JP2012112079A - Polyethylene naphthalate fiber and staple fiber nonwoven fabric therefrom - Google Patents
Polyethylene naphthalate fiber and staple fiber nonwoven fabric therefrom Download PDFInfo
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- JP2012112079A JP2012112079A JP2010263722A JP2010263722A JP2012112079A JP 2012112079 A JP2012112079 A JP 2012112079A JP 2010263722 A JP2010263722 A JP 2010263722A JP 2010263722 A JP2010263722 A JP 2010263722A JP 2012112079 A JP2012112079 A JP 2012112079A
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- polyethylene naphthalate
- fiber
- nonwoven fabric
- naphthalate fiber
- unstretched
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- 239000000835 fiber Substances 0.000 title claims abstract description 148
- -1 Polyethylene naphthalate Polymers 0.000 title claims abstract description 106
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 title claims abstract description 102
- 239000011112 polyethylene naphthalate Substances 0.000 title claims abstract description 102
- 239000004745 nonwoven fabric Substances 0.000 title claims abstract description 41
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 abstract description 5
- 238000009987 spinning Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 239000003921 oil Substances 0.000 description 13
- 239000000123 paper Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000003490 calendering Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 description 4
- 238000002788 crimping Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000001788 irregular Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-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
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012772 electrical insulation material Substances 0.000 description 2
- 238000012681 fiber drawing Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- 239000003981 vehicle Substances 0.000 description 2
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- DLKQHBOKULLWDQ-UHFFFAOYSA-N 1-bromonaphthalene Chemical compound C1=CC=C2C(Br)=CC=CC2=C1 DLKQHBOKULLWDQ-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- GMOYUTKNPLBTMT-UHFFFAOYSA-N 2-phenylmethoxybenzoic acid Chemical compound OC(=O)C1=CC=CC=C1OCC1=CC=CC=C1 GMOYUTKNPLBTMT-UHFFFAOYSA-N 0.000 description 1
- QLIQIXIBZLTPGQ-UHFFFAOYSA-N 4-(2-hydroxyethoxy)benzoic acid Chemical compound OCCOC1=CC=C(C(O)=O)C=C1 QLIQIXIBZLTPGQ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- UUAGPGQUHZVJBQ-UHFFFAOYSA-N Bisphenol A bis(2-hydroxyethyl)ether Chemical compound C=1C=C(OCCO)C=CC=1C(C)(C)C1=CC=C(OCCO)C=C1 UUAGPGQUHZVJBQ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 235000003403 Limnocharis flava Nutrition 0.000 description 1
- 244000278243 Limnocharis flava Species 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-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
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 150000007860 aryl ester derivatives Chemical class 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CCQPAEQGAVNNIA-UHFFFAOYSA-N cyclobutane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCC1 CCQPAEQGAVNNIA-UHFFFAOYSA-N 0.000 description 1
- FDKLLWKMYAMLIF-UHFFFAOYSA-N cyclopropane-1,1-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC1 FDKLLWKMYAMLIF-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WPUMVKJOWWJPRK-UHFFFAOYSA-N naphthalene-2,7-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 WPUMVKJOWWJPRK-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- CGEXUOTXYSGBLV-UHFFFAOYSA-N phenyl benzenesulfonate Chemical compound C=1C=CC=CC=1S(=O)(=O)OC1=CC=CC=C1 CGEXUOTXYSGBLV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920002215 polytrimethylene terephthalate Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000646 scanning calorimetry Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- YXTFRJVQOWZDPP-UHFFFAOYSA-M sodium;3,5-dicarboxybenzenesulfonate Chemical compound [Na+].OC(=O)C1=CC(C(O)=O)=CC(S([O-])(=O)=O)=C1 YXTFRJVQOWZDPP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000012749 thinning agent Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Nonwoven Fabrics (AREA)
Abstract
Description
本発明は、ポリエチレンナフタレート繊維及びそれからなる短繊維不織布に関し、更に詳しくは、改良された未延伸ポリエチレンナフタレート繊維と延伸ポリエチレンナフタレート繊維から構成される接着性能の改善されたポリエチレンナフタレート繊維及びそれからなる短繊維不織布に関する。 The present invention relates to a polyethylene naphthalate fiber and a short fiber nonwoven fabric comprising the same, and more particularly, an improved polyethylene naphthalate fiber having improved adhesion performance composed of an improved unstretched polyethylene naphthalate fiber and a stretched polyethylene naphthalate fiber, and It relates to a short fiber nonwoven fabric comprising the same.
従来、耐熱性を有する不織布の開発が種々の分野で要望されている。例えば保温材料、電気絶縁材料、フィルター、医療材料、建築材料等の分野において、不織布は広く利用されているが、これらの分野の一部において耐熱性が必要とされ、そのため耐熱性を有する不織布の開発の要求が高まっている。 Conventionally, development of a non-woven fabric having heat resistance has been demanded in various fields. For example, non-woven fabrics are widely used in the fields of heat insulating materials, electrical insulating materials, filters, medical materials, building materials, etc., but heat resistance is required in some of these fields. Development demands are increasing.
耐熱性不織布を得るための１つの方向は、その素材として耐熱性のポリマーを使用することである。耐熱性のポリマーの１つであるポリエチレンナフタレートを使用した不織布が既に提案されている。具体的には、ポリエチレンナフタレート繊維と潜在的接着性を有する重合体からの繊維とを混合したウェブを加熱接着した不織布が提案されている（例えば、特許文献１参照。）。この不織布は、接着成分として使用されている繊維が、代表的にはポリエチレンテレフタレート共重合体からの繊維であって、その融点はかなり低いものである。そのため、この不織布は接着成分の融点の影響を受け、ポリエチレンナフタレートの有する本来の耐熱性が生かされていない。 One direction to obtain a heat resistant nonwoven is to use a heat resistant polymer as the material. Nonwoven fabrics using polyethylene naphthalate, which is one of heat-resistant polymers, have already been proposed. Specifically, a non-woven fabric has been proposed in which a web obtained by mixing polyethylene naphthalate fibers and fibers from a polymer having latent adhesiveness is heat-bonded (see, for example, Patent Document 1). In this nonwoven fabric, the fiber used as the adhesive component is typically a fiber from a polyethylene terephthalate copolymer, and its melting point is considerably low. Therefore, this nonwoven fabric is affected by the melting point of the adhesive component, and the original heat resistance of polyethylene naphthalate is not utilized.
ポリエチレンナフタレート繊維から実質的になり、平均繊維径が０．１〜１０μｍであり、縦横の引っ張り強力に優れた不織布が提案されている（例えば、特許文献２参照。）。しかしながら、この不織布は、具体的にはジェット紡糸（メルトブロー）法で製造されたものであり、繊維径が不均一で細く、極細であるが、その繊維の強度は充分高いとは云えず、これが不織布の引裂き強度にも影響している。しかも、この不織布は、ジェット紡糸によるために、種々のタイプの特性を有する不織布を提供することが困難である。 A non-woven fabric that is substantially made of polyethylene naphthalate fiber, has an average fiber diameter of 0.1 to 10 μm, and has excellent longitudinal and transverse tensile strength has been proposed (see, for example, Patent Document 2). However, this non-woven fabric is specifically manufactured by a jet spinning (melt blow) method, and the fiber diameter is non-uniform, thin, and extremely fine. However, the strength of the fiber cannot be said to be sufficiently high. It also affects the tear strength of the nonwoven fabric. Moreover, since this nonwoven fabric is based on jet spinning, it is difficult to provide nonwoven fabrics having various types of characteristics.
また固有粘度及び複屈折率を規定した、繊度４．０デシテックス以下の細繊度繊維及びポリエチレンナフタレート樹脂単独からなる未延伸糸と延伸糸を混合し、加熱接着されてなる、短繊維不織布を提案している（例えば、特許文献３及び特許文献４参照。）。未延伸繊維を規定の範囲の複屈折率とするために紡糸する際の糸条の冷却条件を緩和すると、ポリマーの固化が遅れて、紡糸調子が不良化し、細繊度化が困難となる。また、同様に規定の複屈折率を得るために、紡糸速度を下げた場合には、細繊度を得るために、ポリマーの吐出量を下げる必要が生じ、紡糸調子の不良化を招来する。実施例で示される最も細い繊維は、延伸糸で、１．２１ｄｔｅｘ、未延伸糸で４．２９ｄｔｅｘである。 Also proposed is a short fiber nonwoven fabric in which unstretched yarn made of polyethylene naphthalate resin alone and stretched yarn are mixed and heat-bonded with fine fiber with a fineness of 4.0 decitex or less and specified intrinsic viscosity and birefringence. (For example, see Patent Document 3 and Patent Document 4). If the cooling conditions of the yarn during spinning are relaxed in order to make the unstretched fiber have a birefringence within a specified range, the solidification of the polymer is delayed, the spinning condition becomes poor, and the fineness becomes difficult. Similarly, when the spinning speed is lowered in order to obtain a prescribed birefringence, it is necessary to lower the discharge amount of the polymer in order to obtain fineness, resulting in poor spinning tone. The thinnest fibers shown in the examples are 1.21 dtex for the drawn yarn and 4.29 dtex for the undrawn yarn.
本発明は、上記従来技術を背景になされたもので、その目的は、実質的にポリエチレンナフタレート単独からなる耐熱性に優れ、かつ強度のつよい短繊維不織布を実現するために、優れたバインダー性能を持つ細繊度未延伸ポリエチレンナフタレート繊維と従来ないレベルの細繊度延伸ポリエチレンナフタレート繊維を提供することにある。 The present invention has been made against the background of the above-described prior art, and its purpose is to achieve excellent binder performance in order to realize a short fiber nonwoven fabric that is substantially composed of polyethylene naphthalate alone and has excellent heat resistance and strength. An object of the present invention is to provide unfine-stretched polyethylene naphthalate fiber having a fineness and a non-conventional fineness-stretched polyethylene naphthalate fiber.
本発明者は、上記課題を解決するため鋭意検討を重ねた結果、従来にない高い複屈折率の未延伸繊維を接着成分として使用しても、熱圧処理により繊維同士を接着し、十分な接着強力が得られることを見出し、本発明に到達した。すなわち本発明の１つ目は、未延伸ポリエチレンナフタレート繊維であって、繊度が０．５〜１．２デシテックスであることを特徴とする未延伸ポリエチレンナフタレート繊維であり、本発明の２つ目は延伸ポリエチレンナフタレート繊維であって、繊度が０．２〜０．７デシテックスである延伸ポリエチレンナフタレート繊維である。その延伸ポリエチレンナフタレート繊維はその未延伸ポリエチレンナフタレート繊維を延伸して得られることが好ましく採用できる。そして本発明の３つ目は繊度が規定されたその未延伸ポリエチレンナフタレート繊維１０〜７０質量％と繊度が規定されたその延伸ポリエチレンナフタレート繊維９０〜３０質量％を混合して熱圧着させることを特徴とするポリエチレンナフタレート繊維不織布である。 As a result of intensive studies to solve the above problems, the present inventor has adhered unsatisfied fibers by hot-pressure treatment even when unstretched fibers having a high birefringence that are not conventionally used are used as an adhesive component. The inventors have found that adhesive strength can be obtained, and have reached the present invention. That is, the first aspect of the present invention is an unstretched polyethylene naphthalate fiber, which is an unstretched polyethylene naphthalate fiber and has a fineness of 0.5 to 1.2 dtex. The eyes are stretched polyethylene naphthalate fibers having a fineness of 0.2 to 0.7 dtex. The stretched polyethylene naphthalate fiber can be preferably obtained by stretching the unstretched polyethylene naphthalate fiber. The third aspect of the present invention is to thermocompression-bond the unstretched polyethylene naphthalate fiber 10 to 70% by mass with a specified fineness and the stretched polyethylene naphthalate fiber 90 to 30% by mass with a defined fineness. A polyethylene naphthalate fiber nonwoven fabric characterized by
それぞれの未延伸ポリエチレンナフタレート繊維、延伸ポリエチレンナフタレート繊維にはより好適な複屈折率、繊維長、固有粘度が存在する。好ましくはその未延伸ポリエチレンナフタレート繊維は、複屈折率が０．０４０〜０．１２０で、固有粘度が０．３５〜０．４７ｄＬ／ｇであることを特徴とする未延伸ポリエチレンナフタレート繊維であり、その延伸ポリエチレンナフタレート繊維は、複屈折率が０．３０〜０．４０、１８０℃乾熱収縮率が５．０〜１０．０％で、固有粘度が０．３５〜０．４７ｄＬ／ｇ、繊度が０．２〜０．７デシテックスであることを特徴とする延伸ポリエチレンナフタレート繊維である。 Each unstretched polyethylene naphthalate fiber and stretched polyethylene naphthalate fiber have more preferable birefringence, fiber length, and intrinsic viscosity. Preferably, the unstretched polyethylene naphthalate fiber is an unstretched polyethylene naphthalate fiber having a birefringence of 0.040 to 0.120 and an intrinsic viscosity of 0.35 to 0.47 dL / g. The drawn polyethylene naphthalate fiber has a birefringence of 0.30 to 0.40, a dry heat shrinkage of 180 ° C. of 5.0 to 10.0%, and an intrinsic viscosity of 0.35 to 0.47 dL / g, a drawn polyethylene naphthalate fiber having a fineness of 0.2 to 0.7 dtex.
本発明によれば、従来検討されてきたポリエチレンナフタレート不織布に比べ、強度が著しく向上し、実用に耐えうる耐熱性短繊維不織布の提供を可能とする。その用途は、バグフィルター、Ｆ種以上の電気絶縁材料、電池セパレーター、コンデンサー（スーパーキャパシター）用セパレーター、天井材やフロアマット、エンジン用フィルター、オイル用フィルター等の耐熱性、耐薬品性が要求される車輌用不織布素材など、幅広く適用されることが期待される。 According to the present invention, it is possible to provide a heat-resistant short fiber nonwoven fabric that has significantly improved strength and can withstand practical use as compared with a polyethylene naphthalate nonwoven fabric that has been conventionally studied. Its applications require heat resistance and chemical resistance such as bag filters, F-type and higher electrical insulation materials, battery separators, condenser (supercapacitor) separators, ceiling materials and floor mats, engine filters, oil filters, etc. It is expected to be widely applied such as non-woven materials for vehicles.
以下本発明の実施形態について詳細に説明する。
本発明を構成するポリエチレンナフタレート繊維は実質的にエチレン−２，６−ナフタレート単位よりなるポリエチレンナフタレート繊維であることが必要である。ポリエチレンナフタレート繊維は、好ましくはエチレン−２，６−ナフタレート単位をポリエチレンナフタレート繊維を構成する繰り返し単位あたり９０モル％以上含み、１０モル％未満の割合で適当な第３成分を含む重合体からなる繊維であっても差し支えない。第３成分としては（ａ）１分子当たり２個のエステル形成性官能基を有する化合物、例えば、シュウ酸、コハク酸、アジピン酸、セバシン酸、ダイマー酸などの脂肪族ジカルボン酸；シクロプロパンジカルボン酸、シクロブタンジカルボン酸、ヘキサヒドロテレフタル酸などの脂環族ジカルボン酸；フタル酸、イソフタル酸、ナフタレン−２，７−ジカルボン酸、４，４’−ジフェニルジカルボン酸などの芳香族ジカルボン酸；ジフェニルエーテルジカルボン酸、ジフェニルスルホン酸、ジフェノキシエタンジカルボン酸、３，５−ジカルボキシベンゼンスルホン酸ナトリウムなどのその他のジカルボン酸；グリコール酸、ｐ−ヒドロキシ安息香酸、ｐ−ヒドロキシエトキシ安息香酸などのヒドロオキシカルボン酸；１，２−プロピレングリコール、トリメチレングリコール、ジエチレングリコール、テトラメチレングリコール、ネオペンチレングリコール、ヘキサメチレングリコール、ｐ−キシレングリコール、１，４−シクロヘキサンジメタノール、ｐ，ｐ’−ビス（ヒドロキシエトキシ）ジフェニルスルホン、１，４−ビス（β−ヒドロキシエトキシ）ベンゼン、２，２−ビス（ｐ−β−ヒドロキシエトキシフェニル）プロパン、ポリアルキレングリコールなどのジヒドロキシ化合物；それらの機能的誘導体、すなわち前記カルボン酸、ヒドロキシカルボン酸、ヒドロキシ化合物又はそれらの低級（ジ）アルキルエステル、低級（ジ）アリールエステル、低級（ビス）アルキルアリールエステル等から誘導される高重合度化合物や、（ｂ）１分子当たり１個のエステル形成性官能基を有する化合物、たとえば、安息香酸、ベンジルオキシ安息香酸、メトキシポリアルキレングリコールなどが挙げられる。さらに（ｃ）３個以上のエステル形成性官能基を有する化合物、たとえば、グリセリン、ペンタエリスリトール、トリメチロールプロパン、トリメシン酸、トリメリット酸なども、重合体が実質的に線状である範囲内で使用可能である。
Hereinafter, embodiments of the present invention will be described in detail.
The polyethylene naphthalate fiber constituting the present invention needs to be a polyethylene naphthalate fiber substantially consisting of ethylene-2,6-naphthalate units. The polyethylene naphthalate fiber is preferably made of a polymer containing 90% by mole or more of ethylene-2,6-naphthalate units per repeating unit constituting the polyethylene naphthalate fiber and a suitable third component in a proportion of less than 10% by mole. The resulting fibers can be used. As the third component, (a) a compound having two ester-forming functional groups per molecule, for example, an aliphatic dicarboxylic acid such as oxalic acid, succinic acid, adipic acid, sebacic acid, and dimer acid; cyclopropanedicarboxylic acid , Cycloaliphatic dicarboxylic acids such as cyclobutane dicarboxylic acid and hexahydroterephthalic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, naphthalene-2,7-dicarboxylic acid, 4,4′-diphenyldicarboxylic acid; diphenyl ether dicarboxylic acid , Other dicarboxylic acids such as diphenylsulfonic acid, diphenoxyethanedicarboxylic acid, sodium 3,5-dicarboxybenzenesulfonate; hydroxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid, p-hydroxyethoxybenzoic acid; 1,2-propyleneglyco , Trimethylene glycol, diethylene glycol, tetramethylene glycol, neopentylene glycol, hexamethylene glycol, p-xylene glycol, 1,4-cyclohexanedimethanol, p, p'-bis (hydroxyethoxy) diphenylsulfone, 1, Dihydroxy compounds such as 4-bis (β-hydroxyethoxy) benzene, 2,2-bis (p-β-hydroxyethoxyphenyl) propane, polyalkylene glycol; functional derivatives thereof, ie the carboxylic acids, hydroxycarboxylic acids, High polymerization degree compounds derived from hydroxy compounds or their lower (di) alkyl esters, lower (di) aryl esters, lower (bis) alkylaryl esters, etc., and (b) one ester-forming functional group per molecule Compounds having, for example, benzoic acid, benzyloxy benzoic acid, and the like methoxy polyalkylene glycol. Further, (c) a compound having three or more ester-forming functional groups, for example, glycerin, pentaerythritol, trimethylolpropane, trimesic acid, trimellitic acid, and the like are within the range where the polymer is substantially linear. It can be used.
また、前述の樹脂には必要に応じて、触媒のほか、各種の添加剤、例えば、艶消し剤、熱安定剤、光安定剤、中和剤、造核剤、滑剤、減粘剤、抗菌剤、難燃剤、帯電防止剤、可塑剤、消泡剤、整色剤、酸化防止剤、紫外線吸収剤、蛍光増白剤、染料又は顔料などが添加されていてもよい。また、改質のためにポリエチレンテレフタレートやポリトリメチレンテレフタレート、ポリブチレンテレフタレート、ポリアルキレンオキシド共重合ポリエステルなどのポリエステル樹脂やナイロン−６、ナイロン−６，６、ナイロン−６，１０、ナイロン−１２などのポリアミド類が少量共重合されていてもよい。 In addition to the catalyst, various additives such as matting agents, heat stabilizers, light stabilizers, light stabilizers, neutralizers, nucleating agents, lubricants, thinning agents, antibacterial agents, as necessary, may be added to the resins described above. An agent, a flame retardant, an antistatic agent, a plasticizer, an antifoaming agent, a color adjusting agent, an antioxidant, an ultraviolet absorber, a fluorescent whitening agent, a dye or a pigment may be added. For modification, polyester resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyalkylene oxide copolymer polyester, nylon-6, nylon-6,6, nylon-6,10, nylon-12, etc. A small amount of these polyamides may be copolymerized.
本発明のポリエチレンナフタレート繊維の適正な固有粘度の範囲は、未延伸繊維及び延伸繊維を問わず、０．３５〜０．４７ｄＬ／ｇであり、好ましくは０．４０〜０．４６ｄＬ／ｇの範囲が好適に用いられる。但し、これは溶融前のペレットではなく、口金から吐出された時点での真の繊維としての固有粘度を表す。なぜなら、ポリエチレンナフタレート（以下、ＰＥＮとよぶ）はエクストルーダー等でペレットを溶融する際に、せん断発熱が非常に大きいため、熱分解による固有粘度低下の程度がポリエチレンテレフタレートと対比した場合に、比較的大きいためである。本発明でいう固有粘度はポリエチレンナフタレート繊維をフェノールとオルトジクロロベンゼンとの混合溶媒（容積比６：４）に溶解し、３５℃で測定した粘度から求めた値である。極限粘度が０．３５ｄＬ／ｇ未満では、溶融粘度の割に分子量が小さいため、吐出後固化するまでに紡糸ドラフトにより溶融状態のまま破断するため、目標とする細繊度のＰＥＮ繊維が得られない。固有粘度が０．４７ｄＬ／ｇを越えると、紡糸張力が高くなるため、複屈折率（Δｎ）が大きくなる傾向にあり、未延伸ポリエチレンナフタレート繊維のバインダー性能が十分に得られない。また、固有粘度が大きくなればなるほど、曳糸性及び延伸性が劣化し、目標とする細繊度を得ることができない。 The range of the proper intrinsic viscosity of the polyethylene naphthalate fiber of the present invention is 0.35 to 0.47 dL / g, preferably 0.40 to 0.46 dL / g, irrespective of undrawn fiber and drawn fiber. Ranges are preferably used. However, this represents not the pellet before melting but the intrinsic viscosity as a true fiber at the time when it is discharged from the die. This is because polyethylene naphthalate (hereinafter referred to as PEN) has a very large shearing heat when the pellet is melted with an extruder or the like, so the degree of decrease in intrinsic viscosity due to thermal decomposition is compared with that of polyethylene terephthalate. This is because it is large. The intrinsic viscosity referred to in the present invention is a value obtained by dissolving polyethylene naphthalate fiber in a mixed solvent of phenol and orthodichlorobenzene (volume ratio 6: 4) and measuring the viscosity at 35 ° C. When the intrinsic viscosity is less than 0.35 dL / g, since the molecular weight is small for the melt viscosity, it breaks in a molten state by a spinning draft before solidification after discharge, so that a PEN fiber having a target fineness cannot be obtained. . If the intrinsic viscosity exceeds 0.47 dL / g, the spinning tension increases, and therefore the birefringence (Δn) tends to increase, and the binder performance of unstretched polyethylene naphthalate fibers cannot be sufficiently obtained. In addition, as the intrinsic viscosity increases, the spinnability and stretchability deteriorate, and the target fineness cannot be obtained.
本発明の未延伸ポリエチレンナフタレート繊維の繊度は、バインダー繊維として用いる不織布の目的に応じて適切に選定されるが、逆浸透膜支持体や感熱孔版印刷用原紙に用いるような未延伸（短）繊維と延伸（短）繊維を混抄して加熱圧着させることにより得られる湿式不織布用途においては、地合いの向上、薄葉化、ポアサイズの低減のため、ある程度の細繊度の未延伸ポリエチレンナフタレート（短）繊維及び延伸ポリエチレンナフタレート（短）繊維が必要であり、具体的には、未延伸ポリエチレンナフタレート繊維で単繊維の繊度が０．５〜１．２デシテックス、延伸ポリエチレンナフタレート繊維で単繊維の繊度が０．２〜０．７デシテックスであることが必要となる。未延伸ポリエチレンナフタレート繊維で単繊維の繊度が１．２デシテックス、延伸ポリエチレンナフタレート繊維で単繊維の繊度が０．７デシテックスを超えると、地合いが悪化し、薄葉化が困難である。未延伸ポリエチレンナフタレート繊維で０．５デシテックス、延伸ポリエチレンナフタレート繊維で０．７デシテックス未満とすることは、本発明の手段によっても達成困難である。（短）とは短繊維を用いることが好ましいが、長繊維であっても良いことを示す。 The fineness of the unstretched polyethylene naphthalate fiber of the present invention is appropriately selected according to the purpose of the nonwoven fabric used as the binder fiber, but unstretched (short) as used for a reverse osmosis membrane support or a heat-sensitive stencil printing paper. In wet non-woven fabrics obtained by mixing fibers and stretched (short) fibers and heat-pressing them, unstretched polyethylene naphthalate (short) with a certain degree of fineness is required to improve texture, reduce leaf thickness and reduce pore size. Fiber and drawn polyethylene naphthalate (short) fiber are required. Specifically, the unstretched polyethylene naphthalate fiber has a single fiber fineness of 0.5 to 1.2 dtex, and the stretched polyethylene naphthalate fiber has a single fiber. It is necessary that the fineness is 0.2 to 0.7 dtex. If the fineness of single fibers exceeds 1.2 decitex in unstretched polyethylene naphthalate fibers, and the fineness of single fibers exceeds 0.7 decitex in stretched polyethylene naphthalate fibers, the texture deteriorates and thinning is difficult. It is difficult to achieve by the means of the present invention that the unstretched polyethylene naphthalate fiber is 0.5 decitex and the stretched polyethylene naphthalate fiber is less than 0.7 decitex. (Short) indicates that short fibers are preferably used, but long fibers may be used.
本発明における未延伸ポリエチレンナフタレート繊維は、複屈折率（Δｎ）が０．０４０〜０．１２０、さらに望ましくは０．０６０〜０．１００の範囲であることが必要である。Δｎが０．１２０を超えると、未延伸ポリエチレンナフタレート繊維の熱接着性能が低下し、不織布において目標とする十分な強力が得られない。Δｎが０．０４０より小さいものは、細繊度のＰＥＮを得ることができない。ＰＥＮは紡糸張力が高い傾向にあるので、前述の固有粘度を低目にすることは、溶融張力を小さくし、結果としてΔｎを下げることに繋がるので、未延伸ポリエチレンナフタレート繊維の接着性能が大きくなると考えられる。更に、密度が小さいほど、バインダー性能が大きくなる傾向、かつ延伸性が向上する傾向にあるが、これは固有粘度の差によって大きな変化はない。一般的に密度は１．３２８〜１．３４０ｇ／ｃｍ３の範囲にあることが好ましい。 The unstretched polyethylene naphthalate fiber in the present invention needs to have a birefringence (Δn) of 0.040 to 0.120, more preferably 0.060 to 0.100. When Δn exceeds 0.120, the thermal bonding performance of the unstretched polyethylene naphthalate fiber is lowered, and the target sufficient strength in the nonwoven fabric cannot be obtained. When Δn is smaller than 0.040, fine PEN cannot be obtained. Since PEN tends to have a high spinning tension, lowering the above-mentioned intrinsic viscosity leads to a decrease in melt tension and consequently a decrease in Δn. Therefore, the bonding performance of unstretched polyethylene naphthalate fibers is large. It is considered to be. Furthermore, the smaller the density is, the greater the binder performance tends to be and the stretchability tends to be improved, but this does not change greatly due to the difference in intrinsic viscosity. In general, the density is preferably in the range of 1.328 to 1.340 g / cm 3 .
他方、本発明における延伸ポリエチレンナフタレート繊維は、複屈折率（Δｎ）が０．２０〜０．３０の繊維となることが好ましい。Δｎが０．２０を下回ると、主体繊維の強度が小さくなる傾向であるため、結果として目標とする不織布強度が得られない傾向にある。不織布強度は、未延伸ポリエチレンナフタレート繊維の接着強度のみならず、骨材となる延伸ポリエチレンナフタレート繊維の強度が大きくないと十分に高めることができない。一方、延伸倍率を上げてΔｎが０．３０を超えるとすることは、強度面では望ましいが、ＰＥＮの延伸張力が高いため設備上の負荷が大きく、実際は困難である。密度が大きいほど、結晶化度が高いことを示し、繊維強度が大きくなるが、密度は１．３４０〜１．３６５ｇ／ｃｍ３の範囲であることが好ましい。未延伸ポリエチレンナフタレート繊維の△ｎは溶融紡糸時のポリエチレンナフタレートの溶融温度、紡糸速度、紡糸ドラフトなどを設定することにより、延伸ポリエチレンナフタレート繊維の△ｎは溶融紡糸時のポリエチレンナフタレートの溶融温度、紡糸速度、紡糸ドラフト、延伸倍率などを設定することにより適宜調整することができる。 On the other hand, the stretched polyethylene naphthalate fiber in the present invention is preferably a fiber having a birefringence (Δn) of 0.20 to 0.30. When Δn is less than 0.20, the strength of the main fiber tends to be small, and as a result, the target nonwoven fabric strength tends not to be obtained. The strength of the nonwoven fabric cannot be sufficiently increased unless the strength of the stretched polyethylene naphthalate fiber as an aggregate is high as well as the adhesive strength of the unstretched polyethylene naphthalate fiber. On the other hand, it is desirable in terms of strength that the stretching ratio is increased so that Δn exceeds 0.30. However, since the stretching tension of PEN is high, the load on the equipment is large and is actually difficult. The higher the density, the higher the crystallinity and the higher the fiber strength, but the density is preferably in the range of 1.340 to 1.365 g / cm 3 . Δn of unstretched polyethylene naphthalate fiber is determined by setting the melting temperature, spinning speed, spinning draft, etc. of polyethylene naphthalate at the time of melt spinning, and Δn of stretched polyethylene naphthalate fiber is that of polyethylene naphthalate at the time of melt spinning. The melting temperature, spinning speed, spinning draft, draw ratio, etc. can be appropriately adjusted.
本発明のポリエチレンナフタレート繊維の断面形状は特に限定されないが、円形であっても異型断面であってもよく、中実断面であっても中空断面であってもよい。異型断面の例としては、扁平型、楕円型、長円型、ダンベル形、Ｃ字形、三角形や四角形などの多角形や三葉型、十字型、星型などの多葉体などが挙げられる。中空形状にあっても、円形の他、三角形、楕円形、長円形、十字型などの異型断面でもよく、中空数も繊維横断面につき１個以上あってもよく、特に数は制限されない。 Although the cross-sectional shape of the polyethylene naphthalate fiber of the present invention is not particularly limited, it may be circular or an irregular cross-section, and may be a solid cross-section or a hollow cross-section. Examples of the irregular cross section include a flat shape, an elliptical shape, an oval shape, a dumbbell shape, a C shape, a polygonal shape such as a triangle or a quadrilateral, a multileaf shape such as a trilobal shape, a cross shape, and a star shape. Even if it is in a hollow shape, it may have an irregular cross section such as a triangle, an ellipse, an oval, a cross, etc. in addition to a circle, and the number of hollows may be one or more per fiber cross section, and the number is not particularly limited.
本発明の繊維は、捲縮付与を要求される長繊維であってもよいが、カードにより成型される紡績糸や詰綿、繊維構造体、乾式不織布、湿式不織布の用途に適用するためには、短繊維の形態で使用される。繊維長は未延伸繊維・延伸繊維を問わず、特に限定されないが、２〜２００ｍｍであることが好ましい。詳細には湿式不織布やエアレイド不織布の場合であれば繊維長は２〜２５ｍｍ未満、その他の用途では２５〜２００ｍｍが一般的である。本発明の繊維は、必要に応じて捲縮を付与しても無捲縮であってもよい。捲縮を付与する方法は通常のポリエステル（ポリエチレンテレフタレート）短繊維製造工程で行われている条件を、ＰＥＮに合うように適宜調整した条件で実施可能である。 The fibers of the present invention may be long fibers that are required to be crimped, but in order to be applied to the use of spun yarns and cotton wool, fiber structures, dry nonwoven fabrics, and wet nonwoven fabrics that are molded by cards. Used in the form of short fibers. The fiber length is not particularly limited regardless of whether it is an unstretched fiber or a stretched fiber, but it is preferably 2 to 200 mm. Specifically, in the case of a wet nonwoven fabric or an airlaid nonwoven fabric, the fiber length is generally less than 2 to 25 mm, and in other applications, it is generally 25 to 200 mm. The fibers of the present invention may be crimped or non-crimped as necessary. The method for imparting crimps can be carried out under conditions that are appropriately adjusted so as to match the conditions of PEN in accordance with the conditions used in the normal polyester (polyethylene terephthalate) short fiber manufacturing process.
本発明で提供される不織布の製法としては、カード又はエアレイド不織布製造装置、あるいは円網、短網、あるいは長網抄紙機によってウェブを形成後、ニードルパンチ法、スパンレース法による繊維の絡合、あるいはケミカルボンド、ヤンキードライヤーによる仮接着を行った後、加熱金属ローラーによるカレンダー圧着を行うことで、未延伸ポリエチレンナフタレート繊維が延伸ポリエチレンナフタレート繊維に熱圧着され、結果として未延伸ポリエチレンナフタレート繊維と延伸ポリエチレンナフタレート繊維を接着させる方法が適用される。 As a method for producing a nonwoven fabric provided in the present invention, after forming a web by a card or airlaid nonwoven fabric production apparatus, a circular net, a short net, or a long net paper machine, a fiber entanglement by a needle punch method, a spunlace method, Alternatively, after temporary bonding with a chemical bond or Yankee dryer, unstretched polyethylene naphthalate fibers are thermocompression bonded to stretched polyethylene naphthalate fibers by calendering with a heated metal roller, resulting in unstretched polyethylene naphthalate fibers. And a method of adhering stretched polyethylene naphthalate fibers.
本発明において、延伸ポリエチレンナフタレート繊維の混合比率が低すぎると強度が低くなり、一方、未延伸ポリエチレンナフタレート繊維の混合比率が低く過ぎると、接着性が不十分であり、表面平滑性に欠ける。したがって、本発明の不織布においては、未延伸ポリエチレンナフタレート繊維と延伸ポリエチレンナフタレート繊維との混合比率は重量比率で１０：９０〜７０：３０の範囲が好ましく、２０：８０〜５０：５０の範囲がより好ましい。本発明の不織布の目付量は、細繊度であることにより、低目付けであっても強度を保持することが可能である。したがって、本発明の不織布の目付量は、好ましくは５〜３００ｇ／ｍ２あり、より好ましくは１０〜２００ｇ／ｍ２ある。 In the present invention, if the mixing ratio of the stretched polyethylene naphthalate fiber is too low, the strength is low. On the other hand, if the mixing ratio of the unstretched polyethylene naphthalate fiber is too low, the adhesiveness is insufficient and the surface smoothness is insufficient. . Therefore, in the nonwoven fabric of the present invention, the mixing ratio of unstretched polyethylene naphthalate fiber and stretched polyethylene naphthalate fiber is preferably in the range of 10:90 to 70:30, and in the range of 20:80 to 50:50, by weight. Is more preferable. Since the basis weight of the nonwoven fabric of the present invention is a fineness, the strength can be maintained even if the basis weight is low. Therefore, the basis weight of the nonwoven fabric of the present invention is preferably 5 to 300 g / m 2 , more preferably 10 to 200 g / m 2 .
以上に説明した本発明の未延伸ポリエチレンナフタレート繊維および延伸ポリエチレンナフタレート繊維は、例えば次のように製造することができる。ポリエチレンナフタレート樹脂ペレットを溶融押出機等で溶融するか、若しくは連続重合装置から溶融状態にて口金を装着したスピンパックに供給し、ストランド状で吐出して、口金下５〜２００ｍｍの位置で、紡出糸条に１０〜４０℃の空気を送風して冷却固化させた後、紡糸速度１００〜２０００ｍ／ｍｉｎで引き取って本発明の未延伸ポリエチレンナフタレート繊維を得る。得られた未延伸ポリエチレンナフタレート繊維は、紡糸装置に直結していない公知の短繊維製造用延伸機を用いて、延伸及び熱処理、油剤付与、カットを行う。具体的には、収缶した未延伸ポリエチレンナフタレート繊維を束ねてトウとし、９５℃以上の温水中で１〜数ステップに分けて延伸する。その後、８０〜２６０℃の温度で定長熱処理（例えば、スーパーヒート蒸気加熱ローラーに接触）を行い、油剤を付着させ、ロータリーカッター等で所定の繊維長にカットし、目的となる本発明の延伸ポリエチレンナフタレート繊維を得る。捲縮を付与する場合は、未延伸トウ又は延伸トウを６５℃以上に加熱して押込みクリンパーに供給すればよい。加熱温度が６５℃未満であるとＰＥＮの剛性が高いため、捲縮付与の背圧を極度に大きくする必要があり、クリンパーが不安定（ガタツキ）になりやすい。また、カッター前の油剤乾燥及び弛緩熱処理は必要に応じて実施することができる。乾燥のみを実施し、弛緩熱処理を実施しない場合は、常温空気を循環させることによってトウの風乾してやればよい。 The unstretched polyethylene naphthalate fiber and stretched polyethylene naphthalate fiber of the present invention described above can be produced, for example, as follows. Polyethylene naphthalate resin pellets are melted by a melt extruder or the like, or supplied from a continuous polymerization apparatus to a spin pack equipped with a die in a molten state, discharged in a strand shape, at a position of 5 to 200 mm below the die, The spinning yarn is blown with air at 10 to 40 ° C. to be cooled and solidified, and then taken up at a spinning speed of 100 to 2000 m / min to obtain the unstretched polyethylene naphthalate fiber of the present invention. The obtained unstretched polyethylene naphthalate fiber is stretched and heat-treated, oiled, and cut using a known stretcher for producing short fibers not directly connected to a spinning device. Specifically, bundled unstretched polyethylene naphthalate fibers are bundled into a tow, and stretched in one to several steps in warm water at 95 ° C. or higher. Then, constant-length heat treatment (for example, contact with a superheated steam heating roller) is performed at a temperature of 80 to 260 ° C., an oil agent is adhered, and the fiber is cut into a predetermined fiber length with a rotary cutter or the like. Polyethylene naphthalate fiber is obtained. When crimping is applied, unstretched tow or stretched tow may be heated to 65 ° C. or higher and supplied to the indentation crimper. When the heating temperature is less than 65 ° C., the rigidity of the PEN is high, so the back pressure for crimping needs to be extremely increased, and the crimper tends to become unstable (rattle). Moreover, the oil agent drying and relaxation heat treatment before a cutter can be implemented as needed. When only drying is performed and relaxation heat treatment is not performed, the tow may be air-dried by circulating normal temperature air.
本発明により得られる不織布は、ガラス転移温度が１１３℃、融点が２６５℃以上のものであり、耐熱性に極めて優れたポリエステル不織布であり、リサイクル性にも優れたものである。 The nonwoven fabric obtained by the present invention is a polyester nonwoven fabric having a glass transition temperature of 113 ° C. and a melting point of 265 ° C. or higher, extremely excellent in heat resistance, and excellent in recyclability.
以下、実施例により、本発明を更に具体的に説明するが、本発明は実施例によって何ら限定を受けるものではない。なお、実施例における各項目は次の方法で測定した。
（１）固有粘度（［η］）
フェノールとオルトジクロロベンゼンとの混合溶媒（重量比６：４）を溶媒として、３５℃で測定した。
（２）ガラス転移温度（Ｔｇ）、融点（Ｔｍ）
ＪＩＳ Ｋ ７１２１記載の示査走査熱量測定（ＤＳＣ）に従って、昇温速度２０℃／分の条件で測定した。
（３）単糸繊度
ＪＩＳ Ｌ １０１５：２００５ ８．５．１ Ａ法に記載の方法により測定した。
（４）繊維長
ＪＩＳ Ｌ １０１５：２００５ ８．４．１ Ｃ法に記載の方法により測定した。
（５）繊維強度、繊維伸度
ＪＩＳ Ｌ １０１５：２００５ ８．７．１ に記載の方法により測定した。
（６）捲縮数、捲縮率
ＪＩＳ Ｌ １０１５：２００５ ８．１２に記載の方法により測定した。
（７）油剤付着率
ＪＩＳ Ｌ １０１５：２００５ ８．２２ ｃ）法において、試料量を９ｇ、溶媒であるメタノールをメタノール：アセトン混合液（容量比１：１）に変更した以外は同様の方法により測定した。
（８）１８０℃乾熱収縮率
ＪＩＳ Ｌ １０１５：２００５ ８．１５ ｂ）法に記載の方法により、１８０℃で測定した。
（９）複屈折率
複屈折（Δｎ）：偏光顕微鏡によって光源にナトリウムランプを用い、試料をα−ブロムナフタリン浸漬下Ｂｅｒｅｋコンペンセーター法でレターデーションを求めて算出した。
（１０）目付量（坪量、単位面積当たりの質量）
ＪＩＳ Ｌ１９１３：１９９８ ６．２に記載の方法により測定した。
（１１）引張強度
ＪＩＳ Ｐ８１１３（紙及び板紙の引張強さ試験方法）に基づいて測定した。但し、試長は５０ｍｍ、幅は１５ｍｍとした。
Hereinafter, the present invention will be described more specifically by way of examples. However, the present invention is not limited to the examples. In addition, each item in an Example was measured with the following method.
(1) Intrinsic viscosity ([η])
Measurement was performed at 35 ° C. using a mixed solvent of phenol and orthodichlorobenzene (weight ratio 6: 4) as a solvent.
(2) Glass transition temperature (Tg), melting point (Tm)
According to the scanning scanning calorimetry (DSC) described in JIS K 7121, the temperature was measured at a temperature rising rate of 20 ° C./min.
(3) Single yarn fineness It measured by the method as described in JIS L 1015: 2005 8.5.1 A method.
(4) Fiber length Measured by the method described in JIS L 1015: 2005 8.4.1 Method C.
(5) Fiber strength, fiber elongation Measured by the method described in JIS L 1015: 2005 8.7.1.
(6) Number of crimps and crimp rate The number of crimps was measured by the method described in JIS L 1015: 2005 8.12.
(7) Oil agent adhesion rate In JIS L 1015: 2005 8.22 c) method, except that the sample amount was changed to 9 g and the solvent methanol was changed to a methanol: acetone mixture (volume ratio 1: 1). It was measured.
(8) 180 degreeC dry heat shrinkage rate It measured at 180 degreeC by the method as described in JIS L1015: 2005 8.15 b) method.
(9) Birefringence index Birefringence (Δn): A sodium lamp was used as a light source with a polarizing microscope, and the sample was calculated by obtaining the retardation by the Berek compensator method under α-bromonaphthalene immersion.
(10) Weight per unit area (basis weight, mass per unit area)
It was measured by the method described in JIS L1913: 1998 6.2.
(11) Tensile strength Measured based on JIS P8113 (Test method for tensile strength of paper and paperboard). However, the test length was 50 mm and the width was 15 mm.
［実施例１−１］
融点２６４℃、［η］＝０．５１ｄＬ／ｇのポリエチレンナフタレート樹脂のペレットを１７０℃で５時間乾燥して溶融押出機に供給し、孔径０．１２ｍｍの丸孔キャピラリーを７２孔有する公知のポリエステル用口金を用いて、溶融吐出させた。溶融後の樹脂温度は３１８℃、吐出量は１０ｇ／分であった。これを口金下５７ｍｍで紡出糸条を２７℃の冷風で冷却した後、紡糸速度１２５０ｍ／分で捲き取り、未延伸糸条を得た。
次いで、公知の短繊維延伸機に供給するが、延伸や定長熱処理、捲縮付与は行わず、ドラフト１．０倍のまま、ポリエーテルポリエステル油剤（高松油脂（株）製ＹＭ−８０）のエマルジョンを油剤純分付着率０．５質量％となるように付着し、ロータリーカッターにて繊維長５ｍｍにカットし、目的とする未延伸ポリエチレンナフタレート短繊維を得た。得られた物性を表１に示した。
[Example 1-1]
A polyethylene naphthalate resin pellet having a melting point of 264 ° C. and [η] = 0.51 dL / g is dried at 170 ° C. for 5 hours and supplied to a melt extruder, and has a known number of 72 round hole capillaries having a pore diameter of 0.12 mm. Using a polyester base, it was melted and discharged. The resin temperature after melting was 318 ° C., and the discharge rate was 10 g / min. The spun yarn was cooled with cold air at 27 ° C. at 57 mm below the base, and then wound at a spinning speed of 1250 m / min to obtain an undrawn yarn.
Next, it is supplied to a known short fiber drawing machine, but is not subjected to drawing, constant-length heat treatment, and crimping, and is a polyether polyester oil (YM-80 manufactured by Takamatsu Yushi Co., Ltd.) with a draft of 1.0 times. The emulsion was attached so as to have an oil agent pure content adhesion rate of 0.5% by mass, and was cut into a fiber length of 5 mm with a rotary cutter to obtain a desired unstretched polyethylene naphthalate short fiber. The obtained physical properties are shown in Table 1.
［実施例１−２］
実施例１−１により得た未延伸糸条を束ねてトウとし、９８℃温水中で２．１１倍、更に９８℃温水中で１．１倍に２段延伸し、セットローラー（スーパーヒート蒸気加熱ローラー）によりトウ温度１１０℃に定長熱処理（ドラフト１．００倍）し、ポリエーテルポリエステル系油剤（高松油脂（株）製ＹＭ−８０）のエマルジョンを油剤純分付着率０．５質量％となるように付着し、ロータリーカッターにて繊維長５ｍｍにカットし、目的とする延伸ポリエチレンナフタレート短繊維を得た。得られた物性を表１に示した。
[Example 1-2]
The unstretched yarn obtained in Example 1-1 was bundled to make a tow, and stretched in two stages at 2.11 times in 98 ° C. warm water and further 1.1 times in 98 ° C. warm water. Heating is performed at a tow temperature of 110 ° C. with a heating roller (draft 1.00 times), and an emulsion of a polyether polyester oil (YM-80 manufactured by Takamatsu Oils & Fats Co., Ltd.) is 0.5% by mass. Then, it was cut into a fiber length of 5 mm with a rotary cutter to obtain a target stretched polyethylene naphthalate short fiber. The obtained physical properties are shown in Table 1.
［実施例１−３］（抄紙）
実施例１−１の未延伸短繊維と実施例１−２の延伸短繊維を４０：６０の質量比率でミキサーにて攪拌した後、手漉き抄紙を行い、ロータリー乾燥機で１４０℃×２分間乾燥し、目付け２０ｇ／ｍ２の抄上げ紙を得た。抄上げ紙を金属／ペーパーロール系カレンダー加工機で、金属ロール表面温度２００℃、線圧１２０ｋｇ／ｃｍの条件下で圧着し、厚さ０．０２８ｍｍの不織布を得た。抄上げ紙裂断長及びカレンダー後の裂断長を表２に示した。
[Example 1-3] (papermaking)
After stirring the unstretched short fiber of Example 1-1 and the stretched short fiber of Example 1-2 with a mixer at a mass ratio of 40:60, hand-made paper is made and dried at 140 ° C. for 2 minutes with a rotary dryer. Thus, a paper with a basis weight of 20 g / m 2 was obtained. The paper-making paper was press-bonded with a metal / paper roll system calendering machine under conditions of a metal roll surface temperature of 200 ° C. and a linear pressure of 120 kg / cm to obtain a nonwoven fabric having a thickness of 0.028 mm. Table 2 shows the paper breaking length and the paper breaking length after calendering.
［比較例１−１］
融点２６４℃、［η］＝０．５１ｄＬ／ｇのポリエチレンナフタレート樹脂のペレットを１７０℃で５時間乾燥して溶融押出機に供給し、孔径０．２８ｍｍの丸孔キャピラリーを１３０５孔有する公知のポリエステル用口金を用いて、溶融吐出させた。溶融後の樹脂温度は３１０℃、吐出量は２９０ｇ／分であった。これを口金下２１ｍｍで紡出糸条を２７℃の冷風で冷却した後、紡糸速度１０００ｍ／分で捲き取り、未延伸糸条を得た。
次いで、公知の短繊維延伸機に供給するが、延伸や定長熱処理、捲縮付与は行わず、ドラフト１．０倍のまま、ポリエーテルポリエステル油剤（高松油脂（株）製ＹＭ−８０）のエマルジョンを油剤純分付着率０．５質量％となるように付着し、ロータリーカッターにて繊維長５ｍｍにカットし、目的とする未延伸ポリエチレンナフタレート短繊維を得た。得られた物性を表１に示した。
[Comparative Example 1-1]
Polyethylene naphthalate resin pellets having a melting point of 264 ° C. and [η] = 0.51 dL / g are dried at 170 ° C. for 5 hours and supplied to a melt extruder, and 1305 holes having a round hole capillary with a hole diameter of 0.28 mm are known. Using a polyester base, it was melted and discharged. The resin temperature after melting was 310 ° C., and the discharge rate was 290 g / min. The spun yarn was cooled with cold air at 27 ° C. at 21 mm below the base, and then wound at a spinning speed of 1000 m / min to obtain an undrawn yarn.
Next, it is supplied to a known short fiber drawing machine, but is not subjected to drawing, constant-length heat treatment, and crimping, and is a polyether polyester oil (YM-80 manufactured by Takamatsu Yushi Co., Ltd.) with a draft of 1.0 times. The emulsion was attached so as to have an oil agent pure content adhesion rate of 0.5% by mass, and was cut into a fiber length of 5 mm with a rotary cutter to obtain a desired unstretched polyethylene naphthalate short fiber. The obtained physical properties are shown in Table 1.
［比較例１−２］
比較例１−１により得た未延伸糸条を束ねてトウとし、９８℃温水中で２．１１倍、更に９８℃温水中で１．１倍に２段延伸し、セットローラー（スーパーヒート蒸気加熱ローラー）によりトウ温度１１０℃に定長熱処理（ドラフト１．００倍）し、ポリエーテルポリエステル系油剤（高松油脂（株）製ＹＭ−８０）のエマルジョンを油剤純分付着率０．５質量％となるように付着し、ロータリーカッターにて繊維長５ｍｍにカットし、目的とする延伸ポリエチレンナフタレート短繊維を得た。得られた物性を表１に示した。
[Comparative Example 1-2]
The unstretched yarn obtained in Comparative Example 1-1 was bundled into a tow, and stretched in two stages to 2.11 times in 98 ° C. warm water and further 1.1 times in 98 ° C. warm water. Heating is performed at a tow temperature of 110 ° C. with a heating roller (draft 1.00 times), and an emulsion of a polyether polyester oil (YM-80 manufactured by Takamatsu Oils & Fats Co., Ltd.) is 0.5% by mass. Then, it was cut into a fiber length of 5 mm with a rotary cutter to obtain a target stretched polyethylene naphthalate short fiber. The obtained physical properties are shown in Table 1.
［比較例１−３］（抄紙）
比較例１−１の未延伸短繊維と比較例１−２の延伸短繊維を４０：６０の質量比率でミキサーにて攪拌した後、手漉き抄紙を行い、ロータリー乾燥機で１４０℃×２分間乾燥し、目付け５０ｇ／ｍ２の抄上げ紙を得た。抄上げ紙を金属／ペーパーロール系カレンダー加工機で、金属ロール表面温度２００℃、線圧１２０ｋｇ／ｃｍの条件下で圧着し、厚さ０．０２８ｍｍの不織布を得た。カレンダー後の引張強度を表２に示した。
[Comparative Example 1-3] (papermaking)
After stirring the unstretched short fiber of Comparative Example 1-1 and the stretched short fiber of Comparative Example 1-2 at a mass ratio of 40:60, hand-made paper is made and dried at 140 ° C. for 2 minutes using a rotary dryer. Thus, a paper with a basis weight of 50 g / m 2 was obtained. The paper-making paper was press-bonded with a metal / paper roll system calendering machine under conditions of a metal roll surface temperature of 200 ° C. and a linear pressure of 120 kg / cm to obtain a nonwoven fabric having a thickness of 0.028 mm. Table 2 shows the tensile strength after calendering.
本発明によれば、従来検討されてきたポリエチレンナフタレート不織布に比べ、強度が著しく向上し、実用に耐えうる耐熱性短繊維不織布の提供を可能とする。その用途は、バグフィルター、Ｆ種以上の電気絶縁材料、電池セパレーター、コンデンサー（スーパーキャパシター）用セパレーター、天井材やフロアマット、エンジン用フィルター、オイル用フィルター等の耐熱性、耐薬品性が要求される車輌用不織布素材など、幅広く適用されることが期待され、産業上の意義は大きい。 According to the present invention, it is possible to provide a heat-resistant short fiber nonwoven fabric that has significantly improved strength and can withstand practical use as compared with a polyethylene naphthalate nonwoven fabric that has been conventionally studied. Its applications require heat resistance and chemical resistance such as bag filters, F-type and higher electrical insulation materials, battery separators, condenser (supercapacitor) separators, ceiling materials and floor mats, engine filters, oil filters, etc. It is expected to be widely applied, such as non-woven materials for vehicles.
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| JP2010263722A JP2012112079A (en) | 2010-11-26 | 2010-11-26 | Polyethylene naphthalate fiber and staple fiber nonwoven fabric therefrom |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014133959A (en) * | 2013-01-10 | 2014-07-24 | Japan Vilene Co Ltd | Nonwoven fabric for printing and printed nonwoven fabric |
| WO2018139651A1 (en) * | 2017-01-30 | 2018-08-02 | 帝人フロンティア株式会社 | Method for producing uncrimped short fibers and wet-laid nonwoven fabric comprising obtained uncrimped short fibers |
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|---|---|---|---|---|
| JP2000118163A (en) * | 1998-10-19 | 2000-04-25 | Toray Ind Inc | Unwoven fabric for heat sensitive stencil printing original paper |
| JP2006207085A (en) * | 2005-01-31 | 2006-08-10 | Teijin Techno Products Ltd | Nonwoven fabric |
| WO2008130019A1 (en) * | 2007-04-17 | 2008-10-30 | Teijin Fibers Limited | Wet-laid non-woven fabric and filter |
| JP2010100963A (en) * | 2008-10-23 | 2010-05-06 | Teijin Fibers Ltd | Method for producing polyethylene naphthalate fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000118163A (en) * | 1998-10-19 | 2000-04-25 | Toray Ind Inc | Unwoven fabric for heat sensitive stencil printing original paper |
| JP2006207085A (en) * | 2005-01-31 | 2006-08-10 | Teijin Techno Products Ltd | Nonwoven fabric |
| WO2008130019A1 (en) * | 2007-04-17 | 2008-10-30 | Teijin Fibers Limited | Wet-laid non-woven fabric and filter |
| JP2010100963A (en) * | 2008-10-23 | 2010-05-06 | Teijin Fibers Ltd | Method for producing polyethylene naphthalate fiber |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014133959A (en) * | 2013-01-10 | 2014-07-24 | Japan Vilene Co Ltd | Nonwoven fabric for printing and printed nonwoven fabric |
| WO2018139651A1 (en) * | 2017-01-30 | 2018-08-02 | 帝人フロンティア株式会社 | Method for producing uncrimped short fibers and wet-laid nonwoven fabric comprising obtained uncrimped short fibers |
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