester composition exhibiting deep color dyeability, its production method and fiber.
ポリエステル、特にポリエチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート及びポリテトラメチレンテレフタレートは、その機械的、物理的、化学的性能が優れているため、繊維、フィルム、その他の成形物に広く利用されている。特にポリエチレンテレフタレートはその特性、価格の面から非常に幅広い用途で利用されている。しかしながらポリエステルは衣料用繊維としては染色性が良好とは言えず、色の深みに劣るものであった。 Polyesters, especially polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate and polytetramethylene terephthalate are widely used in fibers, films and other molded products because of their excellent mechanical, physical and chemical performance. Yes. In particular, polyethylene terephthalate is used in a very wide range of applications because of its characteristics and price. However, polyester cannot be said to have good dyeability as a fiber for clothing, and is inferior in color depth.
従来、このような欠点を補うため、ポリエステル中に微粒子を含有させたり、重合反応中に該ポリエステルに不溶な粒子種を析出させて、得られたポリエステル組成物を製糸化した後にアルカリ減量等の方法で、繊維表面に凹凸を形成させ、深色化されたポリエステル繊維を得る方法が知られている。（例えば特許文献１、特許文献２参照） Conventionally, in order to make up for such drawbacks, fine particles are contained in the polyester, or particle types insoluble in the polyester are precipitated during the polymerization reaction, and then the resulting polyester composition is knitted to produce an alkali weight loss, etc. As a method, a method is known in which unevenness is formed on the fiber surface to obtain a deep-colored polyester fiber. (For example, see Patent Document 1 and Patent Document 2)
このような深色染色用ポリエステル組成物を得るために通常用いられるポリエチレンテレフタレートは、通常例えばテレフタル酸とエチレングリコールとを直接エステル化反応させるか、テレフタル酸ジメチルのようなテレフタル酸の低級アルキルエステルとエチレングリコールとをエステル交換反応させるか、又はテレフタル酸とエチレンオキサイドとを反応さて、テレフタル酸のエチレングリコールエステル及び／又はその低重合体を生成させる。次いでこの反応生成物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって製造されている。 Polyethylene terephthalate, which is usually used to obtain such a deep color dyeing polyester composition, is usually obtained by directly esterifying terephthalic acid and ethylene glycol, or a lower alkyl ester of terephthalic acid such as dimethyl terephthalate. Ethylene glycol is transesterified or terephthalic acid and ethylene oxide are reacted to produce an ethylene glycol ester of terephthalic acid and / or a low polymer thereof. Next, the reaction product is produced by heating under reduced pressure in the presence of a polycondensation catalyst to carry out a polycondensation reaction until a predetermined polymerization degree is reached.
これらのポリエステルにおいては、重縮合反応段階で使用する触媒の種類によって、反応速度および得られるポリエステルの品質が大きく左右されることはよく知られている。この点について従来から検討の結果、ポリエチレンテレフタレートの重縮合触媒としては、優れた重縮合触媒性能を有し、かつ色相の良好なポリエステルが得られるなどの理由からアンチモン化合物が最も広く使用されている。 In these polyesters, it is well known that the reaction rate and the quality of the resulting polyester greatly depend on the type of catalyst used in the polycondensation reaction stage. As a result of conventional studies on this point, as a polycondensation catalyst for polyethylene terephthalate, an antimony compound is most widely used because it has excellent polycondensation catalyst performance and a polyester having a good hue. .
しかしながら、アンチモン化合物を重縮合触媒として使用したポリエステルを例えば長時間にわたって連続的に溶融紡糸し繊維化しようとした場合、口金孔周辺に異物（以下、単に口金異物と称することがある。）が付着堆積し、溶融ポリマー流れの曲がり現象（ベンディング）が発生することがある。するとこれが原因となって紡糸、延伸工程において毛羽及び／又は断糸などを発生するという成形性の問題がある。 However, when a polyester using an antimony compound as a polycondensation catalyst is continuously melt-spun for a long time to obtain a fiber, foreign matter (hereinafter sometimes referred to simply as a base foreign matter) adheres to the periphery of the base hole. Accumulation and bending of the molten polymer flow (bending) may occur. As a result, there is a problem of formability that fluff and / or yarn breakage occurs in the spinning and drawing processes.
またペットボトル用などのポリエステル触媒としては、一般的にゲルマニウム化合物が使用されているが、ゲルマニウムは稀少金属であり、高価な為、得られる製品の価格が高くなってしまうことが問題となっている。 In addition, germanium compounds are generally used as polyester catalysts for PET bottles, but germanium is a rare metal and is expensive, so the price of the resulting product becomes high. Yes.
該アンチモン化合物やゲルマニウム化合物以外の重縮合触媒として、チタンテトラブトキシドのようなチタン化合物を用いることも提案されている。このようなチタン化合物を使用した場合、上記のような口金異物の堆積に起因する成形性の問題は解決できる。しかし、得られたポリエステル自身が黄色く着色されており、また溶融熱安定性も不良であるという新たな問題が発生する。この着色問題を解決するために、コバルト化合物をポリエステルに添加して黄味を抑えることが一般的に行われている。確かにコバルト化合物を添加することによってポリエステルの色相（ｂ値）は改善することができるが、コバルト化合物を添加することによってポリエステルの溶融熱安定性がさらに低下し、ポリマーの分解も起こりやすくなるという問題がある。 It has also been proposed to use a titanium compound such as titanium tetrabutoxide as a polycondensation catalyst other than the antimony compound and germanium compound. When such a titanium compound is used, the above-described problem of formability due to the accumulation of foreign matter in the die can be solved. However, there is a new problem that the obtained polyester itself is colored yellow and that the heat stability of the melt is poor. In order to solve this coloring problem, it is a common practice to suppress yellowishness by adding a cobalt compound to polyester. Certainly, the hue (b value) of the polyester can be improved by adding a cobalt compound. However, the addition of a cobalt compound further lowers the thermal stability of the polyester and facilitates polymer degradation. There's a problem.
また、他のチタン化合物として、水酸化チタン、またはα−チタン酸をポリエステル製造用触媒として使用することが開示されている（それぞれ例えば特許文献３、特許文献４参照。）。しかしながら、前者の方法では水酸化チタンの粉末化が容易でなく、一方後者の方法ではα−チタン酸が変質し易いため、その保存、取扱いが容易でない。したがっていずれも工業的に採用するには適当ではなく、さらに、良好な色相（ｂ値）のポリマーを得ることも困難である。 Further, it is disclosed that titanium hydroxide or α-titanic acid is used as a catalyst for polyester production as another titanium compound (see, for example, Patent Document 3 and Patent Document 4). However, in the former method, powdering of titanium hydroxide is not easy, whereas in the latter method, α-titanic acid is likely to be altered, so that storage and handling are not easy. Accordingly, none of them are suitable for industrial use, and it is also difficult to obtain a polymer having a good hue (b value).
このような問題を解決する為に、チタン化合物と特定のリン化合物とを反応させて得られた生成物を（例えば特許文献５、特許文献６参照。）、またチタン化合物と特定のリン化合物の未反応混合物あるいは反応生成物を（例えば特許文献７参照。）、それぞれポリエステル製造用触媒として使用することが開示されている。確かにこの方法によればポリエステルの溶融熱安定性は向上し、得られるポリマーの色相も大きく改善されるが、これらの方法ではポリエステル製造時の重合反応速度が遅い為、ポリエステルの生産性がやや劣ってしまう問題を有している。 In order to solve such a problem, a product obtained by reacting a titanium compound with a specific phosphorus compound (see, for example, Patent Document 5 and Patent Document 6), or a titanium compound and a specific phosphorus compound are used. It is disclosed that an unreacted mixture or a reaction product (see, for example, Patent Document 7) is used as a catalyst for polyester production. Certainly, this method improves the melt heat stability of the polyester and greatly improves the hue of the resulting polymer. However, in these methods, the polymerization reaction rate during the production of the polyester is slow, so that the productivity of the polyester is slightly higher. Has the problem of being inferior.
ポリエステルの成形の安定性を向上させるには、前記のように触媒としてアンチモンを使用しないことが有効な手段であるが、アンチモンを使用しない方法では、糸のカラー（色相）が低下してしまうため、従来は使用に供することができなかった。したがって触媒としてアンチモンを使用せず、かつ色相に優れたポリエステルが求められていた。 In order to improve the molding stability of polyester, it is effective means not to use antimony as a catalyst as described above. However, in the method not using antimony, the color (hue) of the thread is lowered. In the past, it could not be used. Therefore, there has been a demand for a polyester that does not use antimony as a catalyst and has an excellent hue.
一方ポリエステルの色相を改善する試みとしては染料を混練したポリエステルが開示されているが（例えば特許文献８〜１０参照。）、色相改善のレベルとしてはまだ十分なものではなかった。
本発明の目的は色相に優れ、長時間連続的に紡糸しても、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステル組成物を提供することにある。また別の目的は鮮明な外観を有し、染色性の改善された繊維を得ることができるポリエステル組成物を提供することである。 An object of the present invention is to provide a polyester composition that has excellent hue and generates a very small amount of deposits on the die even when spinning continuously for a long time, and has excellent moldability. Another object is to provide a polyester composition having a clear appearance and capable of obtaining fibers with improved dyeability.
本発明者らは上記従来技術に鑑み鋭意検討を重ねた結果、本発明を完成するに至った。 As a result of intensive studies in view of the above prior art, the present inventors have completed the present invention.
すなわち本発明は、真比重５．０以上の金属元素の含有量が０〜１０質量ｐｐｍ以下である芳香族ポリエステルを主たる構成成分とし、該芳香族ポリエステルは下記一般式（Ｉ）で表わされる化合物と下記一般式（ＩＩ）で表わされる芳香族多価カルボン酸若しくは無水物とを反応させた生成物であるチタン化合物を含有するものであり、ポリエステル組成物の全質量を基準として整色剤を０．１〜１０質量ｐｐｍ含有し、かつ該整色剤は、青色系整色用色素及び紫色系整色用色素を９０：１０〜４０：６０の質量比で含むものであり、窒素雰囲気下中、昇温速度１０℃／分の条件で熱天秤にて測定したときの質量減少開始温度が２５０℃以上である整色用色素から選ばれるものであって、
更に平均粒径が０．０１〜０．５μｍの範囲であってかつ粒径が０．５μｍを超える粒子の頻度分率が２０質量％以下である不活性粒子を０．１〜５質量％含有し、当該不活性粒子が炭酸カルシウム、第三リン酸カルシウム、珪酸カルシウム、酸化ケイ素、酸化アルミニウム、シリコーンパウダー、カオリナイト、硫酸バリウム及び酸化チタンよりなる群から選ばれる少なくとも１つに該当するポリエステル組成物であって、該整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ該最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記数式（１）〜（４）のすべてを満たすポリエステル組成物、及びこれを溶融成形して得られる繊維であり、これによって上記の課題が解決できる。
Further, 0.1 to 5% by mass of inert particles having an average particle size in the range of 0.01 to 0.5 μm and a frequency fraction of particles having a particle size exceeding 0.5 μm is 20% by mass or less. And the inert particle is a polyester composition corresponding to at least one selected from the group consisting of calcium carbonate, tricalcium phosphate, calcium silicate, silicon oxide, aluminum oxide, silicone powder, kaolinite, barium sulfate and titanium oxide. When the visible light absorption spectrum in the wavelength range of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L in the color adjusting agent at an optical path length of 1 cm, the maximum absorption wavelength was in the range of 540 to 600 nm, and the maximum The ratio of the absorbance at each wavelength below to the absorbance at the absorption wavelength satisfies all of the following formulas (1) to (4). The polyester composition and the fiber obtained by melt-molding the polyester composition, thereby solving the above-mentioned problems.
本発明によればポリエステルの優れた特性を保持しながら、ＳｂやＧｅ触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。また、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステルを提供することが出来、その結果、色相に優れ、深みのある染色性を有するポリエステル繊維を提供することができる。 According to the present invention, it is possible to eliminate the deterioration of hue, which is a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent properties of polyesters. Further, it is possible to provide a polyester having excellent moldability with a very small amount of deposits on the die, and as a result, to provide a polyester fiber having excellent hue and deep dyeability. it can.
以下本発明を詳しく説明する。 The present invention will be described in detail below.
本発明における芳香族ポリエステルとは、テレフタル酸若しくはナフタレンジカルボン酸、又はこれらのエステル形成性誘導体に代表される芳香族ジカルボン酸成分と、グリコール成分を重縮合反応せしめて得られるポリエステルのことである。この芳香族ポリエステルは、共重合ポリエステルであってもよく、共重合成分として、芳香族ジカルボン酸成分とグリコール成分以外の成分、例えば脂肪族ジカルボン酸成分、芳香族ジヒドロキシ化合物、オキシカルボン酸成分が共重合されていても良い。 The aromatic polyester in the present invention is a polyester obtained by a polycondensation reaction of an aromatic dicarboxylic acid component typified by terephthalic acid or naphthalenedicarboxylic acid or an ester-forming derivative thereof with a glycol component. This aromatic polyester may be a copolymer polyester, and as a copolymer component, a component other than an aromatic dicarboxylic acid component and a glycol component, for example, an aliphatic dicarboxylic acid component, an aromatic dihydroxy compound, and an oxycarboxylic acid component are co-polymerized. It may be polymerized.
該芳香族ポリエステルとしては、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリトリメチレンテレフタレート、ポリトリメチレンナフタレート、ポリテトラメチレンテレフタレート、ポリテトラメチレンナフタレートよりなる群から少なくとも１種選ばれるポリエステルであることが好ましく、これらの中でも特にポリエチレンテレフタレートを主たる構成成分とするポリエステルであることが好ましい。なお「主たる構成成分」とはポリエステルの全繰り返し単位の８０モル％以上が芳香族ポリエステルであることを示す。 The aromatic polyester is preferably a polyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polytetramethylene terephthalate, and polytetramethylene naphthalate. Of these, polyesters having polyethylene terephthalate as the main constituent are particularly preferred. The “main constituent component” indicates that 80 mol% or more of all repeating units of the polyester is an aromatic polyester.
本発明における真比重５．０以上の金属元素とは通常芳香族ポリエステル中に含有される触媒や金属系の整色剤、艶消剤等に含有されている金属化合物に由来するものである。具体的には、アンチモン、ゲルマニウム、マンガン、コバルト、セリウム、錫、亜鉛、鉛又はカドミウム等が該当する。これらに対し、チタン、アルミニウム、カルシウム、マグネシウム、ナトリウム又はカリウム等はここでいう真比重５．０以上の金属には該当しない。 The metal element having a true specific gravity of 5.0 or more in the present invention is derived from a metal compound usually contained in a catalyst, a metal color adjuster, a matting agent, etc. contained in an aromatic polyester. Specifically, antimony, germanium, manganese, cobalt, cerium, tin, zinc, lead, cadmium, and the like are applicable. On the other hand, titanium, aluminum, calcium, magnesium, sodium, potassium, and the like do not correspond to a metal having a true specific gravity of 5.0 or more.
本発明のポリエステル組成物は真比重５．０以上の金属元素の含有量が０〜１０質量ｐｐｍ以下である必要がある。含有される金属の種類によってその特徴、特性は変わるが、例えばアンチモン金属含有量が１０質量ｐｐｍより多い場合、溶融紡糸時やフィルムの製膜時に異物となって口金やダイ周辺に付着し、長期間の連続成形性に悪影響を与える。ゲルマニウム金属の場合は、それ自体が高価な為、含有量が多くなると得られるポリエステル組成物の価格が上昇してしまい好ましくない。また、鉛、カドミウムなどの金属場合は金属元素そのものに毒性がある為、ポリエステル中に多量に含有していることは好ましくない。該真比重５．０以上の金属元素の含有量は０〜７質量ｐｐｍ以下であることが好ましく、０〜５質量ｐｐｍ以下であることが更に好ましい。 In the polyester composition of the present invention, the content of a metal element having a true specific gravity of 5.0 or more needs to be 0 to 10 mass ppm or less. The characteristics and properties vary depending on the type of metal contained. For example, when the content of antimony metal is more than 10 ppm by mass, it becomes a foreign substance during melt spinning or film formation and adheres to the periphery of the die or die. This will adversely affect the continuous formability of the period. In the case of germanium metal, since it is expensive per se, an increase in the content increases the price of the resulting polyester composition, which is not preferable. In addition, in the case of metals such as lead and cadmium, since the metal element itself is toxic, it is not preferable to contain a large amount in the polyester. The content of the metal element having a true specific gravity of 5.0 or more is preferably 0 to 7 mass ppm or less, and more preferably 0 to 5 mass ppm or less.
本発明のポリエステル組成物はその全質量を基準として整色剤を０．１〜１０質量ｐｐｍ含有する必要がある。なおその整色剤とは、有機の多芳香族環系染料又は顔料を表す。具体的には後述のように青色系整色用色素、紫色系整色用色素、赤色系整色用色素、橙色系整色用色素等が挙げられる。これらは単一種で用いても複数種を併用して用いても良い。後述のような可視光吸収スペクトルに関する要件を満たしやすい点において、複数種を併用することが好ましい。さらにその整色剤は、濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ該最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記数式（１）〜（４）のすべてを満たす必要がある。 The polyester composition of the present invention needs to contain 0.1 to 10 mass ppm of the color adjusting agent based on the total mass. The color adjusting agent represents an organic polyaromatic ring dye or pigment. Specific examples thereof include a blue color adjusting dye, a purple color adjusting dye, a red color adjusting dye, and an orange color adjusting dye as described later. These may be used alone or in combination of two or more. It is preferable to use a plurality of types in combination in terms of easily satisfying the requirements regarding the visible light absorption spectrum as described later. Further, when the visible light absorption spectrum in the wavelength range of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L at a light path length of 1 cm, the color adjusting agent had a maximum absorption wavelength in the range of 540 to 600 nm and the maximum absorption. The ratio of the absorbance at each wavelength below to the absorbance at the wavelength needs to satisfy all of the following formulas (1) to (4).
ここで可視光吸収スペクトルとは、通常分光光度計によって測定されるスペクトルであるが、本発明のポリエステル組成物に含有される整色剤溶液の可視光吸収スペクトルの最大吸収波長が５４０ｎｍ未満の場合は得られるポリエステル組成物の赤味が強くなり、また６００ｎｍを超える場合は得られるポリエステル組成物の青味が強くなる為好ましくない。最大吸収波長の範囲は５４５〜５９５ｎｍの範囲が好ましく、５５０〜５９０ｎｍの範囲が更に好ましい。
Here, the visible light absorption spectrum is a spectrum usually measured by a spectrophotometer, but when the maximum absorption wavelength of the visible light absorption spectrum of the color matching agent solution contained in the polyester composition of the present invention is less than 540 nm. Is not preferable because the reddishness of the obtained polyester composition becomes strong, and when it exceeds 600 nm, the blueness of the obtained polyester composition becomes strong. The range of the maximum absorption wavelength is preferably 545 to 595 nm, and more preferably 550 to 590 nm.
また本発明のポリエステル組成物に含有される整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて可視光吸収スペクトルを測定したとき、最大吸収波長での吸光度に対する上記に示す各波長での吸光度の割合が上記数式（１）〜（４）のいずれか一つでも外れる場合、得られるポリエステル組成物の着色が大きくなり好ましくない。上記式（１）〜（４）はそれぞれ下記数式（５）〜（８）のいずれか１つ以上の範囲にあることが好ましく、更に下記数式（５）〜（８）すべてを満たしていることが好ましい。 Further, when a visible light absorption spectrum was measured at an optical path length of 1 cm for a chloroform solution having a concentration of 20 mg / L of the color adjusting agent contained in the polyester composition of the present invention, the absorbance at each wavelength shown above with respect to the absorbance at the maximum absorption wavelength. When the absorbance ratio is out of any one of the above formulas (1) to (4), the resulting polyester composition is unfavorably colored. It is preferable that said formula (1)-(4) exists in the range of any one or more of following numerical formula (5)-(8), respectively, and also satisfy | fills all following numerical formula (5)-(8). Is preferred.
更に本発明のポリエステル組成物に含有される上述の整色剤の含有量が、０．１質量ｐｐｍ未満の場合、ポリエステル組成物の黄色味が強くなる。一方、１０質量ｐｐｍを超える場合、明度が弱くなり見た目に黒味が強くなる為好ましくない。該整色剤の含有量は０．３質量ｐｐｍ〜９質量ｐｐｍの範囲が好ましく、０．５〜８質量ｐｐｍの範囲にあることが更に好ましい。 Furthermore, when content of the above-mentioned color adjusting agent contained in the polyester composition of this invention is less than 0.1 mass ppm, the yellowishness of a polyester composition will become strong. On the other hand, if it exceeds 10 ppm by mass, the brightness becomes weak and the blackness becomes strong visually, which is not preferable. The content of the color adjusting agent is preferably in the range of 0.3 mass ppm to 9 mass ppm, and more preferably in the range of 0.5 to 8 mass ppm.
本発明に使用する整色剤は、窒素雰囲気下中、昇温速度１０℃／分の条件で熱天秤にて測定したときの質量減少開始温度が２５０℃以上である整色用色素から選ばれることが好ましい。ここで、熱天秤で測定したときの質量減少開始温度とは、ＪＩＳ Ｋ−７１２０に記載の質量減少開始温度（Ｔ１）のことであり、整色剤が有している耐熱性の指標となる。該質量減少開始温度が２５０℃未満である場合、整色剤の耐熱性が不十分であることから最終的に得られるポリエステル組成物の着色の原因となり好ましくない。該質量減少開始温度は３００℃以上であることが更に好ましい。また芳香族ポリエステルが溶融状態にある温度下で分解しないことが更に好ましい。 The color adjusting agent used in the present invention is selected from color adjusting dyes having a mass decrease starting temperature of 250 ° C. or higher when measured with a thermobalance in a nitrogen atmosphere at a temperature rising rate of 10 ° C./min. It is preferable. Here, the mass decrease start temperature when measured with a thermobalance is the mass decrease start temperature (T 1 ) described in JIS K-7120, and is a heat resistance index possessed by the color adjuster. Become. When the mass decrease starting temperature is less than 250 ° C., the heat resistance of the color adjusting agent is insufficient, which is not preferable because it causes coloring of the finally obtained polyester composition. The mass decrease starting temperature is more preferably 300 ° C. or higher. It is further preferable that the aromatic polyester does not decompose at a temperature at which it is in a molten state.
本発明のポリエステル組成物は、平均粒径が０．０１〜０．５μｍの範囲であって、かつ粒径が０．５μｍを超える粒子の頻度分率が２０質量％以下である不活性粒子をポリエステル組成物の全質量を基準として０．１〜５質量％含有している必要がある。 The polyester composition of the present invention comprises inert particles having an average particle size in the range of 0.01 to 0.5 μm and a frequency fraction of particles having a particle size exceeding 0.5 μm of 20% by mass or less. It is necessary to contain 0.1-5 mass% on the basis of the total mass of the polyester composition.
不活性粒子としては、炭酸カルシウム、リン酸カルシウム、珪酸カルシウム、酸化ケイ素、酸化アルミニウム、シリコーンパウダー、カオリナイト、硫酸バリウム、酸化チタン等が上げられ、これらよりなる群から少なくとも１つに該当することが好ましい。また不活性粒子は単一種であっても、複数種を併用してもよい。更にこれらの中でも特に炭酸カルシウム、リン酸カルシウム、シリカゾルが好ましく使用される。また、リン酸カルシウムとしては活性水素原子を有さない第三リン酸カルシウムが特に好ましく使用される。 Examples of the inert particles include calcium carbonate, calcium phosphate, calcium silicate, silicon oxide, aluminum oxide, silicone powder, kaolinite, barium sulfate, titanium oxide, and the like, and preferably corresponds to at least one from the group consisting of these. . Further, the inert particles may be a single type or a combination of multiple types. Of these, calcium carbonate, calcium phosphate, and silica sol are particularly preferably used. As calcium phosphate, tricalcium phosphate having no active hydrogen atom is particularly preferably used.
本発明における不活性粒子は平均粒径が０．０１〜０．５μｍの範囲である必要がある。平均粒径が０．５μｍを超えるとゾル又は芳香族ポリエステル反応原液中等の製造工程中で沈降しやすく、安定に供給・分散することができない。一方、平均粒径が０．０１μｍ未満では粒子の比表面積が大きすぎ、芳香族ポリエステル反応中に容易に凝集粒子を形成し、製糸時の断糸が増大するため、好ましくない。該不活性粒子の平均粒径は０．０２〜０．４μｍの範囲が好ましく、０．０３〜０．３μｍの範囲が更に好ましい。 The inert particles in the present invention need to have an average particle size in the range of 0.01 to 0.5 μm. If the average particle size exceeds 0.5 μm, it tends to settle during the production process such as in the sol or aromatic polyester reaction stock solution and cannot be stably supplied and dispersed. On the other hand, an average particle size of less than 0.01 μm is not preferable because the specific surface area of the particles is too large, and aggregated particles are easily formed during the aromatic polyester reaction, and the yarn breakage during yarn production increases. The average particle diameter of the inert particles is preferably in the range of 0.02 to 0.4 μm, and more preferably in the range of 0.03 to 0.3 μm.
本発明における不活性粒子においては、粒径が０．５μｍを超える粒子の頻度分率が２０質量％以下である必要がある。粒径が０．５μｍを超える粒子の頻度分率が２０質量％を超えると、得られたポリエステル組成物を製糸化後、アルカリ減量しても繊維表面に形成される微細孔が大きくなり、染色時の深色効果が得られないので好ましくない。該不活性粒子中の粒径が０．５μｍを超える粒子の頻度分率は１５質量％以下の範囲が好ましく１０質量％以下の範囲が更に好ましい。 In the inert particles in the present invention, the frequency fraction of particles having a particle size exceeding 0.5 μm needs to be 20% by mass or less. When the frequency fraction of particles having a particle size exceeding 0.5 μm exceeds 20% by mass, fine pores formed on the fiber surface become large even after alkali reduction after the obtained polyester composition is made into yarn, and dyeing is performed. Since the deep color effect at the time cannot be obtained, it is not preferable. The frequency fraction of particles having a particle size exceeding 0.5 μm in the inert particles is preferably in the range of 15% by mass or less, and more preferably in the range of 10% by mass or less.
本発明における不活性粒子含有量は０．１〜５質量％の範囲にある必要がある。該含有量が０．１質量％未満の場合、最終的に得られる繊維の深色染色性が不十分となり、また、５質量％を超える場合は得られるポリエステル繊維の強度や耐熱性、耐光性が低下する為好ましくない。該粒子含有量は０．１５〜３質量％の範囲が好ましく、０．２〜１．０質量％の範囲が更に好ましい。 Inert particle content in this invention needs to exist in the range of 0.1-5 mass%. When the content is less than 0.1% by mass, the deep color dyeability of the finally obtained fiber becomes insufficient, and when it exceeds 5% by mass, the strength, heat resistance, and light resistance of the obtained polyester fiber are insufficient. Is unfavorable because of lowering. The particle content is preferably in the range of 0.15 to 3% by mass, more preferably in the range of 0.2 to 1.0% by mass.
本発明のポリエステル組成物の固有粘度（溶媒：オルトクロロフェノール、測定温度：３５℃）は特に制限は無いが、通常、繊維やフィルム、ボトル等の樹脂成形品において通常使用することが出来る範囲であることが好ましく、具体的には０．４０〜１．００の範囲にあることが好ましい。また、該ポリエステル組成物は固相重合によって固有粘度を高めることも好ましく実施される。 The intrinsic viscosity (solvent: orthochlorophenol, measurement temperature: 35 ° C.) of the polyester composition of the present invention is not particularly limited, but is usually within a range that can be normally used in resin molded products such as fibers, films, and bottles. It is preferable that there exists, and it is preferable that it exists in the range of 0.40-1.00 specifically. In addition, it is also preferable to increase the intrinsic viscosity of the polyester composition by solid phase polymerization.
本発明のポリエステル組成物の色相は特に厳密な制限はないが、本発明に使用されるべき整色剤が添加されていないと、得られるポリエステルの色相が黄色味を帯びた色相となり好ましくない。該ポリエステル組成物の色相は、１４０℃、２時間熱処理により結晶化を進めた後のＬ＊ａ＊ｂ＊表色系におけるカラーａ＊値が−９〜０、カラーｂ＊値が−２〜１０の範囲にあることが好ましい。該カラー値は含有される整色剤の量によって変化してくるが、カラーａ＊値が−９より小さい場合、ポリエステル組成物は緑色味が強くなり、０より大きい場合は赤味が強くなり好ましくない。またカラーｂ＊値が−２より小さい場合、ポリエステル組成物は青味が強くなり、１０より大きい場合は黄色味が強くなるため好ましくない。 The hue of the polyester composition of the present invention is not particularly limited. However, if the color adjusting agent to be used in the present invention is not added, the hue of the resulting polyester becomes a yellowish hue, which is not preferable. The hue of the polyester composition is such that the color a * value is −9 to 0 and the color b * value is −2 to 2 in the L * a * b * color system after crystallizing by heat treatment at 140 ° C. for 2 hours. A range of 10 is preferable. The color value varies depending on the amount of the color adjusting agent contained. When the color a * value is less than −9, the polyester composition has a strong green color, and when the color value is greater than 0, the red color becomes strong. It is not preferable. Further, when the color b * value is less than −2, the polyester composition has a strong bluish color.
また本発明におけるポリエステル組成物は、必要に応じて少量の添加剤、例えば酸化防止剤、固相重合促進剤、蛍光増白剤、帯電防止剤、抗菌剤、紫外線吸収剤、光安定剤、熱安定剤、遮光剤又は艶消剤等を含んでいてもよい。 Further, the polyester composition in the present invention contains a small amount of additives as necessary, for example, an antioxidant, a solid phase polymerization accelerator, a fluorescent whitening agent, an antistatic agent, an antibacterial agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer. A stabilizer, a light-shielding agent, a matting agent, or the like may be included.
本発明における芳香族ポリエステルの製造方法は、通常知られているポリエステルの製造方法が用いられる。すなわち、まずテレフタル酸の如きジカルボン酸成分とエチレングリコールの如きグリコール成分とを直接エステル化反応させる、又はテレフタル酸ジメチル（以下ＤＭＴと称することがある。）の如きジカルボン酸成分の低級アルキルエステルとエチレングリコールの如きグリコール成分とをエステル交換反応させ、ジカルボン酸のグリコールエステル及び／又はその低重合体を製造する。次いでこの反応生成物を重縮合触媒の存在下で減圧加熱して所定の重合度になるまで重縮合反応させることによって目的とする芳香族ポリエステルが製造される。芳香族ポリエステル以外の他のポリエステルを含む場合についても、芳香族ポリエステルと共重合する、若しくは芳香族ポリエステル以外の他のポリエステルについて通常知られている製造方法を用い、重縮合後芳香族ポリエステルとブレンドする等の手法を採用することができる。 As a method for producing an aromatic polyester in the present invention, a conventionally known polyester production method is used. That is, first, a dicarboxylic acid component such as terephthalic acid is directly esterified with a glycol component such as ethylene glycol, or a lower alkyl ester of a dicarboxylic acid component such as dimethyl terephthalate (hereinafter sometimes referred to as DMT) and ethylene. A glycol component such as glycol is transesterified to produce a glycol ester of dicarboxylic acid and / or a low polymer thereof. Then, the reaction product is heated under reduced pressure in the presence of a polycondensation catalyst and subjected to a polycondensation reaction until a predetermined degree of polymerization is obtained, thereby producing the desired aromatic polyester. Also in the case of containing other polyesters other than aromatic polyester, blend with aromatic polyester after polycondensation using copolymerization with aromatic polyester or using a production method generally known for other polyesters other than aromatic polyester It is possible to adopt a technique such as.
更に詳説すると、芳香族ポリエステルを製造する際において用いる重縮合触媒は、チタン化合物及び／又はアルミニウム化合物であることが好ましい。ここで、チタン化合物としては特に限定されず、ポリエステルの重縮合触媒として一般的なチタン化合物、例えば、酢酸チタンやテトラ−ｎ−ブトキシチタンなどが挙げられる。チタン化合物としてより好ましいのは、下記一般式（Ｉ）で表わされるチタン化合物、一般式（Ｉ）で表わされるチタン化合物と下記一般式（ＩＩ）で表わされる芳香族多価カルボン酸若しくはその無水物とを反応させた生成物、又は下記一般式（ＩＩＩ）で表されるチタン化合物を用いることである。 More specifically, the polycondensation catalyst used when producing the aromatic polyester is preferably a titanium compound and / or an aluminum compound. Here, it does not specifically limit as a titanium compound, A titanium compound common as a polycondensation catalyst of polyester, for example, titanium acetate, tetra-n-butoxy titanium, etc. are mentioned. More preferable as the titanium compound is a titanium compound represented by the following general formula (I), a titanium compound represented by the general formula (I) and an aromatic polyvalent carboxylic acid represented by the following general formula (II) or an anhydride thereof. Or a titanium compound represented by the following general formula (III).
一方、アルミニウム化合物としても特に限定はないが、触媒活性の点で有機アルミニウム化合物であることが好ましく、中でもアルミニウムアセチルアセトネートなどが安定で取扱いが容易な点において優れているので好ましい。また、これらチタン化合物とアルミニウム化合物はそれぞれの化合物を単独で用いても、両化合物を併用して用いても、又はそれぞれの化合物を２種類以上を併用しても良いが、チタン化合物を単独で用いるのが特に好ましい。なかでも最も好ましいのが上記一般式（Ｉ）で表わされる化合物、又は一般式（Ｉ）で表わされる化合物と上記一般式（ＩＩ）で表わされる芳香族多価カルボン酸若しくはその無水物とを反応させた生成物を単独で用いることである。 On the other hand, the aluminum compound is not particularly limited, but is preferably an organoaluminum compound from the viewpoint of catalytic activity. Among them, aluminum acetylacetonate is preferable because it is stable and easy to handle. In addition, these titanium compounds and aluminum compounds may be used alone or in combination of both compounds, or two or more of each compound may be used in combination. It is particularly preferable to use it. Of these, the compound represented by the above general formula (I) or the compound represented by the general formula (I) is preferably reacted with the aromatic polycarboxylic acid represented by the above general formula (II) or its anhydride. The product obtained is used alone.
一般式（Ｉ）で表わされるチタン化合物の中でテトラアルコキサイドチタンおよび／またはテトラフェノキサイドチタンとしては、Ｒ１〜Ｒ４がアルキル基および／またはフェニル基であれば特に限定されないが、テトライソプロポキシチタン、テトラ−ｎ−プロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラエトキシチタン又はテトラフェノキシチタンなどが好ましく用いられる。また、かかるチタン化合物と反応させる一般式（ＩＩ）で表される芳香族多価カルボン酸またはその無水物としては、フタル酸、トリメリット酸、ヘミメリット酸若しくはピロメリット酸又はこれらの酸の無水物が好ましく用いられる。上記チタン化合物と芳香族多価カルボン酸又はその無水物とを反応させる場合には、溶媒に芳香族多価カルボン酸又はその無水物の全部又は一部を溶解し、これにチタン化合物を滴下し、０〜２００℃の温度で３０分以上反応させれば良い。また必要に応じてチタン化合物滴下後、残りの芳香族多価カルボン酸又はその無水物を加えればよい。 Among the titanium compounds represented by the general formula (I), tetraalkoxide titanium and / or tetraphenoxide titanium are not particularly limited as long as R 1 to R 4 are an alkyl group and / or a phenyl group. Isopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetraethoxy titanium, tetraphenoxy titanium and the like are preferably used. In addition, the aromatic polyvalent carboxylic acid represented by the general formula (II) to be reacted with the titanium compound or an anhydride thereof includes phthalic acid, trimellitic acid, hemimellitic acid, pyromellitic acid, or anhydrous anhydrides of these acids. The product is preferably used. When the titanium compound and the aromatic polyvalent carboxylic acid or anhydride thereof are reacted, all or part of the aromatic polyvalent carboxylic acid or anhydride thereof is dissolved in a solvent, and the titanium compound is dropped into this. What is necessary is just to make it react for 30 minutes or more at the temperature of 0-200 degreeC. Moreover, what is necessary is just to add the remaining aromatic polyhydric carboxylic acid or its anhydride after dripping a titanium compound as needed.
本発明のポリエステル組成物は上述した通り、チタン化合物及び／又はアルミニウム化合物を重縮合触媒として用いられていることが好ましいが、更に耐熱性や色相を改善すべく、リン化合物を安定剤として併用することが好ましい。該リン化合物としては特に制限はないが、好ましくはリン酸、亜リン酸、ホスホン酸若しくはホスフィン酸又はこれらのアルキル、アリールエステル、ホスホノアセテート系化合物が特に好ましい。該リン化合物のポリエステル組成物中への添加方法は、エステル交換反応又はエステル化反応が実質的に終了した後であればいつでもよいが、通常はエステル化反応、若しくはエステル交換反応が終了した後すぐに添加し、その後重縮合反応せしめることが好ましい。 As described above, the polyester composition of the present invention preferably uses a titanium compound and / or an aluminum compound as a polycondensation catalyst, but further uses a phosphorus compound as a stabilizer in order to further improve heat resistance and hue. It is preferable. Although there is no restriction | limiting in particular as this phosphorus compound, Preferably phosphoric acid, phosphorous acid, phosphonic acid, or phosphinic acid or these alkyl, aryl ester, and a phosphono acetate type compound are especially preferable. The phosphorus compound may be added to the polyester composition at any time after the ester exchange reaction or the esterification reaction is substantially completed, but usually immediately after the esterification reaction or the ester exchange reaction is completed. The polycondensation reaction is preferably carried out thereafter.
さらに本発明のポリエステル組成物の製造方法は上述した芳香族ポリエステル製造工程の任意の段階で整色剤を添加することによって製造されることが好ましい。なかでも整色剤が芳香族ポリエステル製造工程における重縮合反応工程が終了するまでの任意の段階で添加されることが更に好ましい。特にエステル化反応もしくはエステル交換反応が終了した後に整色剤を添加することが最も好ましい。 Furthermore, it is preferable that the manufacturing method of the polyester composition of this invention is manufactured by adding a color adjusting agent in the arbitrary steps of the aromatic polyester manufacturing process mentioned above. Especially, it is still more preferable that a color adjusting agent is added in the arbitrary steps until the polycondensation reaction process in an aromatic polyester manufacturing process is complete | finished. In particular, it is most preferable to add the color adjusting agent after completion of the esterification reaction or transesterification reaction.
本発明のポリエステル組成物の製造方法においては、整色剤として青色系整色用色素と紫色系整色用色素を質量比９０：１０〜４０：６０の範囲で併用すること、又は青色系整色用色素と赤色系又は橙色系整色用色素を質量比９８：２〜８０：２０の範囲で併用することが好ましい。ここで青色系整色用色素とは、一般に市販されている整色用色素の中で「Ｂｌｕｅ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が５８０〜６２０ｎｍ程度にあるものを示す。同様に紫色系整色用色素とは市販されている整色用色素の中で「Ｖｉｏｌｅｔ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が５６０〜５８０ｎｍ程度にあるものを示す。赤色系整色用色素とは市販されている整色用色素の中で「Ｒｅｄ」と表記されているものであって、具体的には溶液中の可視光吸収スペクトルにおける最大吸収波長が４８０〜５２０ｎｍ程度にあるものである。橙色系系整色用色素とは市販されている整色用色素の中で「Ｏｒａｎｇｅ」と表記されているものである。 In the method for producing a polyester composition of the present invention, a blue color adjusting dye and a purple color adjusting dye are used in combination in a mass ratio of 90:10 to 40:60, or a blue color adjusting agent. It is preferable to use the color dye and the red or orange color adjusting dye in a mass ratio of 98: 2 to 80:20. Here, the blue color-modifying dye is generally indicated as “Blue” among commercially available color-adjusting dyes, and specifically, the maximum absorption in the visible light absorption spectrum in the solution. The wavelength is about 580 to 620 nm. Similarly, the purple color-modifying dye is the one described as “Violet” among commercially available color-adjusting dyes, and specifically has a maximum absorption wavelength in a visible light absorption spectrum in a solution. The thing in about 560-580 nm is shown. The red color-modifying dyes are those listed as “Red” among commercially available color-adjusting dyes. Specifically, the maximum absorption wavelength in the visible light absorption spectrum in the solution is 480 to 480. It is about 520 nm. The orange-based color-adjusting colorant is the one described as “Orange” among commercially available color-adjusting colorants.
これらの整色用色素としては油溶染料が特に好ましく、具体的な例としては、青色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ １１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ３６、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ４５ （Ｔｅｌａｓｏｌ Ｂｌｕｅ ＲＬＳ）、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ５５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ６３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ７８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ８７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｂｌｕｅ ９４等が挙げられる。紫色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １３、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ １４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ２８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｖｉｏｌｅｔ ３６等が挙げられる。赤色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２４、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ２７、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ３０、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ４９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ ５２、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １００、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １０９、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １１１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １２１、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １３５、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １６８、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｒｅｄ １７９等が例示される。橙色系整色用色素には、Ｃ．Ｉ．Ｓｏｌｖｅｎｔ Ｏｒａｎｇｅ ６０等が挙げられる。 As these color adjusting pigments, oil-soluble dyes are particularly preferable. Specific examples of blue color adjusting pigments include C.I. I. Solvent Blue 11, C.I. I. Solvent Blue 25, C.I. I. Solvent Blue 35, C.I. I. Solvent Blue 36, C.I. I. Solvent Blue 45 (Telasol Blue RLS), C.I. I. Solvent Blue 55, C.I. I. Solvent Blue 63, C.I. I. Solvent Blue 78, C.I. I. Solvent Blue 83, C.I. I. Solvent Blue 87, C.I. I. Solvent Blue 94 and the like. Examples of purple color adjusting pigments include C.I. I. Solvent Violet 8, C.I. I. Solvent Violet 13, C.I. I. Solvent Violet 14, C.I. I. Solvent Violet 21, C.I. I. Solvent Violet 27, C.I. I. Solvent Violet 28, C.I. I. Solvent Violet 36 etc. are mentioned. Examples of red color adjusting pigments include C.I. I. Solvent Red 24, C.I. I. Solvent Red 25, C.I. I. Solvent Red 27, C.I. I. Solvent Red 30, C.I. I. Solvent Red 49, C.I. I. Solvent Red 52, C.I. I. Solvent Red 100, C.I. I. Solvent Red 109, C.I. I. Solvent Red 111, C.I. I. Solvent Red 121, C.I. I. Solvent Red 135, C.I. I. Solvent Red 168, C.I. I. Solvent Red 179 etc. are illustrated. Examples of the orange color adjusting dye include C.I. I. Solvent Orange 60 etc. are mentioned.
ここで青色系整色用色素と紫色系整色用色素を併用する場合、質量比９０：１０より青色系整色用色素の質量比が大きい場合は、得られるポリエステル組成物のカラーａ＊値が小さくなって緑色を呈し、４０：６０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。同様に青色系整色用色素と赤色系又は橙色系整色用色素を併用する場合、質量比９８：２より青色系整色用色素の質量比が大きい場合は、得られるポリエステル組成物のカラーａ＊値が小さくなって緑色を呈し、８０：２０より青色整色用色素の質量比が小さい場合は、カラーａ＊値が大きくなって赤色を呈してくる為好ましくない。該整色用色素は、青色系整色用色素と紫色系整色用色素を質量比８０：２０〜５０：５０の範囲で併用すること、あるいは青色系整色用色素と赤色系または橙色系整色用色素を質量比９５：５〜９０：１０の範囲で併用することが更に好ましい。 Here, when the blue color adjusting dye and the purple color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than the mass ratio 90:10, the color a * value of the obtained polyester composition Is small and exhibits a green color, and when the mass ratio of the blue color adjusting pigment is smaller than 40:60, the color a * value increases and a red color is exhibited, which is not preferable. Similarly, in the case where a blue color adjusting dye and a red or orange color adjusting dye are used in combination, when the mass ratio of the blue color adjusting dye is larger than 98: 2, the color of the resulting polyester composition If the a * value is small and green, and the mass ratio of the blue color-changing dye is smaller than 80:20, the color a * value becomes large and red is not preferable. The color adjusting dye is a combination of a blue color adjusting dye and a purple color adjusting dye in a mass ratio of 80:20 to 50:50, or a blue color adjusting dye and a red or orange color. It is more preferable to use the color adjusting dye in a mass ratio of 95: 5 to 90:10.
さらに本発明のポリエステル繊維を製造する時の製造方法としては特に限定はなく、従来公知の溶融紡糸方法が用いられる。例えば乾燥したポリエステル組成物を２７０℃〜３００℃の範囲で溶融紡糸して製造することが好ましく、溶融紡糸の引き取り速度は４００〜５０００ｍ／分で紡糸することが好ましい。紡糸速度がこの範囲にあると、得られる繊維の強度も十分なものであると共に、安定して巻き取りを行うこともできる。また紡糸時に使用する口金の形状についても特に制限は無く、円形、異形、中実、中空などのいずれも採用することが出来る。また延伸は未延伸ポリエステル繊維を一旦巻き取ってから行う、あるいは巻き取ることなく連続的に行うことによって、延伸糸を得ることができる。更に本発明のポリエステル繊維は風合や染色性を高める為に、アルカリ減量処理も好ましく実施されるが、特に得られたポリエステル繊維を用いて織編物の状態にした後にアルカリ減量処理を施すことにより、本発明の課題である染色性を改善することが可能となる。 Further, the production method for producing the polyester fiber of the present invention is not particularly limited, and a conventionally known melt spinning method is used. For example, it is preferable to produce the dried polyester composition by melt spinning at a temperature in the range of 270 ° C. to 300 ° C., and the spinning speed of the melt spinning is preferably 400 to 5000 m / min. When the spinning speed is in this range, the strength of the obtained fiber is sufficient, and the winding can be stably performed. Further, the shape of the die used at the time of spinning is not particularly limited, and any of circular, irregular, solid and hollow can be adopted. Further, the drawn yarn can be obtained by drawing the undrawn polyester fiber once or by continuously drawing it without winding. Furthermore, the polyester fiber of the present invention is preferably subjected to an alkali weight reduction treatment in order to improve the texture and dyeability. In particular, the polyester fiber is made into a woven or knitted fabric using the obtained polyester fiber and then subjected to the alkali weight loss treatment. It becomes possible to improve the dyeability which is the subject of the present invention.
本発明をさらに下記実施例により具体的に説明するが、本発明の範囲はこれら実施例により限定されるものではない。尚、固有粘度、色相、チタン含有量及び紡糸口金に発生する付着物の層等については、下記記載の方法により測定した。 The present invention will be further described in the following examples, but the scope of the present invention is not limited by these examples. The intrinsic viscosity, hue, titanium content, and the layer of deposits generated on the spinneret were measured by the methods described below.
（ア）固有粘度：
ポリエステル組成物チップを１００℃、６０分間でオルトクロロフェノールに溶解した希薄溶液を、３５℃でウベローデ粘度計を用いて測定した値から求めた。
(A) Intrinsic viscosity:
A dilute solution obtained by dissolving a polyester composition chip in orthochlorophenol at 100 ° C. for 60 minutes was determined from a value measured at 35 ° C. using an Ubbelohde viscometer.
（イ）ジエチレングリコール含有量：
ヒドラジンヒドラート（抱水ヒドラジン）を用いてポリエステル組成物チップを分解し、この分解生成物中のジエチレングリコールの含有量をガスクロマトグラフィ−（ヒューレットパッカード社製（ＨＰ６８５０型））を用いて測定した。
(A) Diethylene glycol content:
The polyester composition chip was decomposed using hydrazine hydrate (hydrated hydrazine), and the content of diethylene glycol in the decomposed product was measured using gas chromatography (manufactured by Hewlett-Packard (HP 6850 type)).
（ウ）色相（Ｌ＊値、ａ＊値、ｂ＊値）：
・チップ：
ポリエステル組成物チップを２８５℃、真空下で１０分間溶融し、これをアルミニウム板上で厚さ３．０±１．０ｍｍのプレートに成形後ただちに氷水中で急冷し、該プレートを１４０℃、１時間乾燥結晶化処理を行った。その後、色差計調整用の白色標準プレート上に置き、プレート表面のハンターＬ＊及びｂ＊を、ミノルタ株式会社製ハンター型色差計（ＣＲ−２００型）を用いて測定した。Ｌ＊は明度を示し、その数値が大きいほど明度が高いことを示し、ｂ＊はその値が大きいほど黄着色の度合いが大きいことを示す。また他の詳細な操作はＪＩＳ Ｚ−８７２９に準じて行った。
・繊維：
繊維を常法により筒編とした後、編地を４枚重ね合わせ、ミノルタ株式会社製ハンター型色差計（ＣＲ−２００型）を用いて測定した。
(C) Hue (L * value, a * value, b * value):
・ Chip:
The polyester composition chip was melted at 285 ° C. under vacuum for 10 minutes, formed into a plate having a thickness of 3.0 ± 1.0 mm on an aluminum plate, and immediately cooled in ice water. A time dry crystallization treatment was performed. Then, it placed on the white standard plate for color difference adjustment, and measured Hunter L * and b * of the plate surface using Minolta Co., Ltd. Hunter type color difference meter (CR-200 type). L * indicates lightness, and the larger the value, the higher the lightness, and b * the greater the value, the greater the degree of yellowing. Other detailed operations were performed according to JIS Z-8729.
·fiber:
After making the fiber into a tubular knitting by a conventional method, four knitted fabrics were overlapped and measured using a Hunter type color difference meter (CR-200 type) manufactured by Minolta Co., Ltd.
（エ）真比重５．０以上の金属成分定性分析：
ポリエステル組成物サンプルを硫酸アンモニウム、硫酸、硝酸、過塩素酸とともに混合して約３００℃で９時間湿式分解後、蒸留水で希釈し、理学電機工業株式会社製ＩＣＰ発光分析装置（ＪＹ１７０ ＵＬＴＲＡＣＥ）を用いて定性分析し、真比重５．０以上の金属元素の有無を確認した。１質量ｐｐｍ以上の存在が確認された金属元素について、その元素含有量を示した。
(D) Metal component qualitative analysis with true specific gravity of 5.0 or more:
A polyester composition sample was mixed with ammonium sulfate, sulfuric acid, nitric acid, and perchloric acid, wet-decomposed at about 300 ° C. for 9 hours, diluted with distilled water, and then used with an ICP emission analyzer (JY170 ULTRACE) manufactured by Rigaku Corporation. Qualitative analysis was conducted to confirm the presence or absence of a metal element having a true specific gravity of 5.0 or more. About the metal element by which presence of 1 mass ppm or more was confirmed, the element content was shown.
（オ）チタン、アルミニウム、アンチモン、リン含有量：
ポリエステル組成物中のポリエステルに可溶性のチタン元素量、アルミニウム元素量、アンチモン元素量、リン元素量は粒状のポリエステル組成物サンプルをスチール板上で加熱溶融した後、圧縮プレス機で平坦面を有する試験成形体を作成し、蛍光Ｘ線装置（理学電機工業株式会社製 ＺＳＸ１００ｅ型）を用いて求めた。ただし、艶消剤として酸化チタンを添加したポリエステル組成物中のチタン元素量については、ポリエステル組成物中サンプルをオルトクロロフェノールに溶解した後、０．５規定塩酸で抽出操作を行った。この抽出液について日立製作所製Ｚ−８１００型原子吸光光度計を用いて定量を行った。ここで０．５規定塩酸抽出後の抽出液中に酸化チタンの分散が確認された場合は遠心分離機で酸化チタン粒子を沈降させた。次に傾斜法により上澄み液のみを回収して、同様の操作を行った。これらの操作によりポリエステル組成物中に酸化チタンを含有していてもポリエステルに可溶性のチタン元素の定量が可能となる。
(E) Titanium, aluminum, antimony, phosphorus content:
Polyester composition soluble titanium element amount, aluminum element amount, antimony element amount, phosphorus element amount is a test in which a granular polyester composition sample is heated and melted on a steel plate and then flattened with a compression press. A molded body was prepared and obtained using a fluorescent X-ray apparatus (ZSX100e type, manufactured by Rigaku Corporation). However, regarding the amount of elemental titanium in the polyester composition to which titanium oxide was added as a matting agent, a sample in the polyester composition was dissolved in orthochlorophenol, and then extracted with 0.5 N hydrochloric acid. The extract was quantified using a Hitachi Z-8100 atomic absorption spectrophotometer. Here, when dispersion of titanium oxide was confirmed in the extract after extraction with 0.5 N hydrochloric acid, titanium oxide particles were precipitated using a centrifuge. Next, only the supernatant was recovered by the gradient method, and the same operation was performed. By these operations, even if the polyester composition contains titanium oxide, the titanium element soluble in the polyester can be quantified.
（カ）紡糸口金に発生する付着物の層：
ポリエステル組成物をチップとなし、これを２９０℃で溶融し、孔径０．１５ｍｍφ、孔数１２個の紡糸口金から吐出し、６００ｍ／分で２日間紡糸し、口金の吐出口外縁に発生する付着物の層の高さを測定した。この付着物層の高さが大きいほど吐出されたポリエステル組成物の溶融物のフィラメント状流にベンディングが発生しやすく、このポリエステルの成形性は低くなる。すなわち、紡糸口金に発生する付着物層の高さは、当該ポリエステルの成形性の指標である。
(F) Layer of deposits generated on the spinneret:
The polyester composition is made into chips, melted at 290 ° C., discharged from a spinneret having a hole diameter of 0.15 mmφ and 12 holes, spun at 600 m / min for 2 days, and generated at the outer edge of the discharge outlet of the base. The height of the kimono layer was measured. As the height of the adhered layer increases, bending tends to occur in the filamentous flow of the melted polyester composition, and the moldability of the polyester decreases. That is, the height of the deposit layer generated in the spinneret is an index of the moldability of the polyester.
（キ）深色染色性評価：
繊維を布帛に形成した試験片を、沸騰した０．５質量％水酸化ナトリウム水溶液に浸して、布帛の質量減少率が２０％となるまでアルカリ減量処理を施した。取り出した布帛を水洗後、住友化学工業製分散染料Ｓｕｍｉｋａｒｏｎ Ｎａｖｙ Ｂｌｕｅ Ｓ−２ＧＬの２％ｏｗｆ溶液で浴比１：５０に調製し、１３０℃で１時間染色した。染色布をグレタマクベス社製測色色差計（ＣＥ−３０００型）により測色し、下記のクベルカ・ムンクの式により、深色度（Ｋ／Ｓ）を求めた。
(G) Evaluation of deep color dyeability:
The test piece in which the fiber was formed on the fabric was immersed in a boiled 0.5% by mass sodium hydroxide aqueous solution and subjected to an alkali reduction treatment until the mass reduction rate of the fabric reached 20%. The fabric taken out was washed with water, adjusted to a bath ratio of 1:50 with a 2% owf solution of disperse dye Sumikaron Navy Blue S-2GL manufactured by Sumitomo Chemical Co., Ltd., and dyed at 130 ° C. for 1 hour. The dyed cloth was measured with a colorimetric color difference meter (CE-3000 type) manufactured by Greta Macbeth Co., and the deep chromaticity (K / S) was determined by the following Kubelka-Munk equation.
（ク）整色剤の質量減少開始温度：
理学電機工業株式会社製ＴＡＳ−２００熱天秤を用いてＪＩＳ Ｋ７１２０に従い、窒素雰囲気下中昇温速度１０℃／分で測定した。
(H) Mass reduction start temperature of color adjusting agent:
Using a TAS-200 thermobalance manufactured by Rigaku Denki Kogyo Co., Ltd., the temperature was measured in a nitrogen atmosphere at a heating rate of 10 ° C./min according to JIS K7120.
（ケ）不活性粒子の特性評価
不活性粒子の平均粒径及び粒度分布を、株式会社島津製作所製ＳＡＬＤ−７０００型（レーザー散乱型粒度分布測定装置）で測定した。さらに測定した粒度分布より粒径が０．５μｍを超える不活性粒子の頻度分率を算出した。
(I) Characteristic evaluation of inert particles The average particle size and particle size distribution of the inert particles were measured with a SALD-7000 type (laser scattering type particle size distribution measuring device) manufactured by Shimadzu Corporation. Further, the frequency fraction of inert particles having a particle size exceeding 0.5 μm was calculated from the measured particle size distribution.
［参考例１］チタン触媒Ａの合成
無水トリメリット酸のエチレングリコール溶液（０．２質量％）にテトラ−ｎ−ブトキシチタンを無水トリメリット酸に対して１／２モル添加し、空気中常圧下で８０℃に保持して６０分間反応せしめた。その後常温に冷却し、１０倍量のアセトンによって生成触媒を再結晶化させた。析出物をろ紙によって濾過し、１００℃で２時間乾燥せしめ、目的の化合物を得た。これをチタン触媒Ａとする。
[Reference Example 1] Synthesis of Titanium Catalyst A Tetra-n-butoxytitanium is added to an ethylene glycol solution (0.2% by mass) of trimellitic anhydride in an amount of ½ mol with respect to trimellitic anhydride, and under normal pressure in air. And kept at 80 ° C. for 60 minutes. Thereafter, it was cooled to room temperature, and the produced catalyst was recrystallized with 10 times the amount of acetone. The precipitate was filtered through filter paper and dried at 100 ° C. for 2 hours to obtain the target compound. This is designated as titanium catalyst A.
［参考例２］整色剤（整色用色素）の可視光吸収スペクトル測定、整色剤調製
表１に示す整色用色素を室温で濃度２０ｍｇ／Ｌのクロロホルム溶液とし、光路長１ｃｍの石英セルに充填し、対照セルにはクロロホルムのみを充填して、日立分光光度計Ｕ−３０１０型を用いて、３８０〜７８０ｎｍの可視光領域での可視光吸収スペクトルを測定した。整色用色素２種を混合する場合は合計で濃度２０ｍｇ／Ｌとなるようにした。最大吸収波長とその波長における吸光度に対する、４００、５００、６００及び７００ｎｍの各波長での吸光度の割合を測定した。更に粉末の整色用色素の熱質量減少開始温度を測定した。結果を表１に示す。尚、実施例、比較例でこれら整色剤をポリエステル製造工程で添加する場合は、１００℃の温度で、原料として用いるグリコール溶液に対し、濃度０．１質量％となるように溶解又は分散させて調製した。
[Reference Example 2] Visible light absorption spectrum measurement of color-adjusting agent (color-adjusting dye), preparation of color-adjusting agent The color-adjusting dye shown in Table 1 was made into a chloroform solution at a concentration of 20 mg / L at room temperature, and quartz having an optical path length of 1 cm. The cell was filled, and the control cell was filled with chloroform alone, and a visible light absorption spectrum in a visible light region of 380 to 780 nm was measured using a Hitachi spectrophotometer U-3010 type. In the case of mixing the two color adjusting dyes, the total concentration was 20 mg / L. The ratio of the absorbance at each wavelength of 400, 500, 600, and 700 nm to the maximum absorption wavelength and the absorbance at that wavelength was measured. Further, the thermal mass decrease start temperature of the powder color adjusting dye was measured. The results are shown in Table 1. In addition, when adding these color adjusters in the polyester production process in the Examples and Comparative Examples, the solution is dissolved or dispersed at a temperature of 100 ° C. so as to have a concentration of 0.1% by mass with respect to the glycol solution used as a raw material. Prepared.
［実施例１］
・ポリエステル組成物チップの製造
テレフタル酸ジメチル１００質量部とエチレングリコール７０質量部との混合物に、酢酸カルシウム一水和物０．０６３質量部（ＤＭＴ1モルに対して７０ｍｍｏｌ％）を撹拌機、精留塔及びメタノール留出コンデンサーを設けた反応器に仕込み、１４０℃から２４０℃まで徐々に昇温しつつ、反応の結果生成するメタノールを系外に留出させながら、エステル交換反応を行った。その後、５６質量％のリン酸水溶液０．０４５質量部（ＤＭＴ1モルに対して５０ｍｍｏｌ％）を添加し、エステル交換反応を終了させた。その後反応生成物に表２に示す整色剤Ａの０．１質量％エチレングリコール溶液０．４部（ポリエステル組成物質量に対して４質量ｐｐｍ）、参考例１で調製したチタン触媒Ａ ０．０３２質量部（ＤＭＴ1モルに対して１０ｍｍｏｌ％）及び平均粒径０．０６μｍの第三リン酸カルシウムの２０質量％エチレングリコールスラリー２．５質量部（ポリエステル組成物質量に対して０．５質量％）を添加して、撹拌装置、窒素導入口、減圧口及び蒸留装置を備えた反応容器に移し、２８５℃まで昇温し、３０Ｐａ以下の高真空で重縮合反応を行って、固有粘度０．６５、ジエチレングリコール含有量が０．８質量％であるポリエステル組成物を得た。さらに常法に従いチップ化した。結果を表３に示す。
・ポリエステル繊維の製造
ポリエステル組成物チップを１６０℃、４時間乾燥後、紡糸温度２８５℃、巻取速度４００ｍ／分で３３３ｄｔｅｘ／３６ｆｉｌの原糸を作り、４．０倍に延伸して８３．２５ｄｔｅｘ／３６ｆｉｌの延伸糸を得た。得られた延伸糸は更に常法により筒編みとした。結果を表４に示す。
[Example 1]
-Manufacture of polyester composition chip To a mixture of 100 parts by mass of dimethyl terephthalate and 70 parts by mass of ethylene glycol, 0.063 parts by mass of calcium acetate monohydrate (70 mmol% with respect to 1 mol of DMT) was stirred and rectified. A reactor equipped with a tower and a methanol distillation condenser was charged, and the ester exchange reaction was carried out while gradually raising the temperature from 140 ° C. to 240 ° C. while distilling methanol produced as a result of the reaction out of the system. Thereafter, 0.045 parts by mass of a 56% by mass phosphoric acid aqueous solution (50 mmol% with respect to 1 mol of DMT) was added to complete the transesterification reaction. Thereafter, the reaction product was 0.4 parts of 0.1 wt% ethylene glycol solution of the color adjusting agent A shown in Table 2 (4 ppm by mass with respect to the amount of the polyester composition material), and the titanium catalyst A prepared in Reference Example 1. 032 parts by mass (10 mmol% with respect to 1 mol of DMT) and 2.5 parts by mass of 20 mass% ethylene glycol slurry of calcium triphosphate having an average particle size of 0.06 μm (0.5 mass% with respect to the amount of the polyester composition material) Added, transferred to a reaction vessel equipped with a stirrer, a nitrogen inlet, a vacuum port and a distillation device, heated to 285 ° C., and subjected to a polycondensation reaction at a high vacuum of 30 Pa or less, an intrinsic viscosity of 0.65, A polyester composition having a diethylene glycol content of 0.8% by mass was obtained. Furthermore, it was made into a chip according to a conventional method. The results are shown in Table 3.
-Manufacture of polyester fiber A polyester composition chip is dried at 160 ° C for 4 hours, a spinning temperature of 285 ° C and a winding speed of 400 m / min. A / 36 fil drawn yarn was obtained. The obtained drawn yarn was further knitted into a cylinder by a conventional method. The results are shown in Table 4.
［実施例２−７、実施例９、参考例８、比較例１−４］
実施例１において、リン酸、重縮合触媒、整色剤、不活性粒子を表２に示す種類、量に変更したこと以外は実施例１と同様に実施した。結果を表３、４に示す。
[Example 2-7, Example 9, Reference Example 8 , Comparative Example 1-4]
In Example 1, it implemented like Example 1 except having changed phosphoric acid, the polycondensation catalyst, the color adjusting agent, and the inert particle into the kind and quantity shown in Table 2. The results are shown in Tables 3 and 4.
本発明によればポリエステルの優れた特性を保持しながら、ＳｂやＧｅ触媒を使用しないポリエステルの欠点であった色相の悪化を解消することができる。また、口金への付着物の発生量が非常に少なく、優れた成形性を有するポリエステルを提供することが出来、その結果、色相に優れ、深みのある染色性を有するポリエステル繊維を提供することができる。これらの事項における工業的な意義は大きい。 According to the present invention, it is possible to eliminate the deterioration of hue, which is a drawback of polyesters that do not use Sb or Ge catalyst, while maintaining the excellent properties of polyesters. Further, it is possible to provide a polyester having excellent moldability with a very small amount of deposits on the die, and as a result, to provide a polyester fiber having excellent hue and deep dyeability. it can. The industrial significance of these matters is great.
Claims (7)
更に平均粒径が０．０１〜０．５μｍの範囲であってかつ粒径が０．５μｍを超える粒子の頻度分率が２０質量％以下である不活性粒子を０．１〜５質量％含有し、当該不活性粒子が炭酸カルシウム、第三リン酸カルシウム、珪酸カルシウム、酸化ケイ素、酸化アルミニウム、シリコーンパウダー、カオリナイト、硫酸バリウム及び酸化チタンよりなる群から選ばれる少なくとも１つに該当するポリエステル組成物であって、該整色剤の濃度２０ｍｇ／Ｌのクロロホルム溶液について光路長１ｃｍにおいて波長３８０〜７８０ｎｍ領域の可視光吸収スペクトルを測定したとき、最大吸収波長が５４０〜６００ｎｍの範囲にあり、且つ該最大吸収波長における吸光度に対する下記各波長での吸光度の割合が下記数式（１）〜（４）のすべてを満たすポリエステル組成物。
Further, 0.1 to 5% by mass of inert particles having an average particle size in the range of 0.01 to 0.5 μm and a frequency fraction of particles having a particle size exceeding 0.5 μm is 20% by mass or less. And the inert particle is a polyester composition corresponding to at least one selected from the group consisting of calcium carbonate, tricalcium phosphate, calcium silicate, silicon oxide, aluminum oxide, silicone powder, kaolinite, barium sulfate and titanium oxide. When the visible light absorption spectrum in the wavelength range of 380 to 780 nm was measured for a chloroform solution having a concentration of 20 mg / L in the color adjusting agent at an optical path length of 1 cm, the maximum absorption wavelength was in the range of 540 to 600 nm, and the maximum The ratio of the absorbance at each wavelength below to the absorbance at the absorption wavelength satisfies all of the following formulas (1) to (4). Polyester composition.
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| JPH08199428A (en) * | 1995-01-17 | 1996-08-06 | Teijin Ltd | Production of titanium dioxide-containing polyester fiber |
| WO2000026301A1 (en) * | 1998-10-30 | 2000-05-11 | Asahi Kasei Kabushiki Kaisha | Polyester resin composition and fiber |
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