CN100467693C - Nonwoven fabric of polyester composite fiber - Google Patents
Nonwoven fabric of polyester composite fiber Download PDFInfo
- Publication number
- CN100467693C CN100467693C CN 200380108344 CN200380108344A CN100467693C CN 100467693 C CN100467693 C CN 100467693C CN 200380108344 CN200380108344 CN 200380108344 CN 200380108344 A CN200380108344 A CN 200380108344A CN 100467693 C CN100467693 C CN 100467693C
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- CN
- China
- Prior art keywords
- mentioned
- polyester
- nonwoven fabric
- fiber
- composition
- 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
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- 229920000728 polyester Polymers 0.000 title claims abstract description 159
- 239000000835 fiber Substances 0.000 title claims abstract description 150
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 40
- 239000000203 mixture Substances 0.000 claims abstract description 140
- -1 phosphorus compound Chemical class 0.000 claims abstract description 130
- 229920000642 polymer Polymers 0.000 claims abstract description 111
- 239000003054 catalyst Substances 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 64
- 239000011574 phosphorus Substances 0.000 claims abstract description 64
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 48
- 239000010936 titanium Substances 0.000 claims abstract description 35
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 116
- 239000004744 fabric Substances 0.000 claims description 59
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 58
- 238000006068 polycondensation reaction Methods 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 53
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 48
- 238000009941 weaving Methods 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 34
- 150000002148 esters Chemical class 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 24
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 150000008065 acid anhydrides Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 11
- 125000004437 phosphorous atom Chemical group 0.000 claims description 11
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 10
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 239000000806 elastomer Substances 0.000 claims description 7
- 230000002093 peripheral effect Effects 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 235000013305 food Nutrition 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 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 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical class OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- WVJGICATWRJGOQ-UHFFFAOYSA-N dioctyl benzene-1,2-dicarboxylate;ethane Chemical compound CC.CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC WVJGICATWRJGOQ-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 229920002635 polyurethane Polymers 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 claims description 3
- 238000007613 slurry method Methods 0.000 claims description 3
- 238000011282 treatment Methods 0.000 claims description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 abstract description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 3
- 239000004615 ingredient Substances 0.000 abstract 4
- 239000000047 product Substances 0.000 description 53
- 239000000243 solution Substances 0.000 description 51
- 238000012360 testing method Methods 0.000 description 18
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000003963 antioxidant agent Substances 0.000 description 8
- 235000006708 antioxidants Nutrition 0.000 description 8
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229920001707 polybutylene terephthalate Polymers 0.000 description 8
- 238000009987 spinning Methods 0.000 description 8
- 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 8
- 230000003078 antioxidant effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- 229920001634 Copolyester Polymers 0.000 description 5
- 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 5
- 150000002009 diols Chemical group 0.000 description 5
- 230000032050 esterification Effects 0.000 description 5
- 238000005886 esterification reaction Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 238000012856 packing Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002799 BoPET Polymers 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005041 Mylar™ Substances 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000000536 complexating effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 3
- 238000004383 yellowing Methods 0.000 description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920000305 Nylon 6,10 Polymers 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 244000269722 Thea sinensis Species 0.000 description 2
- 238000001467 acupuncture Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
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- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000007860 aryl ester derivatives Chemical class 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
- 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
- 235000013361 beverage Nutrition 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000000994 depressogenic effect Effects 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- GHLKSLMMWAKNBM-UHFFFAOYSA-N dodecane-1,12-diol Chemical compound OCCCCCCCCCCCCO GHLKSLMMWAKNBM-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
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- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 2
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- XUYJLQHKOGNDPB-UHFFFAOYSA-N phosphonoacetic acid Chemical compound OC(=O)CP(O)(O)=O XUYJLQHKOGNDPB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
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- 238000012545 processing Methods 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical class CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 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
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- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical class CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 206010067868 Skin mass Diseases 0.000 description 1
- 235000006468 Thea sinensis Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 1
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 235000020279 black tea Nutrition 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 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
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000009960 carding Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000010675 chips/crisps Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 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
- 238000012544 monitoring process Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000003605 opacifier Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 235000012771 pancakes Nutrition 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- NOJQSZZIXRYAFK-UHFFFAOYSA-N propane-1,2-diol;terephthalic acid Chemical compound CC(O)CO.OC(=O)C1=CC=C(C(O)=O)C=C1 NOJQSZZIXRYAFK-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 235000013616 tea Nutrition 0.000 description 1
- 150000003504 terephthalic acids Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Abstract
A nonwoven fabric of polyester composite fibers which has a satisfactory color tone (low value of b*). It is formed from short composite fibers obtained from a polyester polymer obtained with the following catalyst and a fusion-bondable polymer. The catalyst comprises: (1) a mixture of a phosphorus compound ingredient comprising a phosphorus compound represented by the formula (III) with a titanium compound ingredient comprising a titanium alkoxide represented by the following formula (I) and/or a product of the reaction of the titanium alkoxide with a carboxylic acid represented by the formula (II) or anhydride thereof; and/or (2) a product of the reaction of a phosphorus compound ingredient comprising a phosphorus compound represented by the formula (V) with a titanium compound ingredient comprising a titanium alkoxide (IV) represented by the formula (IV) and/or a product of the reaction of the titanium alkoxide with a carboxylic acid represented by the formula (III) or anhydride thereof.
Description
Technical field
The present invention relates to nonwoven fabric of polyester composite fiber.In more detail, the present invention relates to use and have good color and be in harmonious proportion the nonwoven fabric of polyester composite fiber that the mylar of excellent melt spinning makes.Nonwoven fabric of polyester composite fiber of the present invention can be used as the sheet material that contacts with food and drink, for example be used for filter cloth that the food such as material, black tea bag, tea bag, coffee filter cloth of packaging for foodstuff use, filtering lye cloth sheet, oil strain cloth sheet, kitchen rag, be used for reverse osmosis membrane the base material hygienic material, be used for the filter cloth of various beverages etc.
Background technology
Mylar, particularly polyethylene terephthalate, PEN, polytrimethylene terephthalate and polybutylene terephthalate (PBT) have excellent machinery, physics, chemical property, thereby be widely used in fiber, film and other molded item field, particularly known in the non-weaving cloth purposes, have excellent mechanical strength, DIMENSIONAL STABILITY and heat resistance, light resistance.
Such fiber polymer, for example polyethylene terephthalate can prepare by following method usually: the glycol ester and/or its oligomer that prepare common terephthalic acid (TPA), in the presence of the polycondensation catalyst, under the decompression heating condition, make its reaction then to the predetermined degree of polymerization.Other polyester, for example PEN, poly-naphthalenedicarboxylic acid propylene glycol ester, polybutylene terephthalate (PBT) etc. also can be by preparing with above-mentioned same method.
Generally known: this moment the gained polyester quality be subjected to a great extent the polycondensation catalyst kind about, the polycondensation catalyst of widely used polyethylene terephthalate is an antimonial.
But, when using antimonial, polyester is carried out the long-time continuous melt-spun, to adhere to around the spinneret orifice and pile up foreign matter (being designated hereinafter simply as the spinnerets foreign matter), bending phenomenon occurs for molten polymer flow (bending), this will become cause fluffing in the back operation such as spinning, stretching, the reason of problem such as fracture of wire or fibrous physical property are irregular.Particularly wish to solve the above-mentioned shortcoming of (must utilize fibrous physical property to greatest extent) filament fiber.
For fear of this problem, knownly can use titanium compounds such as four butanols titaniums, but this deterioration will make heat endurance variation, the fusion of resulting polymers the time is strong, thereby is difficult to obtain the high fiber of mechanical strength.And the yellowing of gained polyester own, there is the fiber tone finally make this problem that can not meet the demands.
For addressing these problems, people have proposed following method: use the catalyst (reference example such as patent documentation 1) of the product of titanium compound and trimellitic acid reaction formation as the preparation polyester; Use the catalyst (reference example such as patent documentation 2) of the product of titanium compound and phosphite reactions formation as the preparation polyester.These methods can improve the melting heat stability of polyester really to a certain extent, but its raising effect is not enough, still need the tone of gained mylar is improved.In addition, the somebody proposes to use the catalyst (reference example such as patent documentation 3) of the complex compound of titanium compound and phosphorus compound as the preparation polyester, though but use this method can improve melting heat stability to a certain extent, but its effect is insufficient, still needs the tone of gained polyester is improved.
Above-mentioned citing document is as described below.
[patent documentation 1]
Japanese Patent Publication 59-46258 communique
[patent documentation 2]
Japanese kokai publication sho 58-38722 communique
[patent documentation 3]
Japanese kokai publication hei 7-138354 communique
Summary of the invention
The object of the invention is to provide a kind of polyester complex fiber, non-weaving cloth that the quality homogeneity is high of containing, and wherein said polyester complex fiber is made by high-quality polyester polymers and heat fused polymer with good tone (high L value and hang down the b value).
Nonwoven fabric of polyester composite fiber of the present invention is to comprise by the non-weaving cloth of heat fused polymer with the compound short fiber of Thermoadhesive that becomes fine thermoplastic polymer to form, and it is characterized in that:
Above-mentioned heat fused polymer forms along the part of the longitudinally extending outer peripheral face of described compound short fiber, and the fine thermoplastic polymer of above-mentioned one-tenth forms the remainder of above-mentioned short fiber,
The fine thermoplastic polymer of above-mentioned one-tenth is selected from the polyester polymers that polycondensation forms in the presence of catalyst by the aromatic dicarboxylic acid ester,
Above-mentioned catalyst contains at least a material that is selected from following mixture (1) and product (2),
Above-mentioned is following compositions (A) and mixture (B) as mixture of catalysts (1): (A) at least a being selected from (a) and titanium compound composition (A) (b),
(a) alkoxytitanium shown in the following general formula (I),
[in the formula (I), R
1, R
2, R
3And R
4A kind of alkyl and phenyl groups that be selected from of independent respectively expression with 1-20 carbon atom, m represents the integer of 1-4, m represents 2,3 or at 4 o'clock, 2,3 or 4 R
2And R
3Can be identical or different respectively.]
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
[in the formula (II), n represents the integer of 2-4];
(B) contain the phosphorus compound composition (B) of phosphorus compound shown at least a following general formula (III),
[in the formula (III), R
5, R
6And R
7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents a kind of being selected from-CH
2-Ji and-group of CH (Y)-Ji (Y represents phenyl)],
The mM value of contained titanium elements is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the above-mentioned titanium compound composition (A)
Ti, the mM value of institute's phosphorus element-containing is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B)
P, the above-mentioned mixture of catalysts (1) that is used as is with M
TiAnd M
PSatisfying following relational expression (i) and combined amount (ii) uses:
1≤M
P/M
Ti≤15 (i)
10≤M
P+M
Ti≤100 (ii)；
Above-mentioned product (2) as catalyst is following compositions (C) and product (D): (C) contain at least a titanium compound composition (C) that is selected from following (c) and material (d),
(c) alkoxytitanium shown in the following general formula (IV),
[in the formula (IV), R
8, R
9, R
10And R
11Independent respectively expression has the alkyl of 1-20 carbon atom, and p represents the integer of 1-3, and p represents 2 or at 3 o'clock, 2 or 3 R
9And R
10Can be identical or different respectively]
(d) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (IV) and the above-mentioned general formula (II),
(D) contain the phosphorus compound composition (D) of phosphorus compound shown at least a following general formula (V),
[in the following formula (V), R
12Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom, and q represents 1 or 2 integer].
In the nonwoven fabric of polyester composite fiber of the present invention, for above-mentioned as mixture of catalysts (1) composition (A) and the composition (C) of above-mentioned product (2) as catalyst separately for, preferably alkoxytitanium (a) and alkoxytitanium (c) separately with the reaction mol ratio of the aromatic polycarboxylic acid of general formula (II) or its acid anhydrides in the 2:1-2:5 scope.
In the nonwoven fabric of polyester composite fiber of the present invention, above-mentioned as the reacting dose ratio of the composition (D) in the product (2) of catalyst with composition (C), be converted into the ratio (P/Ti) of the molar weight of contained titanium atom in the molar weight of contained phosphorus atoms in the composition (D) and the composition (C), preferably in the 1:1-3:1 scope.
In the nonwoven fabric of polyester composite fiber of the present invention, the phosphorus compound of used general formula (V) is selected from phosphoric acid one Arrcostab in the preferred above-mentioned product (2).
In the nonwoven fabric of polyester composite fiber of the present invention, preferred above-mentioned aromatic dicarboxylic acid ester is the ester that the ester exchange reaction by the dialkyl of aromatic dicarboxylic acid and alkylene glycol makes.
In the nonwoven fabric of polyester composite fiber of the present invention, preferred above-mentioned aromatic dicarboxylic acid is selected from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid and biphenoxyl ethane dioctyl phthalate, above-mentioned alkylene glycol is selected from ethylene glycol, butanediol, trimethylene glycol, 1, ammediol, neopentyl glycol, 1,6-hexylene glycol and 1, the 12-dodecanediol.
In the nonwoven fabric of polyester composite fiber of the present invention, preferred above-mentioned polyester polymers is at L
*a
*b
*L in the color specification system (JIS Z 8729)
*Value is 77-85, b
*Value is 2-5.
Nonwoven fabric of polyester composite fiber of the present invention, above-mentioned compound short fiber can be the fiber with parallel type structure.
In the nonwoven fabric of polyester composite fiber of the present invention, above-mentioned compound short fiber can be the fiber with concentric or eccentric skin-core structure, its concentric or eccentric core is formed by the fine thermoplastic polymer of above-mentioned one-tenth, and concentric or eccentric skin zone is formed by the heat fused polymer.
In the nonwoven fabric of polyester composite fiber of the present invention, preferred above-mentioned heat fused polymer is with above-mentioned to become the mass ratio of fine thermoplastic polymer be 30:70-70:30.
In the nonwoven fabric of polyester composite fiber of the present invention, preferred above-mentioned heat fused polymer is selected from polyurethane series elastomer, polyester based elastomers, inelastic polyester homopolymer and copolymer, polyolefin homopolymers and copolymer, vinol series polymer.
In the nonwoven fabric of polyester composite fiber of the present invention, the compound short fiber of preferred above-mentioned polyester has the single fiber fiber number of 0.01-10dtex and the fibre length of 5-100mm.
Nonwoven fabric of polyester composite fiber of the present invention be by above-mentioned polyester complex fiber by combing method, copy the cloth that slurry method, air lay method formed and carried out Overheating Treatment.
Nonwoven fabric of polyester composite fiber of the present invention can be to have carried out the cloth that interlacing is handled before above-mentioned heat treatment.
The ratio that contains of the compound short fiber of contained above-mentioned polyester is the 25-100% quality in the preferred nonwoven fabric of polyester composite fiber of the present invention.
Preferably with nonwoven fabric of polyester composite fiber of the present invention with the purposes of Food Contact in use.
The best mode that carries out an invention
Nonwoven fabric of polyester composite fiber of the present invention is to contain by the non-weaving cloth of heat fused polymer with the compound short fiber of Thermoadhesive that becomes fine thermoplastic polymer to form.
Above-mentioned heat fused polymer forms along the part of the longitudinally extending outer peripheral face of described compound short fiber, and the fine thermoplastic polymer of above-mentioned one-tenth forms the remainder of above-mentioned compound short fiber,
The fine thermoplastic polymer of above-mentioned one-tenth is selected from the polyester polymers that polycondensation forms in the presence of catalyst by the aromatic dicarboxylic acid ester.
The above-mentioned catalyst that is used to prepare polyester polymers contains at least a material that is selected from mixture (1) and product (2), as mixture of catalysts (1) is the mixture of following titanium compound composition (A) and phosphorus compound (B), and above-mentioned product (2) is the product of following titanium compound composition (C) and phosphorus compound composition (D).
The above-mentioned titanium compound composition (A) that is used as in the mixture of catalysts (1) contains at least a being selected from (a) and composition (b),
(a) alkoxytitanium shown in the following general formula (I),
[in the formula (I), R
1, R
2, R
3And R
4A kind of alkyl and phenyl groups that be selected from of independent respectively expression with individual, preferred 1-6 the carbon atom of 1-20, m represents the integer of 1-4, preferred 2-4, when m represents 2,3 or 4 integer, 2,3 or 4 R
2And R
3Can be identical or different respectively.]
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
[in the formula (II), n represents the integer of 2-4, preferred 3-4].
Contain phosphorus compound shown at least a following general formula (III) as the phosphorus compound composition (B) in the mixture (1) of polycondensation catalyst,
[in the formula (III), R
5, R
6And R
7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents a kind of being selected from-CH
2-Ji and-CH
2(Y) group of (Y represents phenyl)].
The above-mentioned titanium compound composition (C) that is used as in the product (2) of polycondensation catalyst contains at least a following (c) and the composition (d) of being selected from,
(c) alkoxytitanium shown in the following general formula (IV),
[in the formula (IV), R
8, R
9, R
10And R
11Independent respectively expression has the alkyl of 1-20, preferred 1-6 carbon atom, and p represents 1-3, preferred 1 or 2 integer, and p represents 2 or at 3 o'clock, 2 or 3 R
9And R
10Can be identical or different respectively];
(d) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (IV) and the above-mentioned general formula (II).
Contain phosphorus compound shown at least a following general formula (V) as the phosphorus compound composition (D) in the product (2) of polycondensation catalyst,
[in the following formula (V), R
12Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom, and q represents 1 or 2 integer].
The mixture (1) that uses above-mentioned titanium compound composition (A) and above-mentioned phosphorus compound composition (B) is during as polycondensation catalyst, dissolubility and the compatibility height of product (b) in polyester polymers as aromatic polycarboxylic acid shown in alkoxytitanium (a) shown in the general formula (I) of titanium compound composition (A) and this alkoxytitanium (a) and the general formula (II) or its acid anhydrides, even therefore residual in the polyester polymers that obtains by polycondensation have a titanium compound composition (A), when its melt spinning, foreign matter can not take place the spinning spinneret periphery yet piles up, thereby can be with the good polyester filament of high spinning efficient spinning quality.
As used among the present invention, preferably use tetraisopropoxy titanium, four titanium propanolates, four titanium n-butoxide, purity titanium tetraethoxide, four phenoxide titaniums, three metatitanic acids, eight Arrcostabs and two metatitanic acids, six Arrcostabs etc. as alkoxytitanium (a) shown in the used general formula (I) of the titanium compound composition (A) of polycondensation catalyst.
As used among the present invention as alkoxytitanium (c) shown in the used general formula (IV) of the titanium compound composition (C) of polycondensation catalyst, four alkoxytitaniums such as preferred use four titanium butoxide, tetraisopropoxy titanium, four titanium propanolates and purity titanium tetraethoxide, and alkyl titanates such as three metatitanic acids, eight Arrcostabs and two metatitanic acids, six Arrcostabs etc.Preferred especially the use and four high titanium butoxide of phosphorus compound composition reactivity.
Aromatic polycarboxylic acid or its acid anhydrides shown in the general formula (II) of reaction are preferably selected from phthalic acid, trimellitic acid, benzene-1,2,3-tricarboxylic acid, pyromellitic acid and their acid anhydrides with alkoxytitanium (a) or (c).When particularly using trimellitic anhydride, the product that obtains (b) demonstrates high-affinity to polyester polymers, can effectively prevent above-mentioned foreign matter accumulation.
Make above-mentioned alkoxytitanium (a) or (c) and when aromatic polycarboxylic acid shown in the general formula (II) or its anhydride reaction, for example preferably aromatic polycarboxylic acid or its acid anhydrides are dissolved in the solvent, drip alkoxytitanium (a) or (c) in this mixed liquor, heating is at least 30 minutes under 0-200 ℃ temperature.Above-mentioned solvent preferably as required from ethanol, ethylene glycol, 1, select in 4-butanediol, benzene and the dimethylbenzene by ammediol, 1.
Here, to alkoxytitanium (a) or (c) and the reaction mol ratio of aromatic polycarboxylic acid shown in the general formula (II) or its acid anhydrides be not particularly limited, if the ratio of alkoxytitanium is too high, then the situation of tone variation, softening point reduction can appear in the gained polyester, otherwise if the ratio of alkoxytitanium is low excessively, then polycondensation reaction is difficult to carry out.Therefore, preferred alkoxytitanium (a) or (c) and the reaction mol ratio of aromatic polycarboxylic acid shown in the general formula (II) or its acid anhydrides be in (2:1)-(2:5) scope.
The product (b) that is obtained by this reaction or (d) can like this directly use also can be used it with the be recrystallized back of purifying such as acetone, methyl alcohol and/or ethyl acetate.
Among the present invention, be preferably selected from the ester class of phosphonate derivative, for example dimethyl ester, diethylester class, dipropyl class and the dibutyl ester class etc. of phosphonate derivatives such as methoxycarbonyl group methane phosphonic acid, carbethoxyl group methane phosphonic acid, the third oxygen carbonyl methane phosphonic acid, butoxy carbonyl methane phosphonic acid, methoxycarbonyl group phenyl methane phosphonic acid, carbethoxy phenyl methane phosphonic acid, the third oxygen carbonyl phenyl methane phosphonic acid and butoxy carbonyl phenyl methane phosphonic acid as phosphorus compound (phosphonate ester) shown in the used general formula (III) of the phosphorus compound composition (B) in the mixture (1) of polycondensation catalyst.
When the phosphorus compound composition (B) that will contain the phosphorus compound (phosphonate compound) of general formula (III) is used for aromatic dicarboxylic acid ester's polycondensation reaction, compare with the phosphorus compound that is used as reaction stabilizer usually, the reaction of itself and titanium compound composition (A) is carried out relatively gentlely, thereby the catalyst activity longer duration of the titanium compound composition (A) in the polycondensation process, thereby can reduce the amount ratio of titanium compound composition (A) with respect to the amount of the aromatic dicarboxylic acid ester in the polycondensation reaction system.And in the polycondensation reaction system that comprises the phosphorus compound composition (B) that contains phosphorus compound shown in the general formula (III),, can not reduce the heat endurance of gained polyester polymers, and can not make its tone variation even add a large amount of stabilizing agents yet yet.
Among the present invention, when using mixture (1), if the ratio (%) of the mM value of contained titanium elements and above-mentioned aromatic dicarboxylic acid ester's mole numerical value is M in the above-mentioned titanium compound composition (A) as polycondensation catalyst
Ti, the mM value of institute's phosphorus element-containing is M with the ratio (%) of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B)
P, then with M
TiAnd M
PSatisfy following relational expression (i) and combined amount (ii) and use mixture (1):
1≤M
P/M
Ti≤15 (i)
10≤M
P+M
Ti≤100 (ii)。
Compare M
p/ M
TiBe more than 1 below 15, be preferably more than 2 below 10.If than M
p/ M
TiLess than 1, then the form and aspect of gained polyester polymers may yellowing, and if this ratio surpasses 15, then the polycondensation reaction of the polycondensation catalyst that constitutes thus is abundant inadequately, is difficult to obtain the target polyesters polymer.The M that compares of the present invention
p/ M
TiScope narrower than traditional Ti-P series catalysts, but by setting such scope for, can obtain with traditional Ti-P series catalysts the excellent effect that can't obtain.
(M
Ti+ M
P) and value be more than 10 below 100, be preferably more than 20 below 70.(M
Ti+ M
P) value was less than 10 o'clock, the fibre forming property of gained polyester polymers is not enough, and the production efficiency in the melt-spun operation does not reach requirement, and the performance of gained fiber is good inadequately.And if (M
Ti+ M
P) value is above 100, when then the gained polyester polymers being carried out melt-spun, spinnerets will be piled up foreign matter on every side, though be small pile-up.Usually preferred M
TiValue be 2-15, more preferably 3-10.
Among the present invention, when using above-mentioned product (2) as polycondensation catalyst, the phosphorus compound of the general formula (V) that phosphorus compound composition (D) is used for example can be following compound: phosphoric acid one alkyl esters, for example oneself ester of phosphoric acid one positive butyl ester, phosphoric acid, phosphoric acid one (dodecyl) ester, phosphoric acid one lauryl and phosphoric acid one oil base ester etc.; Phosphoric acid one aryl ester class, for example phosphoric acid one phenylester, phosphoric acid one benzyl ester, phosphoric acid one (4-ethylphenyl) ester, phosphoric acid one biphenyl ester, phosphoric acid one naphthyl ester, phosphoric acid one anthryl ester etc.; Phosphate dialkyl ester class, for example diethyl phosphate, di(2-ethylhexyl)phosphate propyl ester, dibutylphosphoric acid ester, di(2-ethylhexyl)phosphate lauryl and di(2-ethylhexyl)phosphate oil base ester etc.; And di(2-ethylhexyl)phosphate aryl ester class, for example di(2-ethylhexyl)phosphate phenylester etc.Wherein, preferably using q in the above-mentioned formula (V) is 1 o'clock phosphoric acid one Arrcostab or phosphoric acid one aryl ester.
Used phosphorus compound composition (D) can be the mixture of the phosphorus compound of two or more general formulas (V) among the present invention, and for example the mixture of the mixture of phosphoric acid one Arrcostab and phosphate dialkyl ester, phosphoric acid one phenyl ester and diphenyl phosphate is preferred combination.Be benchmark with the mixture gross mass especially preferably, phosphoric acid one Arrcostab accounts for more than 50% in the mixture, particularly accounts for the composition more than 90%.
The method for preparing the product of above-mentioned titanium compound composition (C) and above-mentioned phosphorus compound composition (D) for example can be with two kinds of compositions (C) and (D) mixing, heats to be prepared in glycol.That is, if the glycol solution that contains titanium compound composition (C) and phosphorus compound composition (D) is heated, then glycol solution will become muddy, and the product of two kinds of compositions (C), (D) is separated out as precipitation.Can collect this precipitation, as the catalyst that is used to prepare polyester polymers.
As can be used for preparing the glycol of catalyst, the preferred use and the identical composition of diol component that constitutes the polyester polymers that makes with the gained catalyst with product (2).For example, when polyester polymers is polyethylene terephthalate, preferably make spent glycol; When polyester polymers is the poly terephthalic acid propylene glycol, preferably use 1, ammediol; When polyester polymers is polybutylene terephthalate (PBT), preferably use 1, the 4-butanediol.
Product (2) as polycondensation catalyst of the present invention can be prepared as follows: titanium compound composition (C) is mixed simultaneously with phosphorus compound composition (D) and glycol three, it is heated, can make.But because be to make titanium compound composition (C) and phosphorus compound composition (D) reaction by heating, the product that is insoluble to glycol is separated out as precipitation, carries out so preferred precipitation is separated out reaction homogeneous before.Therefore, in order effectively to obtain reaction precipitation, preferably by preparing titanium compound composition (C) and phosphorus compound composition (D) glycol solution separately in advance, the method with these solution mixing and heating is prepared then.
Composition (C) and reaction temperature (D) are preferably 50 ℃-200 ℃, and the reaction time was preferably 1 minute-4 hours.If it is low that reaction temperature is spent, then reaction becomes insufficient, perhaps reacts required time and increases, thereby can't effectively obtain reaction precipitation by the reaction of homogeneous.
About the titanium compound composition (C) that adds thermal response in the glycol blending ratio with phosphorus compound composition (D), the molar ratio of phosphorus atoms and titanium atom is preferably 1.0-3.0, more preferably 1.5-2.5.If blending ratio is in above-mentioned scope, phosphorus compound composition (D) and titanium compound composition (C) complete reaction roughly then, there is not the not reactant of complete reaction, even thereby directly use this product, the tone of gained polyester polymers also is good, and have excessive unreacted phosphorus compound (V) hardly, so can not hinder the polyester reactivity, the production efficiency height.
The polycondensation catalyst that uses among the present invention preferably contains compound shown in the following general formula (VI) with product (2).
(the R in the formula (VI)
13And R
14Independently represent a kind of following group that is selected from separately: come from the R in the general formula (IV) of representing the used alkoxytitanium of above-mentioned titanium compound composition (C)
8, R
9, R
10, R
11R with the general formula (V) of representing the used phosphorus compound of above-mentioned phosphorus compound composition (D)
12, and have the alkyl of 1-10 carbon atom; Perhaps from the R of above-mentioned phosphorus compound (V)
12, and have the aryl of 6-12 carbon atom.)
The product of titanium compound shown in the formula (VI) and phosphorus compound (V) has high catalyst activity, and has good color tone (low b value) with the polyester polymers that it makes, the content of acetaldehyde, kish and cyclic trimer is enough low on reality is used, and has sufficient polymer performance in actual applications.The content of product in polycondensation catalyst is more than 50% quality shown in the preferred formula (VI), more preferably more than 70% quality.
In the presence of above-mentioned product (2) during the polycondensation aromatic dicarboxylic acid ester, needn't from the glycol solution that contains product precipitation (2) that as above obtains, reaction product isolated precipitate (2) and glycol, but can be with it directly as the catalyst for preparing polyester polymers.Also can from the glycol solution that contains product precipitation (2), isolate sediment by means and methodses such as centrifugation processing or filtrations, then with this product precipitation (2) with for example recrystallization agent such as acetone, methyl alcohol and/or the water purification that is recrystallized, then this purifying thing is used as polycondensation catalyst.The chemical constitution that is used as the product (2) of polycondensation catalyst can be confirmed by the metal quantitative analysis of solid NMR and XMA.
Polyester polymers used among the present invention can obtain by polycondensation aromatic dicarboxylic acid ester in the presence of catalyst, and wherein said catalyst contains above-mentioned titanium compound composition (A) and phosphorus compound (phosphonate compound) mixture (1) (B) and/or the product (2) of titanium compound composition (C) and phosphorus compound composition (D).Among the present invention, preferred aromatic dicarboxylic acid ester is the diester that aromatic dicarboxylic acid composition and aliphatic dihydric alcohol composition form.
Here said aromatic dicarboxylic acid composition preferably is main component with the terephthalic acid (TPA).More particularly, be benchmark with the content of aromatic dicarboxylic acid composition, preferred terephthalic acid (TPA) accounts for more than 70% mole.Here, the preferred aromatic dicarboxylic acids beyond the terephthalic acid (TPA) for example has phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid, diphenyl dicarboxylic acid, biphenoxyl ethane dioctyl phthalate etc.
The preferred aliphatic series glycol component contains alkylene glycol, for example can make spent glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexylene glycol and 1,12-dodecanediol, preferred especially ethylene glycol.
Among the present invention, the preferred polyester polymer is to be the polyester polymers of main repetitive with terephthalic acid (TPA) and the formed ethylene glycol terephthalate of ethylene glycol.Here, with in the polyester all the amount of repetitives be benchmark, preferred above-mentioned ethylene glycol terephthalate repetitive accounts for more than 70% mole.
Used polyester polymers can be the copolyester that is formed by sour composition that constitutes polyester or diol component copolymerization among the present invention.
As the co-poly carboxylic acid composition, except that can using above-mentioned aromatic dicarboxylic acid, can also use aliphatic dicarboxylic acids such as adipic acid, decanedioic acid, azelaic acid, decane dicarboxylic acid; Cyclohexyl dicarboxylic acid waits difunctionality carboxylic acid composition such as ester ring type dicarboxylic acids or its to become ester derivant as raw material.The copolymerization diol component can also use ester ring type glycol such as cyclohexanedimethanol except that can using above-mentioned aliphatic diol; Bis-phenol, hydroquinones, 2, aromatic diols such as 2-two (4-beta-hydroxy ethoxyl phenenyl) propane class etc. are as raw material.
And, also can use the copolyester polymer that obtains as the copolymer composition copolymerization with multi-functional compounds such as trimesic acid, trimethylolethane, trimethylolpropane, Pehanorm, pentaerythrites.
Above-mentioned polyester polymers and copolyester polymer can be used alone, and also can be used in combination of two or more.
Among the present invention, polyester polymers preferably uses the aromatic dicarboxylic acid ester's of above-mentioned aromatic dicarboxylic acid and aliphatic diol formation polycondensation product.This aromatic dicarboxylic acid ester can also can prepare by the dialkyl of aromatic dicarboxylic acid and the ester exchange reaction of aliphatic diol by two esterification prepared in reaction of aromatic dicarboxylic acid and aliphatic diol.Just, employing is the method for raw material via ester exchange reaction with the dialkyl of aromatic dicarboxylic acid, with be that the method that raw material carries out two esterifications reactions is compared with the aromatic dicarboxylic acid, have less this benefit of dispersing of the phosphorus compound that adds as the phosphorus stabilizer agent in the polycondensation reaction.
And, preferably before beginning, ester exchange reaction adds the titanium compound composition (A) of part or all amount or (C), it is used as ester exchange reaction and two catalyst for reaction of polycondensation reaction.Do like this, can reduce the titanium compound content in the final gained polyester.For example the situation of polyethylene terephthalate is carried out more specific description, preferably carry out in the presence of titanium compound composition (A) based on the dialkyl of the aromatic dicarboxylic acid of terephthalic acid (TPA) and the ester exchange reaction of ethylene glycol, wherein said titanium compound composition (A) contains at least a composition that is selected from the product (b) of aromatic polycarboxylic acid shown in alkoxytitanium shown in alkoxytitanium (a) shown in the above-mentioned general formula (I), the above-mentioned general formula (I) and the above-mentioned general formula (II) or its acid anhydrides.In the reactant mixture of the diester that contains aromatic dicarboxylic acid and ethylene glycol that obtains by this ester exchange reaction, further add phosphorus compound (phosphonate compound) composition (B) shown in the above-mentioned general formula (III), perhaps add the product of titanium compound composition (C) and above-mentioned phosphorus compound composition (D), in the presence of these compositions, carry out polycondensation.
When carrying out above-mentioned ester exchange reaction, usually under normal pressure, implement, if but depress enforcement in adding of 0.05-0.20 MPa, then can further promote the reaction that the catalyst action by titanium compound composition (A) carries out, and the accessory substance diethylene glycol (DEG) is heat release in a large number not, thereby the characteristics such as heat endurance of gained polyester polymers can be better.The temperature of ester exchange reaction is preferably 160-260 ℃.
Among the present invention, when aromatic dicarboxylic acid is terephthalic acid (TPA), can use terephthalic acid (TPA) and dimethyl terephthalate (DMT) initiation material as polyester.In this case, can use the polyalkylene terephthalates diol ester is carried out depolymerization and recovery dimethyl terephthalate (DMT) that obtains or the recovery terephthalic acid (TPA) that its hydrolysis is obtained.In this case, consider recycled polyesters such as the PET bottle that preferred especially use is reclaimed, fiber product, polyester film product from the resources effective utilization.
Polycondensation reaction can be carried out with single groove, also can carry out successively in a plurality of grooves.Like this, the polyester that obtains in the condensation polymerization step is extruded into wire with molten condition usually, with its cooling, granulate then (cutting into the section shape).
The polyester polymers that obtains in the above-mentioned condensation polymerization step further can be supplied to solid phase polycondensation as required.
This solid phase polycondensation step comprises a step at least, under the pressure condition of 190-230 ℃ temperature, 1kPa-200kPa, carries out under inert atmospheres such as nitrogen, argon gas, carbon dioxide.
As required, make the granular polyester made via such solid phase polycondensation step and water, steam, contain the inert gas of steam, the air etc. that contains steam contacts, and implements water treatment, makes catalysqt deactivation contained in the section thus.
Comprise as mentioned above esterif iotacation step and condensation polymerization step polyester manufacture technology can with in batches, semicontinuous, continuous any form carries out.
The inherent viscosity of the used polyester polymers of the present invention that makes like this is preferably 0.40-0.80, and 0.45-0.75 more preferably is preferably the scope of 0.50-0.70 especially.If inherent viscosity is less than 0.40, then the intensity of gained polyester fiber is not enough sometimes.And inherent viscosity surpasses 0.80, then needs the inherent viscosity of excessive raising raw polymer, and this is uneconomical.
Polyester polymers used among the present invention can contain minor amounts of additives as required, for example antioxidant, ultra-violet absorber, fire retardant, fluorescent whitening agent, delustering agent, positive toner, defoamer, antistatic additive, antiseptic, light stabilizer, heat stabilizer, opacifier, especially preferably add titanium dioxide as delustering agent, add antioxidant as stabilizing agent.
Preferred above-mentioned titanium dioxide has the average grain diameter of 0.01-2 μ m, and preferably its content in polyester polymers is the 0.01-10% quality.
In addition, the content of contained titanium from above-mentioned catalyst in the polyester polymers does not comprise as delustering agent and adds titanium in the titanium dioxide of coming in.
When the titanium dioxide that contains in the polyester polymers as delustering agent, can only remove TITANIUM DIOXIDE DELUSTRANT from the polyester polymers test portion that is used for measuring by following operation: this polyester polymers test portion is dissolved in the hexafluoroisopropanol, this solution is carried out centrifugation, make titanium dioxide granule precipitation separation from above-mentioned solution, by decanting process separated and collected supernatant, the solvent in this recovery component is removed in evaporation, makes and treats test agent.
Above-mentioned antioxidant preferably uses the antioxidant of Hinered phenols.The addition of antioxidant is preferably below 1% quality, more preferably the 0.005-0.5% quality.If this addition surpasses 1% quality, then its effect is saturated, and the reason of formation scum silica frost will become melt-spun the time.Can be used in combination hindered phenol anti-oxidants and thioether class antioxidant.
The method that above-mentioned antioxidant is added in the polyester is not particularly limited, can adds in any stage between ester exchange reaction begins to finish to polycondensation reaction.
Polyester polymers used among the present invention has good color tone (L because of used catalyst
*Value and b
*Value).That is, preferably this polyester polymers at L
*a
*b
*L in the color specification system (JIS Z 8729)
*Value is 77-85, b
*Value is 2-5.
In constituting the compound short fiber of Thermoadhesive of non-weaving cloth of the present invention, can be with above-mentioned polyester polymers with making fine thermoplastic polymer composition, also can the while used as the heat fused component of polymer.
In the compound short fiber of above-mentioned Thermoadhesive, above-mentioned heat fused component of polymer forms along the part of the longitudinally extending outer peripheral face of this compound short fiber, and above-mentioned polyester polymers forms the remainder of above-mentioned compound short fiber.That is, in the compound short fiber of the used Thermoadhesive of the present invention, the heat adhesiveness polymer forms at least a portion of the outer peripheral face of compound short fiber, and the part of this outer peripheral face is vertically extended continuously along compound short fiber.That is to say that in the above-mentioned compound short fiber of non-weaving cloth, its heat fused component of polymer is at its infall composition bonded to one another with compound short fiber.
For the used compound short fiber of the present invention, the mass ratio that contains of wherein contained Thermoadhesive component of polymer and polyester polymers composition is preferably 30:70-70:30, more preferably 40:60-60:40.
In the used compound short fiber of the present invention, heat fused component of polymer and polyester polymers composition can be combined into the parallel type structure, perhaps can be combined into concentric or eccentric skin-core structure.When being concentric or eccentric skin-core structure, core is formed by polyester polymers usually, and skin zone is made of the heat fused polymer.As required, in the skin-core structure of off-centre, eccentric core can be formed by the heat fused polymer, and its part exposes in the outside of part short fiber outer peripheral face, and the skin zone of off-centre can be formed by polyester polymers.In parallel type and the eccentric sheath core pattern short fiber, the heat-shrinkable difference of the part that part that forms according to the heat fused polymer and polyester polymers form, fiber will show screw type and curl, thereby be the preferred short fiber that is used to form non-weaving cloth.To the cross sectional shape of above-mentioned compound short fiber without limits, can be common circle, also can be other abnormity (triangle, polygonal, pancakes etc.), these cross sectional shapes can be hollow shape or non-hollow (hollow) shape.
Used heat fused polymer preferably contains more than one polyurethane series elastomers, polyester based elastomers, inelastic polyester based polymer and copolymer thereof, polyolefin polymer and copolymer, vinol series polymer etc. in the compound short fiber of the present invention.Wherein, above-mentioned polyester based elastomers or inelastic polyester based polymer or its copolymer of preferred especially use.According to the melt temperature of polyester polymers, preferably these materials have the melt temperature that is low to moderate 50-200 ℃, and preferably its melt temperature scope is 50-200 ℃.
The copolyester based polymer can use by multiple and be selected from following compound and add copolyesters that forms after the oxyacid classes such as P-hydroxybenzoic acid etc. as required, and described alternative compound is: aliphatic series or ester ring type glycols such as ester ring type dicarboxylic acids such as aromatic dicarboxylic acid class such as aliphatic dicarboxylic acids such as adipic acid, decanedioic acid, phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid and/or hexahydroterephthalic acid, hexahydro M-phthalic acid and diethylene glycol (DEG), polyethylene glycol, propylene glycol, terephthalyl alcohol.For example, preferably in the combination of terephthalic acid (TPA) and ethylene glycol, add M-phthalic acid and 1, the polyester that the copolymerization of 6-hexylene glycol forms.
The said polyolefins polymer can be for example low density polyethylene (LDPE), high density polyethylene (HDPE), polypropylene etc.
Contained polyester polymers is preferably selected from polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate (PBT) and poly terephthalic acid 1, ammediol ester etc. in the above-mentioned compound short fiber.
Polyester polymers can be a kind of merely, also can be the mixture of two or more polyester polymers, can mix component of polymer not of the same race with the combined amount of not damaging polyester polymers characteristic degree as required in the polyester polymers composition.Component of polymer not of the same race can be selected from copolymer such as above-mentioned aliphatic dicarboxylic acid and become to grade.
Can adopt any method of traditional formation and manufacturing composite fibre to make the compound short fiber of the used Thermoadhesive of the present invention.
When above-mentioned Thermoadhesive composite polyester fiber was cut into short fiber, preferred shearing length was in the 5-100mm scope, is preferably 15-95mm especially.The performance that compound short fiber with the fibre length in this scope, its cardability and gained short fiber form non-weaving cloth is all excellent especially.
After non-weaving cloth of the present invention can form sheet short fiber aggregate by following method, it is carried out interlacing/heat treatment, structure is fixed and make, the method for described formation sheet short fiber aggregate has: will have than the short fiber of long fiber length and open fine dry process (combing method) of mixing with the roller with card clothing; The short fiber that will have than staple length is scattered in the water, copies the damp process of getting on the wire netting (copying the slurry method); To have than the short fiber of staple length and send into perforated (bowl) cylinder, it be disperseed shape air lay method into the net (being also referred to as air-laid method, pulp dry method) by air.
The order of non-weaving cloth of the present invention is paid and is preferably 10-500g/m
2, 20-300g/m more preferably
2If order is paid less than 10g/m
2, then production uniform fibers net will become very difficult continuously, and surpass 500g/m
2The time, the rigidity of non-weaving cloth is strong excessively, is unsuitable for actual use.
Non-weaving cloth of the present invention can also contain short fiber not of the same race as required except that the compound short fiber of above-mentioned Thermoadhesive.In this case, the ratio that contains of the compound short fiber of Thermoadhesive contained in the non-weaving cloth of the present invention is not particularly limited, but performance and effect in order to bring into play non-weaving cloth, the preferred mass ratio is more than 25%, more preferably more than 50%.
The fibre bag not of the same race that can be included in the non-weaving cloth of the present invention is drawn together the fiber that is applicable to common dry type non-weaving cloth, for example inorfils such as synthetic fiber, carbon fiber such as semisynthetic fibre such as regenerated fibers such as natural fabric, artificial fibre, acetate such as cotton and PVA fiber, polyamide fiber, nylon fiber, aromatic polyamide fibre, Dralon, composite fibre of being made of the different multiple polymers of fusing point etc.
In the non-weaving cloth of the present invention, the fixing means that constitutes short fiber is fit to adopt following method: make fiber complexing each other (needle point method), make fiber complexing each other (water acupuncture manipulation), carry out bondingly (エ ア-ス Le-Fa), carrying out complexing and suppressing by hot-rolling etc. by contraction with binder fiber by High-Pressure Water by acupuncture.
The fiber number of the contained compound short fiber of above-mentioned Thermoadhesive is preferably 0.01dtex-10dtex in the non-weaving cloth of the present invention, more preferably 0.1dtex-7dtex.If its fiber number is less than 0.01dtex, it is poor then to open fibre, so the decline of the speed of production line, and production efficiency is not high enough, and if surpass 10dtex, then be difficult to obtain uniform net, and/or the gained net is too upright and outspoken.
Can make the used compound short fiber of non-weaving cloth of the present invention take place to curl, it is curled.Be generally and obtained bulk non-weaving cloth, preferably made it have that zigzag machine crimp or screw type are three-dimensional curls.Crispation number is preferably 8-20/25mm, and crimp percent is preferably in the 6-18% scope.When needs obtain having highdensity non-weaving cloth, the preferred straight short fiber that does not curl that uses.
The thickness of non-weaving cloth of the present invention is preferably 0.05mm-10mm, more preferably 0.2mm-5mm.If thickness is less than 0.05mm, then the rigidity of gained non-weaving cloth and elasticity are all not enough, and if surpass 10mm, then are difficult to use.
The Clark method rigidity of non-weaving cloth of the present invention is preferably 0.5cm-10cm, more preferably 2-7cm.Rigidity is less than 0.5cm, and then the independence of gained non-weaving cloth is not enough, and is then too upright and outspoken if surpass 10cm, flexibility deficiency during actual the use.
Embodiment
Further the present invention is carried out more specific description below, but scope of the present invention is not limited to these embodiment by embodiment.In addition, measure the layer of the attachment that produces on inherent viscosity, tone, tenor and the spinning head by following method.
(1) inherent viscosity:
35 ℃ of viscosity of measuring 35 ℃ of o-chlorphenol solution of polyester polymers, with the inherent viscosity of this value as polyester polymers.
(2) tone (look L
*Value and look b
*Value):
With the fusion 10 minutes under 290 ℃, vacuum of polyester polymers test portion, it is shaped to the sheet of thickness 3.0 ± 1.0mm on aluminium sheet, quenching in frozen water immediately.The gained sheet 160 ℃ of drying crystalline processing of carrying out 1 hour, is placed on this test portion the white standard sheet that is used to adjust colour difference meter then, measures the look L on sheet surface with the Hunter colour difference meter CR-200 of Minolta K.K company manufacturing
*Value and b
*Value.L
*Value representation brightness, the big more then brightness of this value is high more, b
*The value of value is big more, and the degree of expression yellowing is big more.
(3) tenor:
Titanium atom concentration in the catalyst system and the following mensuration of phosphorus atoms concentration: under the situation of catalyst solution, directly install among the liquid Xiao Chi, in polyester polymers, contain under the situation of catalyst, sample heating and melting on aluminium sheet of polyester polymers will be waited to try, by the compression stamping machine it is pressed into the molded item with plane then, with the tenor of fluorescent X-ray determinator (3270 types that Liue electrical machinery Industrial Co., Ltd makes) each sample of quantitative analysis.The then following mensuration of titanium, phosphorus atoms concentration of catalyst is separated out in reaction: dried sample is fixed on electronic scanner microscope (SEM, Hitachi's instrumentation machine is made, Service S570 type), (XMA, hole field EMAX-7000) carries out quantitative analysis by coupled energy dispersion type X-ray microanalyzer.
(4) diethylene glycol (DEG) (DEG) amount:
With the sample of hydrazine hydrate decomposing polyester polymer, this catabolite is supplied with gas chromatograph (Hitachi Co., Ltd makes, " 263-70 "), measure the content (% quality) of diethylene glycol (DEG).
(5) the foreign matter layer height that adheres on the spinning head:
Make section with polyester polymers, it 290 ℃ of fusions, from the spinning head ejection of 12 of aperture 0.15mm φ, hole count, is spun 2 days with 600 meters/minute spinning speeds, measure the foreign matter layer height that adheres on the ejiction opening outer rim of spinnerets.This height that adheres to the foreign matter layer is high more, and then the strand shape of Pen Chu polyester fondant flows easy more bending, and the mouldability of this polyester reduces.That is the height of the attachment layer that, produces on the spinnerets is the mouldability index of this polyester.
(6) strength and elongation of non-weaving cloth:
The non-weaving cloth test portion is supplied to constant speed elongation type cupping machine, measures its strength and elongation according to the method for JIS-P8113 record.
(7) quality discrepancy:
Standard deviation value representation quality discrepancy during with the n=30 of TENSILE STRENGTH.(this value is more little, and expression difference is more little, and quality is stable more).
Embodiment 1
The mixture of 100 parts by mass dimethyl terephthalate (DMT)s and the 70 parts by mass ethylene glycol of packing in the rustless steel container that can carry out compressive reaction is to wherein sneaking into 0.009 parts by mass tetra-n-butyl titanate.The gained reactant mixture was depressed in adding of 0.07MPa, from 140 ℃ be warming up to 240 ℃ on one side, carry out ester exchange reaction on one side, to wherein adding 0.04 parts by mass phosphonoacetic acid triethyl, terminated diester exchange reaction.
The gained product is moved into the polycondensation container, its temperature is warming up to 290 ℃, carry out polycondensation reaction under the high vacuum below the 26.67Pa, the preparation inherent viscosity is 0.60, diethylene glycol (DEG) content is 1.5%, fusing point is 254 ℃ polyester polymers (not containing delustering agent).
The gained polyester polymers is extruded the formation strip continuously from the discharge portion of reaction vessel, cooling, section, the granular section of making the about 3mm of length.The quality of gained polyethylene terephthalate is as shown in table 1.In addition, with catalyst same as described above, preparation contains terephthalic acid (TPA) and M-phthalic acid with the composite sour composition of 60/40 (% mole), ethylene glycol and 1, the 6-hexylene glycol is with the composite diol component of 85/15 (% mole), inherent viscosity is 0.36, softening point is 70 ℃ heat fused polyester copolymer (not containing delustering agent), with the above-mentioned the same section for preparing polyester copolymer.Above-mentioned two kinds of sections are supplied to the melt-spun device of making concentric sheath core pattern bicomponent filament yarn, and by stretching, cutting off operation, make the compound polyester fiber of core-skin (the core-skin mass ratio: 50/50, fiber number: 2.2dtex, fibre length: 5mm).The compound polyester fiber of core-skin that this skin zone is formed by the heat fused polyester copolymer mixes with 60/40 mass mixing ratio example with the wood pulp through beating, and with this blended fiber supply random web-laying equipment, the formation Unit Weight is 50g/m
2Net.By ventilation (air through) drying machine 180 ℃ of heat treatments of this net being carried out 10 minutes.The rerum natura of gained non-weaving cloth is as shown in table 1.
Reference example 1
The synthetic method of trimellitic acid titanium:
In the ethylene glycol solution (0.2%) of trimellitic anhydride, interpolation is 1/2 mole four titanium butoxide with respect to the molar weight of trimellitic anhydride, hold it in air, under the normal pressure, reacted 60 minutes, product is cooled to normal temperature, is recrystallized, also collect with filter paper filtering gained precipitation with the acetone of 10 times of amounts, 100 ℃ of dryings 2 hours, make required compound as catalyst.
Embodiment 2
With embodiment 1 the same polyester polymers, the compound short fiber of polyester and the non-weaving cloth of preparing.But, use 0.016 part of trimellitic acid titanium that synthesizes by the method for above-mentioned reference example as titanium compound as catalyst, in addition, carry out same operation.Result of the test is as shown in table 1.
[embodiment 3-5, comparative example 1-3]
In embodiment 3-5 and each example of comparative example 1-3, with embodiment 1 the same polyester polymers, the compound short fiber of polyester and the non-weaving cloth of preparing.But, use compound shown in the table 1 as titanium compound and phosphorus compound as catalyst with addition shown in the table 1.Result of the test is as shown in table 1.
Embodiment 6
With the embodiment 1 the same non-weaving cloth of making.But when making non-weaving cloth, with the mixture feed roller carding machine of compound short fiber of above-mentioned core-skin type and beating wood pulp, the formation order is paid and is 100g/m
2Net, then it is supplied with needing machine, make the fiber interlacing, make the dry type non-weaving cloth.Result of the test is as shown in table 1.
Embodiment 7
Will with the compound polyester fiber of the embodiment 1 the same core-skin of making (core-skin ratio: 50/50, fiber number: 2.2dtex, fibre length: 5mm) with beating after wood pulp mixes with 60/40 mass mixing ratio example, with its supply random web-laying equipment, the formation Unit Weight is 50g/m
2Net.With the ventilation drying machine 180 ℃ of heat treatments of this net being carried out 10 minutes.The result of the test of gained air-laid nonwoven fabric is as shown in table 1.
Comparative example 4
Can carry out in the rustless steel container of compressive reaction, the mixture of pack into 100 parts by mass dimethyl terephthalate (DMT)s and 70 parts by mass ethylene glycol is to wherein sneaking into 0.064 parts by mass calcium acetate monohydrate.The gained mixture was depressed in adding of 0.07MPa, from 140 ℃ be warming up to 240 ℃ on one side, carry out ester exchange reaction on one side, be the phosphate aqueous solution of 56% weight to wherein adding 0.044 weight portion concentration afterwards, the terminated diester exchange reaction.
Above-mentioned product is moved into the polycondensation container, add the antimonous oxide of the amount of Table 1, be warming up to 290 ℃, under the high vacuum of (below the 26.67Pa), carry out polycondensation reaction, make polyester polymers.The same with embodiment 1, make fiber with the gained polyester polymers, make non-weaving cloth then.Result of the test is as shown in table 1.
Embodiment 8
The preparation of titanium compound:
In possessing the 2L three-neck flask that mixes agitating function, the 919g ethylene glycol of packing into and 10g acetate mix, and slowly add 71g four titanium butoxide in this mixture, make the ethylene glycol solution (transparent) of titanium compound.Hereinafter this solution note is made " TB solution ".The titanium atom concentration of this solution is 1.02% mole.
The preparation of phosphorus compound:
To possess the 656g ethylene glycol of packing in the 2L three-neck flask that mixes agitating function, be heated to 100 ℃ while stir.When reaching this temperature, in heated glycol, add 34.5g phosphoric acid one lauryl, add thermal agitation, mixed dissolution is made transparent solution.Below, this solution note is made " P1 solution ".
Preparation of catalysts:
Stir on one side the above-mentioned P1 solution (about 690g) of temperature control to 100 ℃, on one side to wherein slowly adding the above-mentioned TB solution of 310g, after all adding, reaction mixture was stirred 1 hour under 100 ℃ temperature, the reaction of above-mentioned titanium compound and above-mentioned phosphorus compound is finished.Adjust the TB solution of this moment and the combined amount ratio of P1 solution, make with respect to 1 mole of titanium atom, the molar weight of phosphorus atoms is 2.0 moles.The product that this reaction generates is insoluble to ethylene glycol, so reaction mixture presents the gonorrhoea state, product suspends wherein with fine precipitation form.Below, this solution note is made " TP1-2.0 catalyst ".
In order to analyze the composition of gained TP1-2.0 catalyst, its part is filtered with 5 μ/purpose filter, collect the above-mentioned product of separating out of solid form, with its washing, drying.Gained is separated out product carry out the concentration of element analysis by the XMA analytic approach, titanium is 12.0% quality as a result, and phosphorus is 16.4% quality, and phosphorus atoms is 2.1 moles with respect to the molar weight of titanium atom.Further it is carried out the solid NMR analysis, obtain following result.
By C-13CP/MAS (frequency 75.5Hz) determination method, affirmation has disappeared from chemical shift 14ppm, 20ppm, the 36ppm peak of the butoxy of four titanium butoxide.By P-31DD/MAS (frequency 121.5Hz) determination method, confirm the unexistent new chemical shift peak 22ppm of phosphoric acid one lauryl always.By these results as can be known, the precipitation of gained obviously contains the new compound that the reaction of titanium compound and phosphorus compound forms in the present embodiment.
179 parts by mass high purity terephthalic acids are mixed with 95 parts by mass ethylene glycol, reaction mixture slurry is remained under stirring, nitrogen atmosphere, 255 ℃, the condition of normal pressure, be equipped with in advance in the reactor of 225 parts of oligomer (bis-terephthalate's oligomer of ethylene glycol) with the certain speed supply, to react the water and the ethylene glycol that generate on one side distillates outside the reaction system, carry out 4 hours esterification on one side, make reaction terminating then.The esterification yield of this moment is more than 98%, and the degree of polymerization of the oligomer of formation is about 5-7.
The oligomer that 225 parts of these esterifications are obtained moves in the polycondensation reaction groove, adds 3.34 parts of above-mentioned " TP1-2.0 catalyst " of making as polycondensation catalyst.Then, with the reaction temperature in the system from 255 ℃ of temperature-gradient methods to 280 ℃, and with the reaction pressure split reduction to 60Pa, carry out polycondensation reaction.At this moment, water and the ethylene glycol that generates in the reaction has been shifted out outside the reaction system.
The load that stirrer paddle is born in the monitoring system, confirming the degree of carrying out of polycondensation reaction, when reaching the required degree of polymerization, cessation reaction.Afterwards, the reactant in the system is extruded the formation strip continuously from the discharge portion of reaction vessel, cooling, section, the granular section of making the about 3mm of length.The quality of gained polyethylene terephthalate polymer (258 ℃ of fusing points) is as shown in table 1.In addition, with identical catalyst, preparation contains terephthalic acid (TPA) and M-phthalic acid with the composite sour composition of 60/40 (% mole), ethylene glycol and 1, the 6-hexylene glycol is with the composite diol component of 85/15 (% mole), inherent viscosity is 0.36, softening point is 70 ℃ copolymer, and makes section.Use above-mentioned two kinds of polymer chipss to be supplied to make the melt-spun device of concentric sheath core pattern bicomponent filament yarn, use stretch, shearing device, make the compound polyester fiber of core-skin (the core-skin ratio: 50/50, fiber number: 2.2dtex, fibre length: 5mm).The skin zone of this composite fibre is formed by above-mentioned copolymer.With the compound polyester staple fibers of this core-skin with through the wood pulp of beating with 60/40 mixing quality than mixing, this blended fiber is supplied with random web-laying equipment, the formation Unit Weight is 50g/m
2Net.By pneumatic drier 180 ℃ of heat treatments of this net being carried out 10 minutes.The rerum natura of gained non-weaving cloth is as shown in table 2.
Embodiment 9
With the embodiment 1 the same non-weaving cloth of making.Just when the preparation catalyst, replace phosphoric acid one lauryl with monobutyl phosphate.The following change of its addition and reaction condition.
With 28.3g monobutyl phosphate heating for dissolving (below be denoted by " P2 solution ") in 537g ethylene glycol, to wherein adding 435g TB solution, preparation feedback product.The combined amount that makes at this moment TB solution and P2 solution is than for per 1 mole of titanium atom 2.0 moles of phosphorus atoms being arranged.Below gained catalyst note is made " TP2-2.0 catalyst ".Heating-up temperature in the above-mentioned reaction is 70 ℃, and the reaction time is 1 hour.
In order to analyze gained reaction precipitate, the part of the reaction solution filter with 5 μ is filtered, the above-mentioned product of separating out of collection solid form is with its washing, drying.Gained is separated out product carry out the concentration of element analysis, titanium is 17.0% quality as a result, and phosphorus is 21.2% quality, and phosphorus atoms is 1.9 moles with respect to the ratio of 1 mole of titanium atom.Result of the test is as shown in table 2.
Embodiment 10
With the embodiment 1 the same non-weaving cloth of making.Be the preparation amount and the TB solution addition of following change TP1 solution.
With 31.3g phosphoric acid one lauryl heating for dissolving (below be denoted by " P3 solution ") in 594g ethylene glycol,, make its reaction obtain product to wherein adding 375g TB solution.The adjustment TB solution at this moment and the combined amount ratio of P3 solution, making with respect to per 1 mole of titanium atom has 1.5 moles of phosphorus atoms.Below gained catalyst note is made " TP3-1.5 catalyst ".Result of the test is as shown in table 1.
Embodiment 11
With the embodiment 2 the same non-weaving cloths of making.Be the preparation amount and the TB solution addition of following change TP2 solution.
With 33.0g monobutyl phosphate heating for dissolving (below be denoted by " P4 solution ") in 627g ethylene glycol,, make its reaction obtain product to wherein adding 340g TB solution.The adjustment TB solution at this moment and the combined amount ratio of P4 solution, making with respect to per 1 mole of titanium atom has 3.0 moles of phosphorus atoms.Below gained catalyst note is made " TP4-3.0 catalyst ".Result of the test is as shown in table 2.
Comparative example 5
With the embodiment 1 the same non-weaving cloth of making.Just, polycondensation catalyst is become 1.3% concentration ethylene glycol solution of antimony trioxide, its addition is 4.83 parts, and 25% ethylene glycol solution that adds 0.121 part of trimethyl phosphate is as stabilizing agent.Result of the test is as shown in table 2.
Comparative example 6
With the embodiment 1 the same non-weaving cloth of making.Just, the TB solution that only uses preparation among the embodiment 1 is as polycondensation catalyst, and its addition is 1.03 parts.And polycondensation reaction time changed to 95 minutes.Result of the test is as shown in table 2.
Comparative example 7
With the embodiment 1 the same non-weaving cloth of making.Just, do not make TB solution and P1 solution reaction, but add 1.03 parts of TB solution and 2.30 parts of P1 solution in the polycondensation reaction system when preparing polyester respectively as polycondensation catalyst.Result of the test is as shown in table 2.
Comparative example 8
With the embodiment 2 the same non-weaving cloths of making.Just, do not make TB solution and P2 solution reaction, but add 1.03 parts of TB solution and 2.3 parts of P2 solution in the polycondensation reaction system when preparing polyester respectively as polycondensation catalyst.Result of the test is as shown in table 2.
Industrial applicability
Non-weaving cloth of the present invention has good tone (L*Value, b*Value), stay in grade and equal One, particularly with purposes that food and drink contacts in, for example at the packing timber of food and drink The cloth sheet of material, filtering material, filtering lye, oil strain cloth sheet, kitchen rag, be used for reverse osmosis The base material of permeable membrane, hygienic material, very high for the purposes practicality such as filter cloth of various beverages.
Claims (16)
1. nonwoven fabric of polyester composite fiber, this non-weaving cloth comprises by heat fused polymer and the compound short fiber of the Thermoadhesive that becomes fine thermoplastic polymer to form, and it is characterized in that:
Above-mentioned heat fused polymer forms the part along the longitudinally extending outer peripheral face of described compound short fiber, and the fine thermoplastic polymer of above-mentioned one-tenth forms the remainder of above-mentioned compound short fiber,
The fine thermoplastic polymer of above-mentioned one-tenth is selected from the polyester polymers that polycondensation forms in the presence of catalyst by the aromatic dicarboxylic acid ester,
Above-mentioned catalyst contains at least a composition that is selected from following mixture (1) and product (2),
Above-mentioned is following compositions (A) and mixture (B) as mixture of catalysts (1): (A) be the titanium compound composition (A) that contains at least a being selected from (a) and material (b),
(a) alkoxytitanium shown in the following general formula (I),
In the formula (I), R
1, R
2, R
3And R
4A kind of alkyl and phenyl groups that be selected from of independent respectively expression with 1-20 carbon atom, m represents the integer of 1-4, when m represents 2,3 or 4 integer, 2,3 or 4 R
2And R
3Identical or different respectively;
(b) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (I) and the following general formula (II),
In the formula (II), n represents the integer of 2-4;
(B) be the phosphorus compound composition (B) that contains phosphorus compound shown at least a following general formula (III),
In the formula (III), R
5, R
6And R
7Independent separately expression has the alkyl of 1-4 carbon atom, and X represents a kind of being selected from-CH
2-Ji and-group of CH (Y)-Ji, wherein Y represents phenyl;
The mM value of contained titanium elements is M with the ratio of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the above-mentioned titanium compound composition (A)
Ti, the mM value of institute's phosphorus element-containing is M with the ratio of above-mentioned aromatic dicarboxylic acid ester's mole numerical value in the phosphorus compound composition (B)
P, M
TiAnd M
PBe unit all, with M with %
TiAnd M
PSatisfying following relational expression (i) and combined amount (ii) uses above-mentioned as mixture of catalysts (1):
1≤M
P/M
Ti≤15 (i)
10≤M
P+M
Ti≤100 (ii)；
Above-mentioned product (2) as catalyst is following compositions (C) and product (D): (C) be to contain at least a titanium compound composition (C) that is selected from following (c) and material (d),
(c) alkoxytitanium shown in the following general formula (IV),
In the formula (IV), R
8, R
9, R
10And R
11Independent respectively expression has the alkyl of 1-20 carbon atom, and p represents the integer of 1-3, and p represents 2 or at 3 o'clock, 2 or 3 R
9And R
10Identical or different respectively;
(d) product of aromatic polycarboxylic acid or its acid anhydrides shown in the alkoxytitanium of above-mentioned general formula (IV) and the above-mentioned general formula (II),
(D) be the phosphorus compound composition (D) that contains phosphorus compound shown at least a following general formula (V),
In the following formula (V), R
12Expression has the alkyl of 1-20 carbon atom or has the aryl of 6-20 carbon atom, and q represents 1 or 2 integer.
2. the nonwoven fabric of polyester composite fiber of claim 1, wherein in described composition (A) as mixture of catalysts (1) and (C) each composition, alkoxytitanium (a) and alkoxytitanium (c) separately with the reaction mol ratio of the aromatic polycarboxylic acid of general formula (II) or its acid anhydrides in the 2:1-2:5 scope.
3. the nonwoven fabric of polyester composite fiber of claim 1, wherein said as the reacting dose ratio of composition (D) in the product (2) of catalyst with composition (C), be converted into the ratio P/Ti of the molar weight of contained titanium atom in the molar weight of contained phosphorus atoms in the composition (D) and the composition (C), in the 1:1-3:1 scope.
4. the nonwoven fabric of polyester composite fiber of claim 1, the phosphorus compound of used general formula (V) is selected from phosphoric acid one Arrcostab in the wherein said product (2).
5. the nonwoven fabric of polyester composite fiber of claim 1, wherein said aromatic dicarboxylic acid ester is the ester that the ester exchange reaction by the dialkyl of aromatic dicarboxylic acid and alkylene glycol makes.
6. the nonwoven fabric of polyester composite fiber of claim 1, wherein said aromatic dicarboxylic acid is selected from terephthalic acid (TPA), 1,2-naphthalenedicarboxylic acid, phthalic acid, M-phthalic acid, diphenyl dicarboxylic acid and biphenoxyl ethane dioctyl phthalate, described alkylene glycol is selected from ethylene glycol, butanediol, trimethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexylene glycol and 1, the 12-dodecanediol.
7. the nonwoven fabric of polyester composite fiber of claim 1, wherein said polyester polymers is at the L according to JIS Z 8729
*a
*b
*L in the color specification system
*Value is 77-85, b
*Value is 2-5.
8. the nonwoven fabric of polyester composite fiber of claim 1, wherein said compound short fiber has the parallel type structure.
9. the nonwoven fabric of polyester composite fiber of claim 1, wherein said compound short fiber has concentric or eccentric skin-core structure, and its concentric or eccentric core is formed by the fine thermoplastic polymer of described one-tenth, and concentric or eccentric skin zone is formed by the heat fused polymer.
10. the nonwoven fabric of polyester composite fiber of claim 1, wherein said heat fused polymer is with described to become the mass ratio of fine thermoplastic polymer be 30:70-70:30.
11. the nonwoven fabric of polyester composite fiber of claim 1, wherein said heat fused polymer is selected from polyurethane series elastomer, polyester based elastomers, inelastic polyester homopolymer and copolymer, polyolefin homopolymers and copolymer and vinol series polymer.
12. the nonwoven fabric of polyester composite fiber of claim 1, wherein said compound short fiber has the single fiber fiber number of 0.01-10dtex and the fibre length of 5-100mm.
13. the nonwoven fabric of polyester composite fiber of claim 1, this non-weaving cloth be by described polyester complex fiber by combing method, copy the cloth that slurry method or air lay method formed and carried out Overheating Treatment.
14. the nonwoven fabric of polyester composite fiber of claim 13, this non-weaving cloth are to have carried out the cloth that interlacing is handled before described heat treatment.
15. the nonwoven fabric of polyester composite fiber of claim 1, the ratio that contains of compound short fiber described in this non-weaving cloth is the 25-100% quality.
16. the nonwoven fabric of polyester composite fiber of claim 1, this non-weaving cloth with the purposes of Food Contact in use.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003001876A JP4056397B2 (en) | 2003-01-08 | 2003-01-08 | Non-woven fabric for food |
| JP1876/2003 | 2003-01-08 | ||
| JP63148/2003 | 2003-03-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1735723A CN1735723A (en) | 2006-02-15 |
| CN100467693C true CN100467693C (en) | 2009-03-11 |
Family
ID=32819784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200380108344 Expired - Fee Related CN100467693C (en) | 2003-01-08 | 2003-12-26 | Nonwoven fabric of polyester composite fiber |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4056397B2 (en) |
| CN (1) | CN100467693C (en) |
| ES (1) | ES2366637T3 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012056619A (en) * | 2010-09-13 | 2012-03-22 | Nakagawa Sangyo Kk | Conveying material and method for manufacturing the same |
| JP6552959B2 (en) * | 2015-12-28 | 2019-07-31 | Ｋｂセーレン株式会社 | Textiles for palatable beverage extraction filter |
| CN105586715A (en) * | 2016-03-30 | 2016-05-18 | 大源非织造（苏州）有限公司 | Coarse-denier high-thickness hot-air nonwoven fabric and making technology thereof |
| CN115029833B (en) * | 2022-06-07 | 2024-02-06 | 江阴市聚鑫花式线有限公司 | Flame-retardant fancy yarn and preparation process thereof |
| CN115012086B (en) * | 2022-06-07 | 2024-02-06 | 江阴市聚鑫花式线有限公司 | Plant dye dyeing fancy yarn and processing technology thereof |
-
2003
- 2003-01-08 JP JP2003001876A patent/JP4056397B2/en not_active Expired - Lifetime
- 2003-12-26 ES ES03768326T patent/ES2366637T3/en not_active Expired - Lifetime
- 2003-12-26 CN CN 200380108344 patent/CN100467693C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1735723A (en) | 2006-02-15 |
| JP2004211260A (en) | 2004-07-29 |
| JP4056397B2 (en) | 2008-03-05 |
| ES2366637T3 (en) | 2011-10-24 |
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Effective date of registration: 20180316 Address after: Osaka City, Osaka of Japan Patentee after: TEIJIN FRONTIER CO.,LTD. Address before: Osaka Japan Patentee before: Teijin Fibers Ltd. |
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