EP3779004B1 - Fabric and textile product - Google Patents
Fabric and textile product Download PDFInfo
- Publication number
- EP3779004B1 EP3779004B1 EP19782317.2A EP19782317A EP3779004B1 EP 3779004 B1 EP3779004 B1 EP 3779004B1 EP 19782317 A EP19782317 A EP 19782317A EP 3779004 B1 EP3779004 B1 EP 3779004B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fiber
- aromatic polyamide
- meta
- cloth
- cloth according
- 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.)
- Active
Links
- 239000004744 fabric Substances 0.000 title claims description 111
- 239000004753 textile Substances 0.000 title description 2
- 239000000835 fiber Substances 0.000 claims description 190
- 238000000034 method Methods 0.000 claims description 70
- 239000004760 aramid Substances 0.000 claims description 65
- 229920003235 aromatic polyamide Polymers 0.000 claims description 65
- 229920002821 Modacrylic Polymers 0.000 claims description 23
- 238000005406 washing Methods 0.000 claims description 20
- 229920002972 Acrylic fiber Polymers 0.000 claims description 19
- 125000003118 aryl group Chemical group 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- -1 aromatic dicarboxylic acid halide Chemical class 0.000 claims description 12
- 239000013557 residual solvent Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 150000004984 aromatic diamines Chemical class 0.000 claims description 6
- 238000005452 bending Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000005647 linker group Chemical group 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- 239000001023 inorganic pigment Substances 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 19
- 238000009987 spinning Methods 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 238000004043 dyeing Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 12
- 229920000297 Rayon Polymers 0.000 description 10
- 238000005345 coagulation Methods 0.000 description 10
- 230000015271 coagulation Effects 0.000 description 10
- 239000010419 fine particle Substances 0.000 description 10
- 238000012545 processing Methods 0.000 description 10
- 239000002964 rayon Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 9
- 150000001408 amides Chemical class 0.000 description 8
- 238000009991 scouring Methods 0.000 description 7
- 125000002091 cationic group Chemical group 0.000 description 6
- 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 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000004677 Nylon Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003063 flame retardant Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 229920001778 nylon Polymers 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000009941 weaving Methods 0.000 description 5
- LEBQTCCCNMTXSF-UHFFFAOYSA-N (2,5-dimethylphenyl)methanol Chemical compound CC1=CC=C(C)C(CO)=C1 LEBQTCCCNMTXSF-UHFFFAOYSA-N 0.000 description 4
- YCGKJPVUGMBDDS-UHFFFAOYSA-N 3-(6-azabicyclo[3.1.1]hepta-1(7),2,4-triene-6-carbonyl)benzamide Chemical compound NC(=O)C1=CC=CC(C(=O)N2C=3C=C2C=CC=3)=C1 YCGKJPVUGMBDDS-UHFFFAOYSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012805 post-processing Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000009999 singeing Methods 0.000 description 3
- 210000004243 sweat Anatomy 0.000 description 3
- BWRBVBFLFQKBPT-UHFFFAOYSA-N (2-nitrophenyl)methanol Chemical compound OCC1=CC=CC=C1[N+]([O-])=O BWRBVBFLFQKBPT-UHFFFAOYSA-N 0.000 description 2
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- OIGWAXDAPKFNCQ-UHFFFAOYSA-N 4-isopropylbenzyl alcohol Chemical compound CC(C)C1=CC=C(CO)C=C1 OIGWAXDAPKFNCQ-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004696 Poly ether ether ketone Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- QSRFYFHZPSGRQX-UHFFFAOYSA-N benzyl(tributyl)azanium Chemical compound CCCC[N+](CCCC)(CCCC)CC1=CC=CC=C1 QSRFYFHZPSGRQX-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 description 2
- VBVCYAZECWLFHP-UHFFFAOYSA-N dodecyl benzenesulfonate;tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC.CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 VBVCYAZECWLFHP-UHFFFAOYSA-N 0.000 description 2
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 229920002530 polyetherether ketone Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000069 polyphenylene sulfide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002166 wet spinning Methods 0.000 description 2
- ICJVQAHPHKYCNU-UHFFFAOYSA-N (2-ethoxyphenyl)methanol Chemical compound CCOC1=CC=CC=C1CO ICJVQAHPHKYCNU-UHFFFAOYSA-N 0.000 description 1
- WYLYBQSHRJMURN-UHFFFAOYSA-N (2-methoxyphenyl)methanol Chemical compound COC1=CC=CC=C1CO WYLYBQSHRJMURN-UHFFFAOYSA-N 0.000 description 1
- ZSRDNPVYGSFUMD-UHFFFAOYSA-N (3-chlorophenyl)methanol Chemical compound OCC1=CC=CC(Cl)=C1 ZSRDNPVYGSFUMD-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- YDYSEBSNAKCEQU-UHFFFAOYSA-N 2,3-diamino-n-phenylbenzamide Chemical compound NC1=CC=CC(C(=O)NC=2C=CC=CC=2)=C1N YDYSEBSNAKCEQU-UHFFFAOYSA-N 0.000 description 1
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical compound NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 1
- MYEWQUYMRFSJHT-UHFFFAOYSA-N 2-(2-aminophenyl)sulfonylaniline Chemical compound NC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1N MYEWQUYMRFSJHT-UHFFFAOYSA-N 0.000 description 1
- LNTGGPJSADTYSG-UHFFFAOYSA-N 2-(2-carbonochloridoylphenoxy)benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1OC1=CC=CC=C1C(Cl)=O LNTGGPJSADTYSG-UHFFFAOYSA-N 0.000 description 1
- KWHVBVJDKLSOTB-UHFFFAOYSA-N 2-(3-methylphenyl)ethanol Chemical compound CC1=CC=CC(CCO)=C1 KWHVBVJDKLSOTB-UHFFFAOYSA-N 0.000 description 1
- DAVFJRVIVZOKKS-UHFFFAOYSA-N 2-(4-methylphenyl)ethanol Chemical compound CC1=CC=C(CCO)C=C1 DAVFJRVIVZOKKS-UHFFFAOYSA-N 0.000 description 1
- UIWFKZBONQGUDI-UHFFFAOYSA-M 2-dodecylbenzenesulfonate;tributyl(tetradecyl)phosphanium Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC UIWFKZBONQGUDI-UHFFFAOYSA-M 0.000 description 1
- WEEOFHJAGVFCFD-UHFFFAOYSA-N 2-n-chlorobenzene-1,2-diamine Chemical compound NC1=CC=CC=C1NCl WEEOFHJAGVFCFD-UHFFFAOYSA-N 0.000 description 1
- RPKCLSMBVQLWIN-UHFFFAOYSA-N 2-n-methylbenzene-1,2-diamine Chemical compound CNC1=CC=CC=C1N RPKCLSMBVQLWIN-UHFFFAOYSA-N 0.000 description 1
- QGCCNWSXJHGUNL-UHFFFAOYSA-N 3-iodo-benzyl alcohol Chemical compound OCC1=CC=CC(I)=C1 QGCCNWSXJHGUNL-UHFFFAOYSA-N 0.000 description 1
- QDBOAKPEXMMQFO-UHFFFAOYSA-N 4-(4-carbonochloridoylphenyl)benzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=C(C(Cl)=O)C=C1 QDBOAKPEXMMQFO-UHFFFAOYSA-N 0.000 description 1
- LHSXSRQUGCHBPG-UHFFFAOYSA-N 4-(aminomethoxy)aniline Chemical compound NCOC1=CC=C(N)C=C1 LHSXSRQUGCHBPG-UHFFFAOYSA-N 0.000 description 1
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 1
- IWRVPXDHSLTIOC-UHFFFAOYSA-N 4-phenyldiazenylbenzene-1,3-diamine Chemical compound NC1=CC(N)=CC=C1N=NC1=CC=CC=C1 IWRVPXDHSLTIOC-UHFFFAOYSA-N 0.000 description 1
- HPFMWXQXAHHFAA-UHFFFAOYSA-N 5-chlorobenzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC(Cl)=CC(C(Cl)=O)=C1 HPFMWXQXAHHFAA-UHFFFAOYSA-N 0.000 description 1
- CGXXBHCRXCEKCP-UHFFFAOYSA-N 5-methoxybenzene-1,3-dicarbonyl chloride Chemical compound COC1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 CGXXBHCRXCEKCP-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920006282 Phenolic fiber Polymers 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229920006221 acetate fiber Polymers 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- OORRQYZWSVJKSO-UHFFFAOYSA-N bicyclo[4.4.1]undeca-1,3,5,7,9-pentaene Chemical compound C1=CC=C(C2)C=CC=CC2=C1 OORRQYZWSVJKSO-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- XWTOMWARSPYOAY-UHFFFAOYSA-N dodecyl benzenesulfonate;tetraphenylphosphanium Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1.C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XWTOMWARSPYOAY-UHFFFAOYSA-N 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- KTUVYMAZYSSBKC-UHFFFAOYSA-N hexyl benzenesulfonate Chemical compound CCCCCCOS(=O)(=O)C1=CC=CC=C1 KTUVYMAZYSSBKC-UHFFFAOYSA-N 0.000 description 1
- ASTWQNQEEBYIKI-UHFFFAOYSA-N hexyl benzenesulfonate tetrabutylphosphanium Chemical compound C(CCCCC)OS(=O)(=O)C1=CC=CC=C1.C(CCC)[P+](CCCC)(CCCC)CCCC ASTWQNQEEBYIKI-UHFFFAOYSA-N 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000000077 insect repellent Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229920006277 melamine fiber Polymers 0.000 description 1
- MPXAYYWSDIKNTP-UHFFFAOYSA-N n-(2-aminophenyl)acetamide Chemical compound CC(=O)NC1=CC=CC=C1N MPXAYYWSDIKNTP-UHFFFAOYSA-N 0.000 description 1
- VIUHYPPHBQZSPF-UHFFFAOYSA-N naphthalene-1,4-dicarbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=C(C(Cl)=O)C2=C1 VIUHYPPHBQZSPF-UHFFFAOYSA-N 0.000 description 1
- NZZGQZMNFCTNAM-UHFFFAOYSA-N naphthalene-2,6-dicarbonyl chloride Chemical compound C1=C(C(Cl)=O)C=CC2=CC(C(=O)Cl)=CC=C21 NZZGQZMNFCTNAM-UHFFFAOYSA-N 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical compound C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 239000005080 phosphorescent agent Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 231100000075 skin burn Toxicity 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D1/00—Woven fabrics designed to make specified articles
- D03D1/0035—Protective fabrics
-
- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/20—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads
- D03D15/283—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the material of the fibres or filaments constituting the yarns or threads synthetic polymer-based, e.g. polyamide or polyester fibres
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/08—Heat resistant; Fire retardant
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/08—Heat resistant; Fire retardant
- A41D31/085—Heat resistant; Fire retardant using layered materials
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/04—Pigments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/06—Dyes
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
- D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/16—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated carboxylic acids or unsaturated organic esters, e.g. polyacrylic esters, polyvinyl acetate
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/40—Modacrylic fibres, i.e. containing 35 to 85% acrylonitrile
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
- D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides
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- D—TEXTILES; PAPER
- D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
- D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
- D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
- D02G3/44—Yarns or threads characterised by the purpose for which they are designed
- D02G3/443—Heat-resistant, fireproof or flame-retardant yarns or threads
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/40—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads
- D03D15/47—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the structure of the yarns or threads multicomponent, e.g. blended yarns or threads
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/513—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads heat-resistant or fireproof
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/533—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads antistatic; electrically conductive
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- D—TEXTILES; PAPER
- D03—WEAVING
- D03D—WOVEN FABRICS; METHODS OF WEAVING; LOOMS
- D03D15/00—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used
- D03D15/50—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads
- D03D15/54—Woven fabrics characterised by the material, structure or properties of the fibres, filaments, yarns, threads or other warp or weft elements used characterised by the properties of the yarns or threads coloured
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D10B2321/10—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
- D10B2321/101—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide modacrylic
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2331/00—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products
- D10B2331/02—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides
- D10B2331/021—Fibres made from polymers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polycondensation products polyamides aromatic polyamides, e.g. aramides
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2401/00—Physical properties
- D10B2401/16—Physical properties antistatic; conductive
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- D—TEXTILES; PAPER
- D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
- D10B2501/00—Wearing apparel
- D10B2501/04—Outerwear; Protective garments
Definitions
- the present invention relates to a cloth having extremely excellent flame retardancy and having excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, and a fiber product.
- US2013/055491A1 relates to a yarn having high moisture regain for use in arc and flame protection and fabrics and garments containing the yarn.
- US2014/026303A1 relates to a fiber blend, yarn, fabric, and/or garment suitable for use in arc and flame protection.
- JP2014/210985A relates to a spun yarn having a protective ability against flame, heat, arc, etc., having high dyeing fastness, being difficult to yellow over time, and having excellent moisture absorption and release properties.
- JP2017/008454A relates to a fabric and a textile product excellent in deepness of color, hardly causing skin burn.
- JP2009/221632A relates to a sheath-core conjugate conductive acrylic fiber containing conductive fine particles in the core part at a high concentration and having an optimized core/sheath ratio, thereby establishing compatibility between high electric conductivity and stable processability.
- an object of the invention is to provide a cloth which is advantageous in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, preferably in that the whole of the cloth can be uniformly dyed, and a fiber product.
- the present inventors have conducted extensive and intensive studies with a view toward achieving the above-mentioned object. As a result, it has been found that, by appropriately selecting the type of the fiber constituting the cloth and the like, there can be obtained a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand, but also in that the whole of the cloth can be uniformly dyed, and further extensive and intensive studies have been made, and the present invention has been completed.
- a cloth comprising a spun yarn which comprises a meta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber, wherein the conductive fiber is an acrylic fiber.
- the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more, based on the weight of the spun yarn. Further, it is preferred that the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more, based on the weight of the spun yarn. It is preferred that the spun yarn contains the conductive fiber in an amount of 1% by weight or more, based on the weight of the spun yarn.
- the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber. It is preferred that the meta-type wholly aromatic polyamide fiber has a residual solvent content of 0.1% by weight or less. It is preferred that the meta-type wholly aromatic polyamide fiber has a crystallinity in the range of from 15 to 25%.
- a meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is an aromatic polyamide having an aromatic polyamide skeleton comprising repeating structural units representedby the formula (1) below, wherein an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component is copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide: -(NH-Ar1-NH-CO-Ar1-CO)- Formula (1) wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction.
- the aromatic diamine is the following formula (2) or (3)
- the aromatic dicarboxylic acid halide is the following formula (4) or (5): H 2 N-Ar2-NH 2 Formula (2) H 2 N-Ar2-Y-Ar2-NH 2 Formula (3) XOC-Ar3-COX Formula (4) XOC-Ar3-Y-Ar3-COX Formula (5) wherein Ar2 represents a divalent aromatic group different from Ar1, Ar3 represents a divalent aromatic group different from Ar1, Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom.
- the meta-type wholly aromatic polyamide fiber further contains an organic dye, an organic pigment, or an inorganic pigment.
- the conductive fiber is an acrylic fiber. It is preferred that the modacrylic fiber and the conductive fiber are dyed with the same dye.
- the cloth of the invention it is preferred that the cloth contains an ultraviolet light absorber and/or a reflective agent. Further, it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m 2 . It is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025: 2000 A method. It is preferred that the cloth has a carbonized area of 30 cm 2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077.
- the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 Amethod (cantilever) . It is preferred that the cloth has an antistaticity of 7.0 ⁇ C or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
- a fiber product using the above-mentioned cloth which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing.
- the cloth of the invention comprises a spun yarn which comprises ameta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber.
- the meta-type wholly aromatic polyamide fiber used in the invention is a fiber formed from a polymer in which 85 mol% or more of the repeating units are m-phenyleneisophthalamide.
- the meta-type wholly aromatic polyamide may be a copolymer containing a third component in an amount in the range of less than 15 mol%.
- the meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and there is preferably used the meta-type wholly aromatic polyamide having, in terms of the degree of polymerization of the polymer, an intrinsic viscosity (I.V.) in the range of from 1.3 to 1.9 dl/g, as measured in the form of an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g/100 ml.
- I.V. intrinsic viscosity
- the meta-type wholly aromatic polyamide may contain an alkylbenzenesulfonic acid onium salt.
- alkylbenzenesulfonic acid onium salts include compounds, such as tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributyltetradecylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate.
- tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate because they are easily available and have excellent thermal stability as well as high solubility in N-methyl-2-pyrrolidone.
- the amount of the alkylbenzenesulfonic acid onium salt contained is preferably 2.5 mol% or more, preferably in the range of from 3.0 to 7.0 mol%, based on the mole of the poly-m-phenyleneisophthalamide.
- an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component can be copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide: -(NH-Ar1-NH-CO-Ar1-CO)- Formula (1) wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction.
- aromatic diamines which are represented by the formula (2) or (3), and which can be copolymerized as a third component, include p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, acetylphenylenediamine, aminoanisidine, benzidine, bis(aminophenyl) ether, bis(aminophenyl) sulfone, diaminobenzanilide, and diaminoazobenzene.
- aromatic dicarboxylic acid dichlorides represented by the formula (4) or (5) include terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, and bis(chlorocarbonylphenyl) ether.
- Ar2 represents a divalent aromatic group different from Ar1
- Ar3 represents a divalent aromatic group different from Ar1
- Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group
- X represents a halogen atom.
- the crystallinity of the meta-type wholly aromatic polyamide fiber is preferably 5 to 35% because the absorption for a dye is excellent such that an intended color can be easily achieved even when using the dye in a reduced amount or even under poor dyeing conditions. Further, the crystallinity is more preferably 15 to 25% because localization of a dye in the surface is unlikely to occur and a high resistance to discoloration and color fading is obtained and further dimensional stability required for the practical use can be secured.
- the residual solvent content of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less (preferably 0.001 to 0.1% by weight) because excellent flame retardancy of the meta-type wholly aromatic polyamide fiber is not sacrificed.
- the meta-type wholly aromatic polyamide fiber can be produced by the method mentioned below, and, particularly by the below-mentioned method, the crystallinity and residual solvent content in the above-mentioned respective ranges can be achieved.
- the polymerization method for the meta-type wholly aromatic polyamide polymer there is no particular limitation, and, for example, the solution polymerization method or interfacial polymerization method described in JP-B-35-14399 , U.S. Patent No. 3,360,595 , JP-B-47-10863 , or the like may be used.
- the spinning solution is not particularly limited, but an amide-solvent solution containing an aromatic copolyamide polymer obtained by the above-mentioned solution polymerization, interfacial polymerization, or the like may be used, or a solution obtained by isolating the polymer from the above-mentioned polymerization solution and dissolving the polymer in an amide solvent may be used.
- amide solvents used include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, and especially preferred is N,N-dimethylacetamide.
- the copolymerized aromatic polyamide polymer solution obtained as mentioned above further contains an alkali metal salt or an alkaline earth metal salt
- the solution is stabilized and can be advantageously used in a higher concentration at low temperatures.
- the amount of the alkali metal salt and alkaline earth metal salt is preferably 1% by weight or less, more preferably 0.1% by weight or less, based on the mass of the polymer solution.
- the above-obtained spinning solution (meta-type wholly aromatic polyamide polymer solution) is discharged into a coagulation liquid so as to undergo coagulation.
- the spinning apparatus there is no particular limitation, and a conventionally known wet spinning apparatus can be used. Further, with respect to the number of spinning holes of a spinning nozzle, the arrangement of the holes, the form of the hole, and the like, there is no particular limitation as long as wet spinning can be stably made, and, for example, a multihole spinning nozzle for rayon yarn having 1,000 to 30,000 holes and having a spinning hole diameter of 0.05 to 0.2 mm, or the like may be used.
- the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) being discharged from a spinning nozzle is suitably in the range of from 20 to 90°C.
- an aqueous solution containing substantially no inorganic salt and having an amide solvent, preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C is used.
- the amide solvent (preferably NMP) concentration is less than 45% by weight, a structure having a thick skin is disadvantageously formed, so that the washing efficiency in the washing step is lowered, making it difficult to reduce the residual solvent content of the fiber.
- the amide solvent (preferably NMP) concentration is more than 60% by weight, coagulation throughout the inside of the fiber cannot be achieved, making it difficult to reduce the residual solvent content of the fiber.
- the time for immersing the fiber in the coagulation bath is suitably in the range of from 0.1 to 30 seconds.
- the fiber is subjected to drawing at a draw ratio of 3 to 4 times. After drawing, the resultant fiber is well washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30°C and further through a warm water bath at 50 to 70°C.
- an aqueous solution having an amide solvent preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C.
- the fiber after being washed is subjected to dry heat treatment at a temperature of 270 to 290°C, obtaining a meta-type wholly aromatic aramid fiber which satisfies the crystallinity and residual solvent content in the above-mentioned respective ranges.
- the fiber is preferably in the form of a short fiber having a fiber length of 25 to 200 mm in view of mixing with another fiber.
- the single fiber fineness is preferably in the range of from 1 to 5 dtex.
- the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more (more preferably 5 to 50% by weight), based on the weight of the spun yarn.
- the amount of the meta-type wholly aromatic polyamide fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in flame retardancy.
- the modacrylic fiber is a fiber formed from a linear synthetic polymer comprising repeating units for acrylonitrile group in an amount of 35 to less than 85% by weight, as measured in accordance with JIS L0204-2 (2001).
- the modacrylic fiber is advantageous in that woven fabric formed from the modacrylic fiber is wrinkle resistant and excellent in fireproofness, chemical resistance, beautiful appearance, hand, washing shrinkage resistance, and the like.
- the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more (more preferably 50 to 90% by weight, especially preferably 60 to 80% by weight), based on the weight of the spun yarn.
- the amount of the modacrylic fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in hand, washing shrinkage resistance, and the like.
- the spun yarn contains not only the meta-type wholly aromatic polyamide fiber and modacrylic fiber but also a conductive fiber.
- the cloth of the invention contains the meta-type wholly aromatic polyamide fiber and an acrylic fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed. In this case, it is preferred that the meta-type wholly aromatic polyamide fiber and the conductive fiber are dyed the same color.
- the color difference between the meta-type wholly aromatic polyamide fiber and the conductive fiber, in terms of ⁇ E, is preferably 3 or less.
- the acrylic fiber preferred is a fiber having conductive carbon incorporated into an acrylic fiber, a sheath-core manner conjugate fiber comprising a core portion containing conductive fine particles and a sheath portion containing no conductive fine particle, or the like.
- a sheath-core manner conjugate fiber or an eccentric sheath-core manner conjugate fiber having a sheath portion comprising an acryl containing no conductive fine particle, and a core portion comprising a conductive carbon-containing polymer, or the like.
- an acrylic fiber described in JP-A-2009-221632 is preferred.
- a sheath-core manner conductive acrylic fiber comprising a core portion containing conductive fine particles and a sheath portion containing no conductive fine particle, wherein the acrylic fiber has a core-sheath ratio of 15/85 to 50/50, the content of the conductive fine particles in the core portion is 20 to 60% by mass, and the acrylic fiber has a single fiber specific resistance of 10 1 to 10 6 ⁇ cm.
- the fiber may be in the form of either a continuous fiber (multifilament) or a short fiber.
- a short fiber having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) is preferred.
- the single fiber fineness is preferably in the range of from 1 to 5 dtex.
- the spun yarn contains the conductive fiber in an amount of 1% by weight or more (more preferably 1 to 5% by weight), based on the weight of the spun yarn.
- the weight percentage of the conductive fiber is smaller than the above range, there is a possibility that the cloth becomes poor in antistatic properties.
- the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber, but the spun yarn may further contain an additional fiber.
- a flame-retardant fiber such as a para-type wholly aromatic polyamide fiber, a wholly aromatic polyester fiber, apolybenzoxazole (PBO) fiber, apolybenzimidazole (PBI) fiber, apolybenzothiazole (PBTZ) fiber, apolyimide (PI) fiber, a polysulfonamide (PSA) fiber, a polyether ether ketone (PEEK) fiber, apolyetherimide (PEI) fiber, apolyarylate (PAr) fiber, a melamine fiber, a phenolic fiber, a fluorine fiber, or a polyphenylene sulfide (PPS) fiber, maybe contained in the spun yarn.
- PBO apolybenzoxazole
- PBI apolybenzimidazole
- PBTZ apo
- a cellulose fiber, a polyolefin fiber, an acrylic fiber, a rayon fiber, a cotton fiber, an animal hair fiber, a polyurethane fiber, a polyvinyl chloride fiber, a polyvinylidene chloride fiber, an acetate fiber, a polycarbonate fiber, or the like is contained in the spun yarn, water absorption properties, dyeing properties, comfortability to wear, or the like is advantageously imparted to the cloth.
- the method for producing the cloth there is no particular limitation, and any known method can be used.
- spun yarns of the above-mentioned fibers are mixed to obtain a spun yarn, and then the spun yarn in the form of a single yarn or a two folded yarn is woven using a rapier loom or the like into a weave structure, such as twill weave or plain weave.
- the cloth is constituted solely by the spun yarn, but the spun yarn may be interwoven or interknitted with the above-mentioned additional fiber.
- post-processing steps include steps, such as scouring, drying, relaxation, singeing, dyeing, and a function imparting treatment.
- the cloth is subjected to dyeing processing using a dye bath containing the above-mentioned cationic dye.
- a method can be preferably employed in which the cloth is dyed at 115 to 135°C and then subj ected to reduction treatment, and dried, or the like , but the method is not limited to this.
- a carrier is preferably used, and it is preferred that the cloth is subjected to dyeing treatment in the bath of cationic dye which is the same bath as the carrier . Further, when the cloth is treated with a special surfactant before subjected to cationic dyeing, the cloth can be dyed deep color in the open width dyeing.
- the carrier is, for example, at least one member selected from DL- ⁇ -ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamyl alcohol, p-anisyl alcohol, and benzhydrol.
- benzyl alcohol DOWANOL PPH, manufactured by The Dow Chemical Company, andCINDYE DNK, manufactured by BOZZETTO Group. Further, from the viewpoint of further improving the dyeing properties, benzyl alcohol, especially, 2,5-dimethylbenzyl alcohol or 2-nitrobenzyl alcohol is preferably used.
- the amount of the carrier is preferably 1 to 10 parts by weight (more preferably 1 to 5 parts by weight), relative to 100 parts by weight of the meta-type wholly aromatic polyamide fiber.
- an open width treatment or a jet scouring or relaxation treatment may be employed.
- a method is employed in which a treatment is conducted using an open width non-tension machine in continuous scouring or continuous drying.
- a method using a Sofcer scouring machine, a tenter dryer, a Shrink Surfer, a short loop, a Luciole dryer, or the like is employed.
- the scouring or relaxation step can be optionally omitted.
- the cloth may be subjected to clipping and/or singeing.
- a sweat absorber a water repellent, a thermal storage agent, an ultraviolet light screening agent, an antistatic agent, an anti-fungus agent, a deodorant, a mothproofing agent, a mosquito repellent, a phosphorescent agent, a retroreflective agent, or the like may be applied to the cloth.
- the woven or knitted fabric used may be spun-dyed yarn fabric, fiber or yarn colored fabric, or piece dyed fabric.
- polyethylene glycol diacryate a polyethylene glycol diacryate derivative, a polyethylene terephthalate-polyethylene glycol copolymer, or a water-soluble polyurethane.
- a padding treatment method As examples of the method for applying a sweat absorber to the cloth, there can be mentioned a padding treatment method, and a method in which a treatment is made using the same bath as the dyeing solution during the dyeing processing.
- the thus obtained cloth contains the above-mentioned spun yarn, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties.
- an acrylic fiber is used as the conductive fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed.
- the cloth of the invention it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m 2 . Further, it is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025:2000 A method. It is preferred that the cloth has a carbonized area of 30 cm 2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077.
- the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 A method (cantilever). It is preferred that the cloth has an antistaticity of 7.0 ⁇ C or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
- the fiber product of the invention is a fiber product using the above-described cloth, which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing.
- the fiber product uses the above-described cloth, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties.
- a weight per unit was measured in accordance with the method prescribed in JIS L1096:2010 A method.
- Flammability was measured in accordance with the method prescribed in ISO 15025:2000 A method, or JIS L1091:1999 A-1 method.
- a shrinkage rate was measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
- a thermal shrinkage rate was measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
- a water absorption ability of a cloth to be tested was measured in accordance with the method prescribed in JIS L1907:2010.
- a bending resistance of a cloth to be tested was measured in accordance with the method prescribed in JIS L1096:2010 A method (cantilever).
- a bundle of the basic fiber having a diameter of about 1 mm was prepared and set on a holder for a fiber sample and subjected to measurement of a diffraction profile.
- Conditions for the measurement were such that the source of an X-ray was Cu-K ⁇ (50 kV, 300 mA), the scanning angle range was 10 to 35°, the continuous measurement width was 0.1°, and the scanning speed was 1°/minute. From the actually measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile.
- Crystallinity % Crystal scattering intensity / Total scattering intensity ⁇ 100
- a meta-type wholly aromatic polyamide fiber was produced by the method described below.
- a 2-[2H-benzotriazol-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph enol powder (solubility in water: 0.01 mg/L) was mixed into and dissolved in the polymer solution in an amount of 3.0% by weight, based on the weight of the polymer, followed by deaeration under a reduced pressure, to obtain a spinning solution (spinning dope).
- Spinning was performed by discharging the above-obtained spinning dope from a spinning nozzle having 500 holes and having a hole diameter of 0.07 mm into a coagulation bath at a bath temperature of 30°C.
- the fiber after being washed was subjected to dry heat treatment using a heated roller having a surface temperature of 280°C to obtain a meta-type wholly aromatic polyamide fiber.
- the obtained meta-type wholly aromatic polyamide fiber had physical properties such that the fineness was 1.7 dtex, the residual solvent content was 0.08% by weight, and the crystallinity was 19%.
- crimping and cutting were performed to obtain a staple fiber having a length of 51 mm.
- Post-processing was performed by conducting singeing, scouring, and final setting.
- Procedure was performed in substantially the same manner as in Example 1 except that the conductive fiber was changed to an acrylic conductive fiber (AAS), and that the cloth was dyed with a cationic dye.
- the fabric had 7.0 ⁇ C or less and was acceptable for the antistatic properties. Further, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber were dyed deep color, and the whole of the cloth was uniformly dyed. The results are shown in Table 1.
- Example 1 Example 2* Example 3* Example 4 Comparative Example 1 Comparative Example 2 MA/MD/AS MA/MD/AS MA/MD/AAS MA/MD/RY/PA MA/MD/RY/PA Mixing ratio % 18/80/2 28/70/2 38/60/2 18/80/2 25/30/40/5 35/30/15/20 Weight per unit g/m 2 200 200 200 200 200 200 200 200 200 Flammability Afterflame (second) 0 0 0 0 0 0 0 Washing shrinkage rate % 5 4 3 5 10 7 Dry heat shrinkage % 4 5 5 4 6 5 Hand and comfortability Cantilever (cm) 6.5 6.8 6.4 6.5 8.9 10.0 *Reference example
- a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, but also in that the whole of the cloth can be uniformly dyed, and a fiber product, and the invention is of extremely great industrial significance.
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Description
- The present invention relates to a cloth having extremely excellent flame retardancy and having excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, and a fiber product.
- Conventionally, in the applications of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, flame-retardant workwear, a police uniform, Self-Defense Forces official clothing, military clothing, and the like, a cloth having flame retardancy has been used (see, for example, PTL's 1 to 4).
- Meanwhile, in recent years, a cloth that is not only flame retardant but also comfortable to wear is demanded, but there has not been proposed a cloth which has extremely excellent flame retardancy, and which has excellent resistance to shrinkage due to washing (washing shrinkage resistance), excellent hand, and excellent antistatic properties.
-
- PTL 1:
JP-A-2014-221955 - PTL 2:
JP-A-2015-94043 - PTL 3:
JP-A-8-325934 - PTL 4:
JP-T-2014-529690 -
US2013/055491A1 relates to a yarn having high moisture regain for use in arc and flame protection and fabrics and garments containing the yarn.US2014/026303A1 relates to a fiber blend, yarn, fabric, and/or garment suitable for use in arc and flame protection.JP2014/210985A JP2017/008454A JP2009/221632A - The invention is defined by the appended claims.
- In view of the above, the present invention has been made, and an object of the invention is to provide a cloth which is advantageous in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, preferably in that the whole of the cloth can be uniformly dyed, and a fiber product.
- The present inventors have conducted extensive and intensive studies with a view toward achieving the above-mentioned object. As a result, it has been found that, by appropriately selecting the type of the fiber constituting the cloth and the like, there can be obtained a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand, but also in that the whole of the cloth can be uniformly dyed, and further extensive and intensive studies have been made, and the present invention has been completed.
- Thus, in the present invention, there is provided "a cloth comprising a spun yarn which comprises a meta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber, wherein the conductive fiber is an acrylic fiber".
- In the cloth of the invention, it is preferred that the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more, based on the weight of the spun yarn. Further, it is preferred that the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more, based on the weight of the spun yarn. It is preferred that the spun yarn contains the conductive fiber in an amount of 1% by weight or more, based on the weight of the spun yarn.
- It is preferred that the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber. It is preferred that the meta-type wholly aromatic polyamide fiber has a residual solvent content of 0.1% by weight or less. It is preferred that the meta-type wholly aromatic polyamide fiber has a crystallinity in the range of from 15 to 25%. Particularly, it is preferred that a meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is an aromatic polyamide having an aromatic polyamide skeleton comprising repeating structural units representedby the formula (1) below, wherein an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component is copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide:
-(NH-Ar1-NH-CO-Ar1-CO)- Formula (1)
wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction. - In the above-mentioned cloth, it is preferred that, as the third component, the aromatic diamine is the following formula (2) or (3), or the aromatic dicarboxylic acid halide is the following formula (4) or (5):
H2N-Ar2-NH2 Formula (2)
H2N-Ar2-Y-Ar2-NH2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
wherein Ar2 represents a divalent aromatic group different from Ar1, Ar3 represents a divalent aromatic group different from Ar1, Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom. - Further, it is preferred that the meta-type wholly aromatic polyamide fiber further contains an organic dye, an organic pigment, or an inorganic pigment. The conductive fiber is an acrylic fiber. It is preferred that the modacrylic fiber and the conductive fiber are dyed with the same dye.
- In the cloth of the invention, it is preferred that the cloth contains an ultraviolet light absorber and/or a reflective agent. Further, it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m2. It is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025: 2000 A method. It is preferred that the cloth has a carbonized area of 30 cm2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077. It is preferred that the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 Amethod (cantilever) . It is preferred that the cloth has an antistaticity of 7.0 µC or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
- Further, in the invention, there is provided a fiber product using the above-mentioned cloth, which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing. Advantageous Effects of Invention
- By the present invention, there can be obtained a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand, but also in that the whole of the cloth can be uniformly dyed, and a fiber product. Description of Embodiments
- Hereinbelow, an embodiment of the present invention will be described in detail. First, the cloth of the invention comprises a spun yarn which comprises ameta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber.
- The meta-type wholly aromatic polyamide fiber used in the invention is a fiber formed from a polymer in which 85 mol% or more of the repeating units are m-phenyleneisophthalamide. The meta-type wholly aromatic polyamide may be a copolymer containing a third component in an amount in the range of less than 15 mol%.
- The meta-type wholly aromatic polyamide can be produced by a conventionally known interfacial polymerization method, and there is preferably used the meta-type wholly aromatic polyamide having, in terms of the degree of polymerization of the polymer, an intrinsic viscosity (I.V.) in the range of from 1.3 to 1.9 dl/g, as measured in the form of an N-methyl-2-pyrrolidone solution having a concentration of 0.5 g/100 ml.
- The meta-type wholly aromatic polyamide may contain an alkylbenzenesulfonic acid onium salt. Preferred examples of alkylbenzenesulfonic acid onium salts include compounds, such as tetrabutylphosphonium hexylbenzenesulfonate, tributylbenzylphosphonium hexylbenzenesulfonate, tetraphenylphosphonium dodecylbenzenesulfonate, tributyltetradecylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, and tributylbenzylammonium dodecylbenzenesulfonate. Of these, especially preferred is tetrabutylphosphonium dodecylbenzenesulfonate or tributylbenzylammonium dodecylbenzenesulfonate because they are easily available and have excellent thermal stability as well as high solubility in N-methyl-2-pyrrolidone.
- For obtaining a satisfactory improvement effect for the dyeing properties, the amount of the alkylbenzenesulfonic acid onium salt contained is preferably 2.5 mol% or more, preferably in the range of from 3.0 to 7.0 mol%, based on the mole of the poly-m-phenyleneisophthalamide.
- With respect to the method for mixing poly-m-phenyleneisophthalamide with an alkylbenzenesulfonic acid onium salt, there is used a method in which poly-m-phenyleneisophthalamide is mixed into and dissolved in a solvent and then an alkylbenzenesulfonic acid onium salt is dissolved in the solvent, or the like, and any method may be used. The thus obtained dope is formed into a fiber by a conventionally known method.
- For the purpose of improving the dyeing properties and the resistance to discoloration and color fading and the like, with respect to the polymer used in the meta-type wholly aromatic polyamide fiber, which has an aromatic polyamide skeleton comprising repeating structural units represented by the formula (1) below, an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component can be copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide:
-(NH-Ar1-NH-CO-Ar1-CO)- Formula (1)
wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction. - Specific examples of aromatic diamines, which are represented by the formula (2) or (3), and which can be copolymerized as a third component, include p-phenylenediamine, chlorophenylenediamine, methylphenylenediamine, acetylphenylenediamine, aminoanisidine, benzidine, bis(aminophenyl) ether, bis(aminophenyl) sulfone, diaminobenzanilide, and diaminoazobenzene. Specific examples of aromatic dicarboxylic acid dichlorides represented by the formula (4) or (5) include terephthalic acid chloride, 1,4-naphthalenedicarboxylic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid chloride, 5-methoxyisophthalic acid chloride, and bis(chlorocarbonylphenyl) ether.
H2N-Ar2-NH2 Formula (2)
H2N-Ar2-Y-Ar2-NH2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
Wherein Ar2 represents a divalent aromatic group different from Ar1, Ar3 represents a divalent aromatic group different from Ar1, Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom. - The crystallinity of the meta-type wholly aromatic polyamide fiber is preferably 5 to 35% because the absorption for a dye is excellent such that an intended color can be easily achieved even when using the dye in a reduced amount or even under poor dyeing conditions. Further, the crystallinity is more preferably 15 to 25% because localization of a dye in the surface is unlikely to occur and a high resistance to discoloration and color fading is obtained and further dimensional stability required for the practical use can be secured.
- The residual solvent content of the meta-type wholly aromatic polyamide fiber is preferably 0.1% by weight or less (preferably 0.001 to 0.1% by weight) because excellent flame retardancy of the meta-type wholly aromatic polyamide fiber is not sacrificed.
- The meta-type wholly aromatic polyamide fiber can be produced by the method mentioned below, and, particularly by the below-mentioned method, the crystallinity and residual solvent content in the above-mentioned respective ranges can be achieved.
- With respect to the polymerization method for the meta-type wholly aromatic polyamide polymer, there is no particular limitation, and, for example, the solution polymerization method or interfacial polymerization method described in
JP-B-35-14399 U.S. Patent No. 3,360,595 ,JP-B-47-10863 - The spinning solution is not particularly limited, but an amide-solvent solution containing an aromatic copolyamide polymer obtained by the above-mentioned solution polymerization, interfacial polymerization, or the like may be used, or a solution obtained by isolating the polymer from the above-mentioned polymerization solution and dissolving the polymer in an amide solvent may be used.
- Examples of the amide solvents used include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and dimethylsulfoxide, and especially preferred is N,N-dimethylacetamide.
- When the copolymerized aromatic polyamide polymer solution obtained as mentioned above further contains an alkali metal salt or an alkaline earth metal salt, the solution is stabilized and can be advantageously used in a higher concentration at low temperatures. The amount of the alkali metal salt and alkaline earth metal salt is preferably 1% by weight or less, more preferably 0.1% by weight or less, based on the mass of the polymer solution.
- In the spinning and coagulation step, the above-obtained spinning solution (meta-type wholly aromatic polyamide polymer solution) is discharged into a coagulation liquid so as to undergo coagulation.
- With respect to the spinning apparatus, there is no particular limitation, and a conventionally known wet spinning apparatus can be used. Further, with respect to the number of spinning holes of a spinning nozzle, the arrangement of the holes, the form of the hole, and the like, there is no particular limitation as long as wet spinning can be stably made, and, for example, a multihole spinning nozzle for rayon yarn having 1,000 to 30,000 holes and having a spinning hole diameter of 0.05 to 0.2 mm, or the like may be used.
- Further, the temperature of the spinning solution (meta-type wholly aromatic polyamide polymer solution) being discharged from a spinning nozzle is suitably in the range of from 20 to 90°C.
- As a coagulation bath used for obtaining a fiber, an aqueous solution containing substantially no inorganic salt and having an amide solvent, preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C is used. When the amide solvent (preferably NMP) concentration is less than 45% by weight, a structure having a thick skin is disadvantageously formed, so that the washing efficiency in the washing step is lowered, making it difficult to reduce the residual solvent content of the fiber. On the other hand, when the amide solvent (preferably NMP) concentration is more than 60% by weight, coagulation throughout the inside of the fiber cannot be achieved, making it difficult to reduce the residual solvent content of the fiber. The time for immersing the fiber in the coagulation bath is suitably in the range of from 0.1 to 30 seconds.
- Subsequently, in a plasticized drawing bath containing an aqueous solution having an amide solvent, preferably NMP concentration of 45 to 60% by weight at a bath solution temperature in the range of from 10 to 50°C, the fiber is subjected to drawing at a draw ratio of 3 to 4 times. After drawing, the resultant fiber is well washed through an aqueous solution having an NMP concentration of 20 to 40% by weight at 10 to 30°C and further through a warm water bath at 50 to 70°C.
- The fiber after being washed is subjected to dry heat treatment at a temperature of 270 to 290°C, obtaining a meta-type wholly aromatic aramid fiber which satisfies the crystallinity and residual solvent content in the above-mentioned respective ranges.
- In the meta-type wholly aromatic aramid fiber, the fiber is preferably in the form of a short fiber having a fiber length of 25 to 200 mm in view of mixing with another fiber. Further, the single fiber fineness is preferably in the range of from 1 to 5 dtex.
- In the invention, it is preferred that the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more (more preferably 5 to 50% by weight), based on the weight of the spun yarn. When the amount of the meta-type wholly aromatic polyamide fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in flame retardancy.
- The modacrylic fiber is a fiber formed from a linear synthetic polymer comprising repeating units for acrylonitrile group in an amount of 35 to less than 85% by weight, as measured in accordance with JIS L0204-2 (2001). The modacrylic fiber is advantageous in that woven fabric formed from the modacrylic fiber is wrinkle resistant and excellent in fireproofness, chemical resistance, beautiful appearance, hand, washing shrinkage resistance, and the like.
- In the invention, it is preferred that the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more (more preferably 50 to 90% by weight, especially preferably 60 to 80% by weight), based on the weight of the spun yarn. When the amount of the modacrylic fiber contained is smaller than the above range, there is a possibility that the cloth becomes poor in hand, washing shrinkage resistance, and the like.
- In the invention, the spun yarn contains not only the meta-type wholly aromatic polyamide fiber and modacrylic fiber but also a conductive fiber.
- With respect to the conductive fiber, preferred is an acrylic fiber having incorporated thereinto conductive carbon fine particles. The cloth of the invention contains the meta-type wholly aromatic polyamide fiber and an acrylic fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed. In this case, it is preferred that the meta-type wholly aromatic polyamide fiber and the conductive fiber are dyed the same color. The color difference between the meta-type wholly aromatic polyamide fiber and the conductive fiber, in terms of ΔE, is preferably 3 or less.
- As the acrylic fiber, preferred is a fiber having conductive carbon incorporated into an acrylic fiber, a sheath-core manner conjugate fiber comprising a core portion containing conductive fine particles and a sheath portion containing no conductive fine particle, or the like. Particularly, preferred is a sheath-core manner conjugate fiber (or an eccentric sheath-core manner conjugate fiber) having a sheath portion comprising an acryl containing no conductive fine particle, and a core portion comprising a conductive carbon-containing polymer, or the like. When the cloth contains such an acrylic fiber, static electricity caused due to friction of the cloth can be reduced, so that problems of the deposition of dust, a malfunction due to discharge, ignition in an expansion-proof environment, and the like can be solved.
- As the acrylic fiber, for example, an acrylic fiber described in
JP-A-2009-221632 - In the conductive fiber, the fiber may be in the form of either a continuous fiber (multifilament) or a short fiber. Particularly, in view of mixing with another fiber, a short fiber having a fiber length of 25 to 200 mm (more preferably 30 to 150 mm) is preferred. Further, the single fiber fineness is preferably in the range of from 1 to 5 dtex.
- In the cloth of the invention, it is preferred that the spun yarn contains the conductive fiber in an amount of 1% by weight or more (more preferably 1 to 5% by weight), based on the weight of the spun yarn. When the weight percentage of the conductive fiber is smaller than the above range, there is a possibility that the cloth becomes poor in antistatic properties.
- In the cloth of the invention, it is preferred that the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the conductive fiber, but the spun yarn may further contain an additional fiber. As the additional fiber, a flame-retardant fiber, such as a para-type wholly aromatic polyamide fiber, a wholly aromatic polyester fiber, apolybenzoxazole (PBO) fiber, apolybenzimidazole (PBI) fiber, apolybenzothiazole (PBTZ) fiber, apolyimide (PI) fiber, a polysulfonamide (PSA) fiber, a polyether ether ketone (PEEK) fiber, apolyetherimide (PEI) fiber, apolyarylate (PAr) fiber, a melamine fiber, a phenolic fiber, a fluorine fiber, or a polyphenylene sulfide (PPS) fiber, maybe contained in the spun yarn.
- When a cellulose fiber, a polyolefin fiber, an acrylic fiber, a rayon fiber, a cotton fiber, an animal hair fiber, a polyurethane fiber, a polyvinyl chloride fiber, a polyvinylidene chloride fiber, an acetate fiber, a polycarbonate fiber, or the like is contained in the spun yarn, water absorption properties, dyeing properties, comfortability to wear, or the like is advantageously imparted to the cloth.
- In the invention, with respect to the method for producing the cloth, there is no particular limitation, and any known method can be used. For example, it is preferred that spun yarns of the above-mentioned fibers are mixed to obtain a spun yarn, and then the spun yarn in the form of a single yarn or a two folded yarn is woven using a rapier loom or the like into a weave structure, such as twill weave or plain weave. In this case, it is preferred that the cloth is constituted solely by the spun yarn, but the spun yarn may be interwoven or interknitted with the above-mentioned additional fiber.
- It is preferred that the cloth is then subjected to post-processing. Specific examples of post-processing steps include steps, such as scouring, drying, relaxation, singeing, dyeing, and a function imparting treatment.
- With respect to the dyeing processing, it is preferred that the cloth is subjected to dyeing processing using a dye bath containing the above-mentioned cationic dye. In this instance, a method can be preferably employed in which the cloth is dyed at 115 to 135°C and then subj ected to reduction treatment, and dried, or the like , but the method is not limited to this.
- In the dyeing processing, a carrier is preferably used, and it is preferred that the cloth is subjected to dyeing treatment in the bath of cationic dye which is the same bath as the carrier . Further, when the cloth is treated with a special surfactant before subjected to cationic dyeing, the cloth can be dyed deep color in the open width dyeing.
- It is preferred that the carrier is, for example, at least one member selected from DL-β-ethylphenethyl alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol, 2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol, p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol, 3-methylphenethyl alcohol, 4-methylphenethyl alcohol, 2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamyl alcohol, p-anisyl alcohol, and benzhydrol. As specific commercially available products, preferred are benzyl alcohol, DOWANOL PPH, manufactured by The Dow Chemical Company, andCINDYE DNK, manufactured by BOZZETTO Group. Further, from the viewpoint of further improving the dyeing properties, benzyl alcohol, especially, 2,5-dimethylbenzyl alcohol or 2-nitrobenzyl alcohol is preferably used.
- The amount of the carrier is preferably 1 to 10 parts by weight (more preferably 1 to 5 parts by weight), relative to 100 parts by weight of the meta-type wholly aromatic polyamide fiber.
- As a scouring or relaxation treatment, an open width treatment or a jet scouring or relaxation treatment may be employed. Specifically, a method is employed in which a treatment is conducted using an open width non-tension machine in continuous scouring or continuous drying. For example, a method using a Sofcer scouring machine, a tenter dryer, a Shrink Surfer, a short loop, a Luciole dryer, or the like is employed. The scouring or relaxation step can be optionally omitted.
- For improving other properties, the cloth may be subjected to clipping and/or singeing. Further, as another processing for imparting a function, a sweat absorber, a water repellent, a thermal storage agent, an ultraviolet light screening agent, an antistatic agent, an anti-fungus agent, a deodorant, a mothproofing agent, a mosquito repellent, a phosphorescent agent, a retroreflective agent, or the like may be applied to the cloth. The woven or knitted fabric used may be spun-dyed yarn fabric, fiber or yarn colored fabric, or piece dyed fabric.
- With respect to the sweat absorber, preferred is polyethylene glycol diacryate, a polyethylene glycol diacryate derivative, a polyethylene terephthalate-polyethylene glycol copolymer, or a water-soluble polyurethane.
- As examples of the method for applying a sweat absorber to the cloth, there can be mentioned a padding treatment method, and a method in which a treatment is made using the same bath as the dyeing solution during the dyeing processing.
- The thus obtained cloth contains the above-mentioned spun yarn, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties. Further, an acrylic fiber is used as the conductive fiber, such that when the cloth is dyed with a cationic dye, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber are dyed deep color, and the whole of the cloth is uniformly dyed.
- In the cloth of the invention, it is preferred that the cloth has a weight per unit in the range of from 130 to 300 g/m2. Further, it is preferred that the cloth has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025:2000 A method. It is preferred that the cloth has a carbonized area of 30 cm2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method. It is preferred that the cloth has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077. It is preferred that the cloth has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. It is preferred that the cloth has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method) . It is preferred that the cloth has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 A method (cantilever). It is preferred that the cloth has an antistaticity of 7.0 µC or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
- The fiber product of the invention is a fiber product using the above-described cloth, which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing. The fiber product uses the above-described cloth, and therefore has extremely excellent flame retardancy and has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties.
- Hereinbelow, the present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. The physical properties shown in the Examples were measured by the methods described below.
- A weight per unit was measured in accordance with the method prescribed in JIS L1096:2010 A method.
- Flammability was measured in accordance with the method prescribed in ISO 15025:2000 A method, or JIS L1091:1999 A-1 method.
- A shrinkage rate was measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
- A thermal shrinkage rate was measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493. n (the number of samples) was 5 and the measurement was conducted with respect to the warp direction and the weft direction, and an average of the values measured in the both directions was determined.
- A water absorption ability of a cloth to be tested was measured in accordance with the method prescribed in JIS L1907:2010.
- A bending resistance of a cloth to be tested was measured in accordance with the method prescribed in JIS L1096:2010 A method (cantilever).
- An amount of electric charges was measured in accordance with JIS L1094:2014 (antistatic properties). A sample with 7.0 µC or less is acceptable for the antistatic properties.
- About 8.0 g of a basic fiber was taken and dried at 105°C for 120 minutes, and then cooled in a desiccator, and a weight (M1) of the fiber was measured. Then, the resultant fiber was placed in methanol and subjected to extraction under reflux for the amide solvent contained in the fiber using a Soxhlet's extractor for 1.5 hours. The fiber which had been subjected to extraction was taken out from the extractor, and subjected to vacuum drying at 150°C for 60 minutes, and then cooled in a desiccator, and a weight (M2) of the fiber was measured. An amount of the solvent remaining in the fiber (amide solvent weight) was calculated from the obtained weight values M1 and M2 using the following formula.
- Using an X-ray diffraction measurement apparatus (RINT TTRIII, manufactured by Rigaku Corporation), a bundle of the basic fiber having a diameter of about 1 mm was prepared and set on a holder for a fiber sample and subjected to measurement of a diffraction profile. Conditions for the measurement were such that the source of an X-ray was Cu-Kα (50 kV, 300 mA), the scanning angle range was 10 to 35°, the continuous measurement width was 0.1°, and the scanning speed was 1°/minute. From the actually measured diffraction profile, air scattering and incoherent scattering were corrected by linear approximation to obtain a total scattering profile. Then, an amorphous scattering profile was subtracted from the total scattering profile to obtain a crystal scattering profile. Acrystallinity was determined from an area intensity of the crystal scattering profile (crystal scattering intensity) and an area intensity of the total scattering profile (total scattering intensity) using the following formula.
- A meta-type wholly aromatic polyamide fiber was produced by the method described below.
- 20.0 Parts by weight of a polymetaphenyleneisophthalamide powder having an intrinsic viscosity (I.V.) of 1.9, which had been produced by an interfacial polymerization method in accordance with the method described in
JP-B-47-10863 - Spinning was performed by discharging the above-obtained spinning dope from a spinning nozzle having 500 holes and having a hole diameter of 0.07 mm into a coagulation bath at a bath temperature of 30°C. The coagulation liquid had a composition of water/NMP = 45/55 (parts by weight), and the spinning was made by discharging the spinning dope into the coagulation bath at a yarn speed of 7 m/minute.
- Subsequently, the resultant spun yarn was drawn at a draw ratio of 3.7 times in a plasticized drawing bath having a composition of water/NMP = 45/55 at a temperature of 40°C.
- After drawing, the resultant yarn was washed in a bath having a composition of water/NMP = 70/30 at 20°C (dipping length: 1.8 m), and then washed in a water bath at 20°C (dipping length: 3.6 m), and further well washed through a warm water bath at 60°C (dipping length: 5.4 m) .
- The fiber after being washed was subjected to dry heat treatment using a heated roller having a surface temperature of 280°C to obtain a meta-type wholly aromatic polyamide fiber.
- The obtained meta-type wholly aromatic polyamide fiber had physical properties such that the fineness was 1.7 dtex, the residual solvent content was 0.08% by weight, and the crystallinity was 19%. Using the obtained basic fiber, crimping and cutting were performed to obtain a staple fiber having a length of 51 mm.
- With respect to the other fibers, the staple fibers shown below were used.
- Modacrylic fiber: "ProtexM (registered trademark)", manufactured by Kaneka Corporation
- Conductive fiber (nylon conductive fiber) used in Examples 1 to 3: "NO SHOCK (registered trademark)" (nylon conductive fiber having incorporated thereinto conductive carbon fine particles), manufactured by Solutia Inc.
- Conductive fiber (acrylic conductive fiber) used in Example 4: fineness: 3.3 dtex; fiber length: 38 mm (sheath-core manner acrylic conductive fiber having conductive carbon fine particles incorporated into the core portion)
- Post-processing was performed by conducting singeing, scouring, and final setting.
- Using a spun yarn No. 40/two folded yarn which was made of staple fibers of a meta-type wholly aromatic polyamide fiber (MA) (length: 51 mm) , a modacrylic fiber (MD) (length: 51 mm) , and a nylon conductive fiber (AS) (length: 51 mm), and which was obtained by mixing the fibers in a ratio of MA/MD/AS = 18/80/2, weaving was conducted at a weave density such that the warp yarn number was 100/25.4 mm and the weft yarn number was 55/25.4 mm to obtain twill fabric having a weight per unit of 200 g/m2. Using the obtained fabric, processing was conducted by the above-mentioned method. The fabric had 7.0 µC or less and was acceptable for the antistatic properties . Theresultsare shown in Table 1.
- Using a spun yarn No. 40/two folded yarn which was made of staple fibers of a meta-type wholly aromatic polyamide fiber (MA) (length: 51 mm), a modacrylic fiber (MD) (length: 51 mm), and a nylon conductive fiber (AS) (length: 51 mm), and which was obtained by mixing the fibers in a ratio of MA/MD/AS = 28/70/2, weaving was conducted at a weave density such that the warp yarn number was 100/25.4 mm and the weft yarn number was 55/25.4 mm to obtain twill fabric having a weight per unit of 200 g/m2. Using the obtained fabric, processing was conducted by the above-mentioned method. The fabric had 7.0 µC or less and was acceptable for the antistatic properties . The results are shown in Table 1.
- Using a spun yarn No. 40/two folded yarn which was made of staple fibers of a meta-type wholly aromatic polyamide fiber (MA) (length: 51 mm), a modacrylic fiber (MD) (length: 51 mm), and a nylon conductive fiber (AS) (length: 51 mm), and which was obtained by mixing the fibers in a ratio of MA/MD/AS = 38/60/2, weaving was conducted at a weave density such that the warp yarn number was 100/25.4 mm and the weft yarn number was 55/25.4 mm to obtain twill fabric having a weight per unit of 200 g/m2. Using the obtained fabric, processing was conducted by the above-mentioned method. The fabric had 7.0 µC or less and was acceptable for the antistatic properties . Theresultsare shown in Table 1.
- Procedure was performed in substantially the same manner as in Example 1 except that the conductive fiber was changed to an acrylic conductive fiber (AAS), and that the cloth was dyed with a cationic dye. The fabric had 7.0 µC or less and was acceptable for the antistatic properties. Further, all the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the acrylic fiber were dyed deep color, and the whole of the cloth was uniformly dyed. The results are shown in Table 1.
- Using a spun yarn No. 40/two folded yarn which was made of ameta-type wholly aromatic polyamide fiber (MA), amodacrylic fiber (MD), flame-retardant rayon (RY), and a para-type wholly aromatic polyamide fiber (PA), and which was obtained by mixing the fibers in a ratio of MA/MD/RY/PA = 25/30/40/5, weaving was conducted at a weave density such that the warp yarn number was 100/25.4 mm and the weft yarn number was 55/25. 4 mm to obtain twill fabric having a weight per unit of 200 g/m2. Using the obtained fabric, processing was conducted by the above-mentioned method. The fabric was unacceptable for the antistatic properties. The results are shown in Table 1.
- Using a spun yarn No. 40/two folded yarn which was made of ameta-type wholly aromatic polyamide fiber (MA), amodacrylic fiber (MD), flame-retardant rayon (RY), and a para-type wholly aromatic polyamide fiber (PA), and which was obtained by mixing the fibers in a ratio of MA/MD/RY/PA = 35/30/15/20, weaving was conducted at a weave density such that the warp yarn number was 100/25.4 mm and the weft yarn number was 55/25.4 mm to obtain twill fabric having a weight per unit of 200 g/m2. Using the obtained fabric, processing was conducted by the above-mentioned method. The fabric was unacceptable for the antistatic properties. The results are shown in Table 1.
[Table 1] Example 1* Example 2* Example 3* Example 4 Comparative Example 1 Comparative Example 2 MA/MD/AS MA/MD/AS MA/MD/AS MA/MD/AAS MA/MD/RY/PA MA/MD/RY/PA Mixing ratio % 18/80/2 28/70/2 38/60/2 18/80/2 25/30/40/5 35/30/15/20 Weight per unit g/m2 200 200 200 200 200 200 Flammability Afterflame (second) 0 0 0 0 0 0 Washing shrinkage rate % 5 4 3 5 10 7 Dry heat shrinkage % 4 5 5 4 6 5 Hand and comfortability Cantilever (cm) 6.5 6.8 6.4 6.5 8.9 10.0 *Reference example - In the present invention, there are provided a cloth which is advantageous not only in that the cloth has extremely excellent flame retardancy, and further has excellent washing shrinkage resistance and excellent hand as well as excellent antistatic properties, but also in that the whole of the cloth can be uniformly dyed, and a fiber product, and the invention is of extremely great industrial significance.
Claims (15)
- A cloth comprising a spun yarn which comprises a meta-type wholly aromatic polyamide fiber, a modacrylic fiber, and an electrically conductive fiber; characterized in that the electrically conductive fiber is an acrylic fiber.
- The cloth according to claim 1, wherein the spun yarn contains the meta-type wholly aromatic polyamide fiber in an amount of 5% by weight or more, based on the weight of the spun yarn.
- The cloth according to claim 1 or 2, wherein the spun yarn contains the modacrylic fiber in an amount of 30% by weight or more, based on the weight of the spun yarn.
- The cloth according to any one of claims 1 to 3, wherein the spun yarn contains the electrically conductive fiber in an amount of 1% by weight or more, based on the weight of the spun yarn.
- The cloth according to any one of claims 1 to 4, wherein the spun yarn comprises only the meta-type wholly aromatic polyamide fiber, the modacrylic fiber, and the electrically conductive fiber.
- The cloth according to any one of claims 1 to 5, wherein the meta-type wholly aromatic polyamide fiber has a residual solvent content of 0.1% by weight or less.
- The cloth according to any one of claims 1 to 6, wherein the meta-type wholly aromatic polyamide fiber has a crystallinity in the range of from 15 to 25%.
- The cloth according to any one of claims 1 to 7, wherein a meta-type wholly aromatic polyamide forming the meta-type wholly aromatic polyamide fiber is an aromatic polyamide having an aromatic polyamide skeleton comprising repeating structural units represented by the formula (1) below, wherein an aromatic diamine component different from the main constituent units of the repeating structure, or an aromatic dicarboxylic acid halide component is copolymerized as a third component with the aromatic polyamide skeleton so that the amount of the third component becomes 1 to 10 mol%, based on the total mole of the repeating structural units of the aromatic polyamide:
-(NH-Ar1-NH-CO-Ar1-CO)- Formula (1)
wherein Ar1 is a divalent aromatic group having a bonding group at a position other than the meta position or the parallel axis direction. - The cloth according to claim 8, wherein, as the third component, the aromatic diamine is the following formula (2) or (3), or the aromatic dicarboxylic acid halide is the following formula (4) or (5):
H2N-Ar2-NH2 Formula (2)
H2N-Ar2-Y-Ar2-NH2 Formula (3)
XOC-Ar3-COX Formula (4)
XOC-Ar3-Y-Ar3-COX Formula (5)
wherein Ar2 represents a divalent aromatic group different from Ar1, Ar3 represents a divalent aromatic group different from Ar1, Y represents at least one atom or functional group selected from the group consisting of an oxygen atom, a sulfur atom, and an alkylene group, and X represents a halogen atom. - The cloth according to any one of claims 1 to 9, wherein the meta-type wholly aromatic polyamide fiber further contains an organic dye, an organic pigment, or an inorganic pigment.
- The cloth according to any one of claims 1 to 10, wherein the modacrylic fiber and the electrically conductive fiber are dyed with the same dye.
- The cloth according to any one of claims 1 to 11, which contains an ultraviolet light absorber and/or a reflective agent; and/or which has a weight per unit in the range of from 130 to 300 g/m2.
- The cloth according to any one of claims 1 to 12, which has an afterflame time of 2 seconds or less, as measured by the method prescribed in ISO 15025:2000 A method; and/orwhich has a carbonized area of 30 cm2 or less, as measured by the method prescribed in JIS L1091:1999 A-1 method; and/orwhich has a shrinkage rate of 5% or less, as measured after subjected to washing 5 times in accordance with the method prescribed in ISO 5077.
- The cloth according to any one of claims 1 to 13, which has a thermal shrinkage rate of 10% or less, as measured after subjected to heat treatment at 180°C for 5 minutes in accordance with the method prescribed in ISO 17493; and/orwhich has a water absorbing time of 30 seconds or less, as measured by the method prescribed in JIS L1907:2010 (dropping method); and/orwhich has a bending resistance of 7.0 cm or less, as measured by the method prescribed in JIS L1096:2010 A method (cantilever); and/orwhich has an antistaticity of 7.0 µC or less, as measured by the method prescribed in JIS L1094:2014 (antistatic properties).
- A fiber product using the cloth according to any one of claims 1 to 14, which is any one fiber product selected from the group consisting of protective clothing, fire-fighting fireproof clothing, fire fighting clothing, rescue clothing, workwear, a police uniform, Self-Defense Forces official clothing, and military clothing.
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JP2018071562 | 2018-04-03 | ||
PCT/JP2019/012463 WO2019194001A1 (en) | 2018-04-03 | 2019-03-25 | Fabric and textile product |
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EP3779004A4 EP3779004A4 (en) | 2021-05-12 |
EP3779004B1 true EP3779004B1 (en) | 2022-02-16 |
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US (1) | US20210363668A1 (en) |
EP (1) | EP3779004B1 (en) |
JP (1) | JPWO2019194001A1 (en) |
KR (1) | KR20200138345A (en) |
CN (1) | CN111936684A (en) |
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WO (1) | WO2019194001A1 (en) |
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CN114423893A (en) * | 2019-09-24 | 2022-04-29 | 帝人株式会社 | Fire-resistant cloth and seat |
EP4055218A1 (en) * | 2019-11-04 | 2022-09-14 | W. L. Gore & Associates, Inc. | Flame retardant composite articles and methods for reducing exposure to flames |
US11946173B2 (en) | 2020-05-20 | 2024-04-02 | Glen Raven, Inc. | Yarns and fabrics including modacrylic fibers |
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GB1111974A (en) | 1964-06-16 | 1968-05-01 | Certels Ltd | Improvements in or relating to building blocks |
JPH08325934A (en) | 1995-05-24 | 1996-12-10 | Teijin Ltd | Flame-retardant treatment of meta-aramide fiber structure |
JPH11250A (en) * | 1997-06-10 | 1999-01-06 | Mitsubishi Rayon Co Ltd | Flame retardant blanket provided with antistatic and antibacterial property |
US20050208855A1 (en) * | 2004-03-18 | 2005-09-22 | Reiyao Zhu | Modacrylic/cotton/aramid fiber blends for arc and flame protection |
JP2009221632A (en) * | 2008-03-17 | 2009-10-01 | Mitsubishi Rayon Co Ltd | Sheath-core conjugate conductive acrylic filament |
US9169582B2 (en) | 2011-09-02 | 2015-10-27 | E I Du Pont De Nemours And Company | High moisture regain yarn, fabrics, and garments having superior arc protection |
US20140026303A1 (en) * | 2012-07-27 | 2014-01-30 | E I Du Pont De Nemours And Company | Fiber blends, yarns, fabrics, and garments for arc and flame protection |
JP6162463B2 (en) * | 2013-04-17 | 2017-07-12 | 帝人株式会社 | Spun yarn and fabric and apparel |
CN103266499A (en) * | 2013-05-02 | 2013-08-28 | 常熟市宝沣特种纤维有限公司 | Anti-arc fabric |
JP6199603B2 (en) | 2013-05-14 | 2017-09-20 | 帝人株式会社 | Cloth and clothing |
JP6109026B2 (en) * | 2013-09-20 | 2017-04-05 | 帝人株式会社 | Protective product fabric, manufacturing method thereof and protective product |
JP6170814B2 (en) | 2013-11-12 | 2017-07-26 | 帝人株式会社 | Fabrics and textile products |
EP3192908B1 (en) * | 2014-09-03 | 2018-09-26 | Teijin Limited | Fabric and textile product |
WO2016194766A1 (en) * | 2015-06-01 | 2016-12-08 | 株式会社カネカ | Flame-retardant fabric and protective clothing in which same is used |
JP6595224B2 (en) * | 2015-06-24 | 2019-10-23 | 帝人株式会社 | Fabrics and textile products |
US10590567B2 (en) * | 2016-09-01 | 2020-03-17 | Dupont Safety & Construction, Inc. | Carbon-containing modacrylic and aramid bicomponent filament yarns |
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- 2019-03-25 KR KR1020207031257A patent/KR20200138345A/en not_active Application Discontinuation
- 2019-03-25 WO PCT/JP2019/012463 patent/WO2019194001A1/en unknown
- 2019-03-25 BR BR112020019275-9A patent/BR112020019275A2/en not_active Application Discontinuation
- 2019-03-25 CN CN201980023862.7A patent/CN111936684A/en active Pending
- 2019-03-25 US US17/045,073 patent/US20210363668A1/en not_active Abandoned
- 2019-03-25 JP JP2020511701A patent/JPWO2019194001A1/en active Pending
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EP3779004A1 (en) | 2021-02-17 |
JPWO2019194001A1 (en) | 2021-03-25 |
BR112020019275A2 (en) | 2021-01-05 |
CN111936684A (en) | 2020-11-13 |
KR20200138345A (en) | 2020-12-09 |
US20210363668A1 (en) | 2021-11-25 |
WO2019194001A1 (en) | 2019-10-10 |
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