WO2023171286A1 - Flame retardant cloth and flame retardant work clothing - Google Patents
Flame retardant cloth and flame retardant work clothing Download PDFInfo
- Publication number
- WO2023171286A1 WO2023171286A1 PCT/JP2023/005405 JP2023005405W WO2023171286A1 WO 2023171286 A1 WO2023171286 A1 WO 2023171286A1 JP 2023005405 W JP2023005405 W JP 2023005405W WO 2023171286 A1 WO2023171286 A1 WO 2023171286A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- flame
- fibers
- mass
- retardant
- acrylic
- Prior art date
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 91
- 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 title claims abstract description 90
- 239000004744 fabric Substances 0.000 title claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 114
- 229920002972 Acrylic fiber Polymers 0.000 claims abstract description 59
- -1 zinc stannate compound Chemical class 0.000 claims abstract description 29
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 25
- 238000012360 testing method Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 6
- 229920003043 Cellulose fiber Polymers 0.000 claims description 19
- BHTBHKFULNTCHQ-UHFFFAOYSA-H zinc;tin(4+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Sn+4] BHTBHKFULNTCHQ-UHFFFAOYSA-H 0.000 claims description 19
- 238000002485 combustion reaction Methods 0.000 claims description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 12
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 11
- 229920000433 Lyocell Polymers 0.000 claims description 10
- 239000002759 woven fabric Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 description 25
- 238000004519 manufacturing process Methods 0.000 description 18
- 238000009940 knitting Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 229910052736 halogen Inorganic materials 0.000 description 15
- 150000002367 halogens Chemical class 0.000 description 15
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 229920002554 vinyl polymer Polymers 0.000 description 13
- AUYOHNUMSAGWQZ-UHFFFAOYSA-L dihydroxy(oxo)tin Chemical compound O[Sn](O)=O AUYOHNUMSAGWQZ-UHFFFAOYSA-L 0.000 description 9
- 238000009987 spinning Methods 0.000 description 9
- 238000010998 test method Methods 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000004753 textile Substances 0.000 description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000004627 regenerated cellulose Substances 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- 238000002166 wet spinning Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001463 antimony compounds Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007561 laser diffraction method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000000790 scattering method Methods 0.000 description 3
- 229920002994 synthetic fiber Polymers 0.000 description 3
- 239000012209 synthetic fiber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BNEMLSQAJOPTGK-UHFFFAOYSA-N zinc;dioxido(oxo)tin Chemical compound [Zn+2].[O-][Sn]([O-])=O BNEMLSQAJOPTGK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920006231 aramid fiber Polymers 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920006277 melamine fiber Polymers 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- 229920000536 2-Acrylamido-2-methylpropane sulfonic acid Polymers 0.000 description 1
- XHZPRMZZQOIPDS-UHFFFAOYSA-N 2-Methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid Chemical compound OS(=O)(=O)CC(C)(C)NC(=O)C=C XHZPRMZZQOIPDS-UHFFFAOYSA-N 0.000 description 1
- XEEYSDHEOQHCDA-UHFFFAOYSA-N 2-methylprop-2-ene-1-sulfonic acid Chemical compound CC(=C)CS(O)(=O)=O XEEYSDHEOQHCDA-UHFFFAOYSA-N 0.000 description 1
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 240000008564 Boehmeria nivea Species 0.000 description 1
- 241000282836 Camelus dromedarius Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 244000146553 Ceiba pentandra Species 0.000 description 1
- 235000003301 Ceiba pentandra Nutrition 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 240000000491 Corchorus aestuans Species 0.000 description 1
- 235000011777 Corchorus aestuans Nutrition 0.000 description 1
- 235000010862 Corchorus capsularis Nutrition 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
- 240000006240 Linum usitatissimum Species 0.000 description 1
- 235000004431 Linum usitatissimum Nutrition 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920001407 Modal (textile) Polymers 0.000 description 1
- 240000000907 Musa textilis Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 229920003071 Polyclar® Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241001416177 Vicugna pacos Species 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229910007717 ZnSnO Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 210000000077 angora Anatomy 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 210000000085 cashmere Anatomy 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000004031 devitrification Methods 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 238000007706 flame test Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 210000000050 mohair Anatomy 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol 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
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 229920006297 regenerated protein fiber Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/54—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated nitriles
-
- 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
- D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
- D02G3/04—Blended or other yarns or threads containing components made from different materials
-
- 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
-
- 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
- D03D15/208—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 cellulose-based
- D03D15/217—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 cellulose-based natural from plants, e.g. cotton
-
- 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
- D03D15/208—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 cellulose-based
- D03D15/225—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 cellulose-based artificial, e.g. viscose
-
- 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
-
- 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
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04B—KNITTING
- D04B1/00—Weft knitting processes for the production of fabrics or articles not dependent on the use of particular machines; Fabrics or articles defined by such processes
- D04B1/14—Other fabrics or articles characterised primarily by the use of particular thread materials
Definitions
- the present invention relates to a flame-retardant fabric that has improved flame retardancy while being environmentally friendly, and flame-retardant work clothes using the same.
- halogen-containing fibers such as acrylic fibers and other fibers, such as cellulose fibers
- the conventional method for making halogen-containing fibers such as acrylic fibers flame retardant has been to include about 1 to 50 parts by mass of an antimony compound as a flame retardant (for example, Patent Document 1).
- an antimony compound as a flame retardant
- Patent Documents 2 and 3 propose that halogen-containing fibers contain a tin-based compound as a compound that imparts flame retardancy, and that the halogen-containing fibers are used in combination with cellulose-based fibers.
- Patent Document 2 there was a problem that the cost was high because the halogen-containing fiber contained 20 to 50% by weight of a zinc stannate compound. Further, the fiber composite described in Patent Document 3 may not have sufficient flame retardancy when used for work clothes or the like.
- the present invention provides a flame-retardant fabric and flame-retardant work clothes that are environmentally friendly, reduce costs, and have improved flame retardancy.
- One or more embodiments of the present invention include 30-80% by weight of flame-retardant acrylic fibers and 20-70% by weight of other fibers selected from the group consisting of natural fibers and synthetic fibers,
- the acrylic fiber contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound, and relates to a flame-retardant fabric having an afterflame time of 30 seconds or less in an ISO 15025 combustion test.
- One or more embodiments of the present invention relate to flame-retardant workwear comprising the flame-retardant fabric described above.
- the inventors of the present invention have conducted repeated studies to improve the flame retardancy of fabrics containing acrylic fibers while being environmentally friendly.
- the fabric can improve the flame retardant properties of work clothes. It shows excellent flame retardancy (flame retardancy) in the combustion test used to evaluate the standard, for example, the ISO 15025: 2016 combustion test method, and specifically the afterflame time measured by the ISO 15025: 2016 combustion test method. It was found that it is easy to adjust the time to 30 seconds or less.
- the flame-retardant acrylic fiber contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer.
- a zinc stannate compound based on 100 parts by mass of the acrylic copolymer.
- zinc stannate was added to 100 parts by mass of the acrylic copolymer.
- the content of the compound is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more.
- the flame-retardant acrylic fiber is composed of:
- the zinc stannate compound is preferably contained in 16 parts by mass or less, more preferably in 15 parts by mass or less, even more preferably in 14 parts by mass or less, and even more preferably in 13 parts by mass or less.
- the flame-retardant acrylic fiber preferably contains 1.0 to 15.3% by mass, more preferably 2.0 to 13.8% by mass of a zinc stannate compound, based on the total mass of the fiber. It is more preferable to contain 2.5 to 13.0% by mass, even more preferably to contain 3.0 to 12.3% by mass, and even more preferably to contain 3.5 to 11.5% by mass.
- the content of "zinc stannate compound" in the flame-retardant acrylic fiber can be measured by fluorescent X-ray analysis.
- the zinc stannate compound may be, for example, zinc stannate (ZnSnO 3 ) or zinc hydroxystannate (ZnSn(OH) 6 ). Therefore, zinc hydroxystannate is preferred.
- the zinc stannate compound is not particularly limited, but for example, from the viewpoint of spinnability and fiber strength, the average particle diameter D50 is preferably 5 ⁇ m or less, more preferably 3 ⁇ m or less, and still more preferably 2 ⁇ m or less. Further, the lower limit of the average particle diameter D50 of the zinc stannate compound is not particularly limited, but may be, for example, 0.1 ⁇ m or more from the viewpoint of handleability. In addition, from the viewpoint of improving flame retardancy when the amount of flame-retardant acrylic fiber is reduced, for example, less than 45% by mass or 40% by mass, it is preferably 0.5 ⁇ m or more, and 0.5 ⁇ m or more.
- the halogen-containing monomer includes one or more selected from the group consisting of a halogen-containing vinyl monomer and a halogen-containing vinylidene monomer.
- the other copolymerizable vinyl monomer is not particularly limited as long as it is copolymerizable with acrylonitrile.
- halogen-containing vinyl monomer examples include vinyl chloride and vinyl bromide
- examples of the halogen-containing vinylidene monomer include vinylidene chloride and vinylidene bromide. These halogen-containing monomers may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of vinyl chloride and vinylidene chloride is preferred, and vinylidene chloride is more preferred.
- the other copolymerizable vinyl monomers are not particularly limited, but include, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, salts thereof, and methacrylic esters such as methyl methacrylate. , esters of unsaturated carboxylic acids such as glycidyl methacrylate, vinyl esters such as vinyl acetate and vinyl butyrate, monomers containing sulfonic acid groups, and the like can be used.
- the acrylic copolymer can be obtained by known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these, suspension polymerization, emulsion polymerization, and solution polymerization are preferred from an industrial viewpoint.
- the flame-retardant acrylic fiber optionally contains an antistatic agent, a thermal coloring inhibitor, a light fastness improver, a whiteness improver, a devitrification inhibitor, and a colorant. It may also contain other additives such as.
- the flame-retardant acrylic fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use.
- the single fiber fineness is appropriately selected depending on the purpose of the fabric and textile product used, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. good.
- the fiber length is appropriately selected depending on the use of the fabric or textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
- the flame-retardant acrylic fiber can be produced by spinning a composition preferably including, but not limited to, an acrylic copolymer and a zinc stannate compound.
- a composition preferably including, but not limited to, an acrylic copolymer and a zinc stannate compound.
- known methods such as a wet spinning method, a dry spinning method, and a semi-dry semi-wet method can be used.
- wet spinning the method is similar to the case of general acrylic fibers, except that a spinning stock solution obtained by dissolving the acrylic copolymer in a solvent and adding a zinc stannate compound thereto is used.
- a solution of a zinc stannate compound dissolved in a solvent may be added to a resin solution containing an acrylic copolymer dissolved in a solvent.
- the solvent include organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and acetone, and inorganic solvents such as rhodan salt aqueous solution and nitric acid aqueous solution.
- the flame-retardant fabric according to one or more embodiments of the present invention contains 30 to 80% by mass of the flame-retardant acrylic fibers and 20% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers. Contains ⁇ 70% by mass. This makes it possible to improve the flame retardance of the flame-retardant fabric while imparting the characteristics of other fibers.
- the flame-retardant fabric more preferably contains 35 to 75% by mass of the flame-retardant acrylic fibers and 25 to 65% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers, and even more preferably It contains 40 to 75% by mass of the flame-retardant acrylic fiber and 25 to 60% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers.
- regenerated fibers examples include regenerated cellulose fibers such as rayon, polynosic, cupro, and lyocell, regenerated collagen fibers, regenerated protein fibers, cellulose acetate fibers, and promix fibers.
- the other fibers mentioned above may be used alone or in combination of two or more.
- the other fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use.
- the single fiber fineness is appropriately selected depending on the purpose of the fabric and textile product used, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. good.
- the fiber length is appropriately selected depending on the use of the fabric or textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
- the flame-retardant fabric may be a woven fabric or a knitted fabric.
- Fabrics include plain weave, oblique weave, satin weave, variable plain weave, variable oblique weave, variable satin weave, variable weave, patterned weave, single layer weave, double weave, multiple weave, warp pile weave, weft pile weave, and Examples include twine weave. Plain weave, satin weave, and patterned weave have excellent texture and strength as products.
- the flame retardant fabric may have an afterflame time of 30 seconds or less in the ISO 15025:2016 combustion test, but from the viewpoint of superior flame retardancy (flame resistance), the afterflame time should be 10 seconds or less in the ISO 15025:2016 combustion test.
- the time is preferably at most seconds, more preferably at most 5 seconds, even more preferably at most 3 seconds, particularly preferably at most 2.0 seconds.
- it can be suitably used for flame-retardant work clothes for work involving fire, such as protective clothing and firefighting clothing.
- the flame retardant fabric is not particularly limited, but from the viewpoint of texture, it is preferable that the fabric weight is 150 to 400 g/m 2 , more preferably 200 to 380 g/m 2 , and still more preferably 220 to 350 g/m 2 . m2 .
- Fabrics such as woven and/or knitted fabrics having the following fiber compositions can be suitably used as flame-retardant workwear fabrics for work involving fire, such as protective clothing and firefighting clothing.
- cellulose fibers in combination, it is possible to impart hygroscopicity and comfort to fabrics and work clothes. If the content of cellulose fibers is less than 20% by mass, comfort may not be maintained.
- fabrics such as woven and/or knitted fabrics with the following fiber composition are preferably used as flame-retardant workwear fabrics for work that handles fire, such as protective clothing and firefighting clothing. be able to.
- the combined use of Lyocell and flame-retardant acrylic fibers containing zinc stannate compounds significantly improved flame retardancy, especially in the ISO 15025:2016 flame test method. show. (1) Contains 30 to 80% by mass of the flame-retardant acrylic fiber and 20 to 70% by mass of Lyocell. (2) Contains 35-75% by mass of the flame-retardant acrylic fiber and 25-65% by mass of Lyocell. (3) Contains 40 to 70% by mass of the flame-retardant acrylic fiber and 30 to 60% by mass of Lyocell.
- Zinc hydroxystannate in a dispersion of zinc hydroxystannate or metastannic acid was measured using a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, Ltd., particle size distribution measuring device LA-950V2).
- the particle size distribution of metastannic acid was measured to determine the average particle size D50.
- the combustion test method based on ISO 15025:2016 is a method in which a flame of 25 ⁇ 2 mm is ignited for 10 seconds from a position 17 ⁇ 1 mm away at right angles to the evaluation fabric set in a specified holder.
- the content of the flame retardant (zinc hydroxystannate or metastannic acid) in the acrylic fibers was measured by a fluorescent X-ray analysis method using a fluorescent X-ray device ("SEA2210A" manufactured by SII Nano Technology). Using a standard sample with a known tin content, the fluorescent X-ray intensity of tin was measured in advance to create a calibration curve. Next, the tin content in the acrylic fiber was determined by measuring the fluorescent X-ray intensity of tin in the acrylic fiber and comparing it with a calibration curve.
- the zinc hydroxystannate was added in advance to dimethyl sulfoxide in an amount of 30% by mass, and was uniformly dispersed for use as a prepared dispersion.
- the average particle diameter D50 of zinc hydroxystannate measured by a laser diffraction/scattering method was 1.2 ⁇ m.
- the obtained spinning stock solution was extruded into a 50% by mass dimethyl sulfoxide aqueous solution to solidify it, then washed with water and dried at 120°C, and after drying, it was tripled in size.
- an acrylic fiber was obtained by further performing a heat treatment at 145° C. for 5 minutes.
- the obtained acrylic fiber of Production Example 1 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
- Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 5 parts by mass based on 100 parts by mass of the acrylic copolymer.
- the obtained acrylic fiber of Production Example 2 had a single fiber fineness of 1.6 dtex and a cut length of 38 mm.
- Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 7 parts by mass based on 100 parts by mass of the acrylic copolymer.
- the obtained acrylic fiber of Production Example 3 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
- Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 10 parts by mass based on 100 parts by mass of the acrylic copolymer.
- the obtained acrylic fiber of Production Example 4 had a single fiber fineness of 1.8 dtex and a cut length of 38 mm.
- the acrylic fibers of Production Examples 1 to 4 contain zinc hydroxystannate inside the fibers, and the acrylic fibers of Production Example 5 contain metastannic acid inside the fibers.
- the content of zinc hydroxystannate or metastannic acid in the acrylic fibers was measured as described above, and the results are shown in Table 1 below.
- a roving yarn was produced using a high-speed roving frame FL200 manufactured by Toyota Industries Corporation, and a spun yarn with a count of 20/1 was produced using a high-speed spinning frame UA37 manufactured by Howa Kogyo Co., Ltd.
- a single knit fabric having a basis weight shown in Table 2 below was produced using a computerized flat knitting machine SSG series 122FC manufactured by Shima Seiki Co., Ltd.
- Table 2 below the amounts of zinc hydroxystannate and metastannic acid are based on 100 parts by mass of the acrylic copolymer.
- [1] Contains 30 to 80% by mass of flame-retardant acrylic fibers and 20 to 70% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers,
- the flame-retardant acrylic fiber contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound,
- a flame-retardant fabric having an afterflame time of 30 seconds or less in an ISO15025 combustion test.
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Abstract
Description
本発明は、環境に配慮しつつ、難燃性を高めた難燃性布帛及びそれを用いた難燃性作業服に関する。 The present invention relates to a flame-retardant fabric that has improved flame retardancy while being environmentally friendly, and flame-retardant work clothes using the same.
アクリル系繊維等のハロゲン含有繊維と、他の繊維、例えばセルロース系繊維の組合せは、一般的に、とりわけ作業服の分野で好適に使用されている。一方、アクリル系繊維等のハロゲン含有繊維の難燃化は、従来、難燃剤としてアンチモン化合物を１～５０質量部程度含有させる方法が一般的であった（例えば、特許文献１）。しかし、アンチモン化合物が環境や人体に影響を及ぼす恐れがあることから、アンチモン化合物以外の難燃剤が検討されている。例えば、特許文献２及び３には、ハロゲン含有繊維に難燃性を付与する化合物としてスズ系化合物を含ませ、該ハロゲン含有繊維をセルロース系繊維と組み合わせて使用することが提案されている。 Combinations of halogen-containing fibers such as acrylic fibers and other fibers, such as cellulose fibers, are generally suitably used, particularly in the field of workwear. On the other hand, the conventional method for making halogen-containing fibers such as acrylic fibers flame retardant has been to include about 1 to 50 parts by mass of an antimony compound as a flame retardant (for example, Patent Document 1). However, since antimony compounds may affect the environment and the human body, flame retardants other than antimony compounds are being considered. For example, Patent Documents 2 and 3 propose that halogen-containing fibers contain a tin-based compound as a compound that imparts flame retardancy, and that the halogen-containing fibers are used in combination with cellulose-based fibers.
しかしながら、特許文献２では、ハロゲン含有繊維にスズ酸亜鉛化合物を２０～５０重量％含ませていることから、コストが高いという問題があった。また、特許文献３に記載の繊維複合体は、作業服等に使用した場合、難燃性が十分ではない場合があった。 However, in Patent Document 2, there was a problem that the cost was high because the halogen-containing fiber contained 20 to 50% by weight of a zinc stannate compound. Further, the fiber composite described in Patent Document 3 may not have sufficient flame retardancy when used for work clothes or the like.
本発明は、上記従来の問題を解決するため、環境に配慮しつつ、コストを抑え、難燃性を高めた難燃性布帛及び難燃性作業服を提供する。 In order to solve the above-mentioned conventional problems, the present invention provides a flame-retardant fabric and flame-retardant work clothes that are environmentally friendly, reduce costs, and have improved flame retardancy.
本発明の１以上の実施態様は、難燃性アクリル系繊維を３０～８０質量％、並びに天然繊維及び化学繊維からなる群から選ばれる他の繊維を２０～７０質量％含み、前記難燃性アクリル系繊維は、アクリル系共重合体１００質量部及びスズ酸亜鉛化合物１～１８質量部を含有し、ＩＳＯ１５０２５燃焼試験において残炎時間が３０秒以下である、難燃性布帛に関する。 One or more embodiments of the present invention include 30-80% by weight of flame-retardant acrylic fibers and 20-70% by weight of other fibers selected from the group consisting of natural fibers and synthetic fibers, The acrylic fiber contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound, and relates to a flame-retardant fabric having an afterflame time of 30 seconds or less in an ISO 15025 combustion test.
本発明の１以上の実施態様は、前記難燃性布帛を含む難燃性作業服に関する。 One or more embodiments of the present invention relate to flame-retardant workwear comprising the flame-retardant fabric described above.
本発明によれば、環境に配慮しつつ、コストを抑え、難燃性を高めた難燃性布帛及びそれを含む難燃性作業服を提供する。 According to the present invention, it is possible to provide a flame-retardant fabric that is environmentally friendly, reduces costs, and has improved flame retardancy, and flame-retardant work clothes containing the same.
本発明の発明者らは、環境に配慮しつつ、アクリル系繊維を含む布帛の難燃性を高めるために検討を重ねた。その結果、アクリル系繊維に所定量のスズ酸亜鉛化合物を含ませるとともに、布帛における該アクリル系繊維と他の繊維の配合割合を所定の範囲にすることで、該布帛が作業服の難燃性基準を評価するのに用いる燃焼試験、例えばＩＳＯ１５０２５：２０１６の燃焼試験方法において優れた難燃性（防炎性）を示し、具体的にはＩＳＯ１５０２５：２０１６の燃焼試験方法にて測定した残炎時間を３０秒以下に調整しやすいことを見出した。 The inventors of the present invention have conducted repeated studies to improve the flame retardancy of fabrics containing acrylic fibers while being environmentally friendly. As a result, by incorporating a predetermined amount of zinc stannate compound into acrylic fibers and by adjusting the blending ratio of the acrylic fibers and other fibers within a predetermined range, the fabric can improve the flame retardant properties of work clothes. It shows excellent flame retardancy (flame retardancy) in the combustion test used to evaluate the standard, for example, the ISO 15025: 2016 combustion test method, and specifically the afterflame time measured by the ISO 15025: 2016 combustion test method. It was found that it is easy to adjust the time to 30 seconds or less.
特に、驚くことに、本発明においては、理由は定かではないが、スズ酸亜鉛化合物を含むアクリル系繊維と、リヨセルを併用した場合、スズ酸亜鉛化合物の配合量が少なくても、作業服の難燃性基準を評価するのに用いる燃焼試験、例えばＩＳＯ１５０２５：２０１６の燃焼試験方法において極めて高い難燃性（防炎性）を示し、具体的にはＩＳＯ１５０２５：２０１６の燃焼試験方法にて測定した残炎時間が２秒以下になることを見出した。 In particular, surprisingly, in the present invention, although the reason is not clear, when acrylic fibers containing a zinc stannate compound and Lyocell are used together, even if the amount of the zinc stannate compound is small, the work clothes It showed extremely high flame retardancy (flame retardancy) in the combustion test used to evaluate flame retardant standards, for example, the ISO 15025: 2016 combustion test method, and specifically, it was measured using the ISO 15025: 2016 combustion test method. It was found that the afterflame time was 2 seconds or less.
本明細書において、数値範囲が「～」で示されている場合、該数値範囲は両端値（上限及び下限）を含む。例えば、「Ａ～Ｂ」という数値範囲は、Ａ及びＢという両端値を含む範囲であり、「Ａ以上Ｂ以下」と同じ範囲である。また、本明細書において、数値範囲が複数記載されている場合、異なる数値範囲の上限及び下限を適宜組み合わせた数値範囲を含むものとする。 In this specification, when a numerical range is indicated by "~", the numerical range includes both end values (upper limit and lower limit). For example, the numerical range "A to B" is a range that includes both end values of A and B, and is the same range as "A to B". Moreover, in this specification, when multiple numerical ranges are described, numerical ranges that are appropriately combined with the upper and lower limits of different numerical ranges are included.
本発明の１以上の実施態様において、難燃性アクリル系繊維は、アクリル系共重合体１００質量部に対して、スズ酸亜鉛化合物を１～１８質量部含む。作業服の難燃性基準を評価するのに用いる燃焼試験、特に、ＩＳＯ１５０２５：２０１６の燃焼試験における難燃性基準を満たしやすい観点から、アクリル系共重合体１００質量部に対して、スズ酸亜鉛化合物を２質量部以上含むことが好ましく、３質量部以上含むことがより好ましく、４質量部以上含むことがさらに好ましい。また、本発明の１以上の実施態様において、難燃性アクリル系繊維は、コスト、強度、紡糸性、着色防止、及び染色性等の観点から、アクリル系共重合体１００質量部に対して、スズ酸亜鉛化合物を１６質量部以下含むことが好ましく、１５質量部以下含むことがより好ましく、１４質量部以下含むことがさらに好ましく、１３質量部以下含むことがさらにより好ましい。 In one or more embodiments of the present invention, the flame-retardant acrylic fiber contains 1 to 18 parts by mass of a zinc stannate compound based on 100 parts by mass of the acrylic copolymer. From the viewpoint of easily meeting the flame retardant standards in the flame retardant tests used to evaluate the flame retardant standards of work clothes, especially the ISO15025:2016 flame retardant standards, zinc stannate was added to 100 parts by mass of the acrylic copolymer. The content of the compound is preferably 2 parts by mass or more, more preferably 3 parts by mass or more, and even more preferably 4 parts by mass or more. In addition, in one or more embodiments of the present invention, the flame-retardant acrylic fiber is composed of: The zinc stannate compound is preferably contained in 16 parts by mass or less, more preferably in 15 parts by mass or less, even more preferably in 14 parts by mass or less, and even more preferably in 13 parts by mass or less.
前記難燃性アクリル系繊維は、繊維全質量に対して、スズ酸亜鉛化合物を１．０～１５．３質量％含むことが好ましく、２．０～１３．８質量％含むことがより好ましく、２．５～１３．０質量％含むことがさらに好ましく、３．０～１２．３質量％含むことがさらにより好ましく、３．５～１１．５質量％含むことがさらにより好ましい。本明細書において、難燃性アクリル系繊維中の「スズ酸亜鉛化合物」の含有量は、蛍光Ｘ線分析法で測定することができる。 The flame-retardant acrylic fiber preferably contains 1.0 to 15.3% by mass, more preferably 2.0 to 13.8% by mass of a zinc stannate compound, based on the total mass of the fiber. It is more preferable to contain 2.5 to 13.0% by mass, even more preferably to contain 3.0 to 12.3% by mass, and even more preferably to contain 3.5 to 11.5% by mass. In this specification, the content of "zinc stannate compound" in the flame-retardant acrylic fiber can be measured by fluorescent X-ray analysis.
前記スズ酸亜鉛化合物は、例えば、スズ酸亜鉛（ＺｎＳｎＯ3）でもよく、ヒドロキシ錫酸亜鉛（ＺｎＳｎ（ＯＨ）6）でもよいが、例えば、繊維、布帛及び作業服の難燃性をより高める観点から、ヒドロキシ錫酸亜鉛であることが好ましい。 The zinc stannate compound may be, for example, zinc stannate (ZnSnO 3 ) or zinc hydroxystannate (ZnSn(OH) 6 ). Therefore, zinc hydroxystannate is preferred.
前記スズ酸亜鉛化合物は、特に限定されないが、例えば紡糸性や繊維強度の観点から、平均粒子径Ｄ５０が好ましくは５μｍ以下、より好ましくは３μｍ以下、さらに好ましくは２μｍ以下である。また、前記スズ酸亜鉛化合物の平均粒子径Ｄ５０の下限は、特に限定されないが、例えば、取扱性の観点から、０．１μｍ以上であってもよい。また、難燃性アクリル系繊維の配合量を少なくした場合、例えば、４５質量％未満又は４０質量％以下にした場合の難燃性を高める観点から、０．５μｍ以上であることが好ましく、０．６μｍ以上であることがより好ましく、０．７μｍ以上であることが特に好ましい。本明細書において、化合物の平均粒子径Ｄ５０は、水や有機溶媒に分散した分散体（分散液）を用い、レーザー回折／散乱法又は動的光散乱法で測定することができる。 The zinc stannate compound is not particularly limited, but for example, from the viewpoint of spinnability and fiber strength, the average particle diameter D50 is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. Further, the lower limit of the average particle diameter D50 of the zinc stannate compound is not particularly limited, but may be, for example, 0.1 μm or more from the viewpoint of handleability. In addition, from the viewpoint of improving flame retardancy when the amount of flame-retardant acrylic fiber is reduced, for example, less than 45% by mass or 40% by mass, it is preferably 0.5 μm or more, and 0.5 μm or more. It is more preferably .6 μm or more, and particularly preferably 0.7 μm or more. In this specification, the average particle diameter D50 of a compound can be measured by a laser diffraction/scattering method or a dynamic light scattering method using a dispersion (dispersion liquid) dispersed in water or an organic solvent.
前記アクリル系共重合体は、アクリロニトリル、ハロゲン含有単量体、並びに他の共重合可能なビニル単量体を含むものを用いることができる。耐熱性及び難燃性をより高める観点から、前記アクリル系共重合体は、アクリロニトリルを３０～８５質量％、ハロゲン含有単量体を１５～７０質量％、及び他の共重合可能なビニル単量体を０～３質量％以下含むことが好ましく、アクリロニトリルを３５～７５質量％、ハロゲン含有単量体を２５～６５質量％、及び他の共重合可能なビニル単量体を０～３質量％以下含むことがより好ましく、アクリロニトリルを４０～７０質量％、ハロゲン含有単量体を３０～６０質量％、及び他の共重合可能なビニル単量体を０～３質量％以下含むことがさらに好ましい。前記ハロゲン含有単量体は、ハロゲン含有ビニル単量体及びハロゲン含有ビニリデン単量体からなる群から選ばれる１以上を含む。前記他の共重合可能なビニル系単量体としては、アクリロニトリルと共重合可能なものであればよく特に限定されない。 The acrylic copolymer may contain acrylonitrile, a halogen-containing monomer, and other copolymerizable vinyl monomers. From the viewpoint of further increasing heat resistance and flame retardancy, the acrylic copolymer contains 30 to 85% by mass of acrylonitrile, 15 to 70% by mass of a halogen-containing monomer, and other copolymerizable vinyl monomers. It preferably contains 0 to 3% by mass or less of acrylonitrile, 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of a halogen-containing monomer, and 0 to 3% by mass of other copolymerizable vinyl monomers. It is more preferable to contain the following: 40 to 70% by mass of acrylonitrile, 30 to 60% by mass of a halogen-containing monomer, and even more preferably 0 to 3% by mass of other copolymerizable vinyl monomers. . The halogen-containing monomer includes one or more selected from the group consisting of a halogen-containing vinyl monomer and a halogen-containing vinylidene monomer. The other copolymerizable vinyl monomer is not particularly limited as long as it is copolymerizable with acrylonitrile.
前記ハロゲン含有ビニル単量体としては、例えば、塩化ビニル、臭化ビニル等が挙げられ、ハロゲン含有ビニリデン単量体としては、塩化ビニリデン、臭化ビニリデン等が挙げられる。これらのハロゲン含有単量体は、１種又は２種以上を組み合わせて用いてもよい。中でも、塩化ビニル及び塩化ビニリデンからなる群から選ばれる一種以上が好ましく、塩化ビニリデンがより好ましい。 Examples of the halogen-containing vinyl monomer include vinyl chloride and vinyl bromide, and examples of the halogen-containing vinylidene monomer include vinylidene chloride and vinylidene bromide. These halogen-containing monomers may be used alone or in combination of two or more. Among these, one or more selected from the group consisting of vinyl chloride and vinylidene chloride is preferred, and vinylidene chloride is more preferred.
前記他の共重合可能なビニル系単量体としては、特に限定されないが、例えば、アクリル酸やメタクリル酸に代表される不飽和カルボン酸類及びこれらの塩類、メタクリル酸メチルに代表されるメタクリル酸エステル、グリシジルメタクリレート等に代表される不飽和カルボン酸のエステル類、酢酸ビニルや酪酸ビニルに代表されるビニルエステル類、スルホン酸基を含有する単量体等を用いることができる。前記スルホン酸基を含有する単量体としては、特に限定されないが、アリルスルホン酸、メタリルスルホン酸、スチレンスルホン酸、イソプレンスルホン酸、２－アクリルアミド－２－メチルプロパンスルホン酸並びにこれらのナトリウム塩等の金属塩類及びアミン塩類等を用いることができる。これらの他の共重合可能なビニル系単量体は１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。スルホン酸基を含有する単量体は必要に応じて使用されるが、前記アクリル系共重合体中のスルホン酸基を含有する単量体の含有量が３質量％以下であれば紡糸工程の生産安定性に優れる。 The other copolymerizable vinyl monomers are not particularly limited, but include, for example, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, salts thereof, and methacrylic esters such as methyl methacrylate. , esters of unsaturated carboxylic acids such as glycidyl methacrylate, vinyl esters such as vinyl acetate and vinyl butyrate, monomers containing sulfonic acid groups, and the like can be used. The monomer containing the sulfonic acid group is not particularly limited, but includes allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and sodium salts thereof. Metal salts such as, amine salts, etc. can be used. These other copolymerizable vinyl monomers may be used alone or in combination of two or more. A monomer containing a sulfonic acid group may be used as necessary, but if the content of the monomer containing a sulfonic acid group in the acrylic copolymer is 3% by mass or less, it may be used in the spinning process. Excellent production stability.
前記アクリル系共重合体は、取扱性及び難燃性をより高める観点から、アクリロニトリルを３５～７５質量％、塩化ビニル及び／又は塩化ビニリデンを２５～６５質量％、並びに他の共重合可能なビニル系単量体を０～３質量％含むことが好ましく、アクリルニトリルを４０～７０質量％、塩化ビニル及び／又は塩化ビニリデンを３０～６０質量％、並びに他の共重合可能なビニル系単量体を０～３質量％含むことがより好ましい。また、アクリル系共重合体はアクリロニトリルを３５～７５質量％、塩化ビニリデンを２５～６５質量％、及び他の共重合可能なビニル系単量体を０～３質量％含むことが好ましく、アクリルニトリルを４０～７０質量％、塩化ビニリデンを３０～６０質量％、及び他の共重合可能なビニル系単量体を０～３質量％含むことがより好ましい。 The acrylic copolymer contains 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of vinyl chloride and/or vinylidene chloride, and other copolymerizable vinyls, from the viewpoint of improving handleability and flame retardance. It preferably contains 0 to 3% by mass of monomers, including 40 to 70% by mass of acrylonitrile, 30 to 60% by mass of vinyl chloride and/or vinylidene chloride, and other copolymerizable vinyl monomers. More preferably, it contains 0 to 3% by mass. Further, the acrylic copolymer preferably contains 35 to 75% by mass of acrylonitrile, 25 to 65% by mass of vinylidene chloride, and 0 to 3% by mass of other copolymerizable vinyl monomers. More preferably, it contains 40 to 70% by mass of vinylidene chloride, 30 to 60% by mass of vinylidene chloride, and 0 to 3% by mass of other copolymerizable vinyl monomers.
前記アクリル系共重合体は、塊状重合、懸濁重合、乳化重合、溶液重合等の既知の重合方法で得ることができる。この中でも工業的視点から、懸濁重合、乳化重合又は溶液重合が好ましい。 The acrylic copolymer can be obtained by known polymerization methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Among these, suspension polymerization, emulsion polymerization, and solution polymerization are preferred from an industrial viewpoint.
本発明の１以上の実施態様において、難燃性アクリル系繊維は、必要に応じて帯電防止剤、熱着色防止剤、耐光性向上剤、白度向上剤、失透性防止剤、及び着色剤等の他の添加剤を含有してもよい。 In one or more embodiments of the present invention, the flame-retardant acrylic fiber optionally contains an antistatic agent, a thermal coloring inhibitor, a light fastness improver, a whiteness improver, a devitrification inhibitor, and a colorant. It may also contain other additives such as.
本発明の１以上の実施態様において、難燃性アクリル系繊維は、短繊維でも長繊維でもよく、使用方法において適宜選択することが可能である。単繊維繊度は、使用される布帛、繊維製品の用途により適宜選択されるが、１～５０ｄｔｅｘであってもよく、１．５～３０ｄｔｅｘであってもよく、１．７～１５ｄｔｅｘであってもよい。繊維長は、布帛、繊維製品の用途により適宜選択される。例えば、ショートカットファイバー（繊維長０．１～５ｍｍ）、短繊維（繊維長１５～１７６ｍｍ、２０～１６０ｍｍ、２５～１３８ｍｍ、又は３０～１２８ｍｍ）、及び長繊維（フィラメント）が挙げられる。 In one or more embodiments of the present invention, the flame-retardant acrylic fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use. The single fiber fineness is appropriately selected depending on the purpose of the fabric and textile product used, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. good. The fiber length is appropriately selected depending on the use of the fabric or textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
本発明の１以上の実施態様において、難燃性アクリル系繊維は、例えば耐久性の観点から、単繊維強度が１．０～４．０ｃＮ／ｄｔｅｘであることが好ましく、１．５～３．５ｃＮ／ｄｔｅｘであることがより好ましい。本発明の１以上の実施態様において、難燃性アクリル系繊維は、例えば実用性の観点から、伸度が２０～４０％であることが好ましく、伸度が２０～３０％であることがより好ましい。本明細書において、難燃性アクリル系繊維の単繊維強度及び伸度は、ＪＩＳ Ｌ １０１３：２０２１又はＪＩＳ Ｌ １０１５：２０２１に準じて測定することができる。 In one or more embodiments of the present invention, the flame-retardant acrylic fiber preferably has a single fiber strength of 1.0 to 4.0 cN/dtex, and 1.5 to 3.0 cN/dtex, for example, from the viewpoint of durability. More preferably, it is 5 cN/dtex. In one or more embodiments of the present invention, the flame-retardant acrylic fiber preferably has an elongation of 20 to 40%, and more preferably an elongation of 20 to 30%, for example from a practical standpoint. preferable. In this specification, the single fiber strength and elongation of the flame-retardant acrylic fiber can be measured according to JIS L 1013:2021 or JIS L 1015:2021.
本発明の１以上の実施態様において、難燃性アクリル系繊維は、特に限定されないが、好ましくはアクリル系共重合体と、スズ酸亜鉛化合物を含む組成物を紡糸することにより製造することができる。具体的には、湿式紡糸法、乾式紡糸法、及び半乾半湿式法等の公知の方法で行うことができる。例えば湿式紡糸法の場合は、前記アクリル系共重合体を溶媒に溶解した後、そこへスズ酸亜鉛化合物を添加して得られた紡糸原液を用いる以外は、一般的なアクリル系繊維の場合と同様に、紡糸原液をノズルを通じて凝固浴に押出すことで凝固させ、次いで延伸、水洗、乾燥、熱処理し、必要であれば捲縮を付与して切断することで作製することができる。スズ酸亜鉛化合物を溶媒に溶解したスズ酸亜鉛化合物の溶液を、アクリル系共重合体を溶媒に溶解した樹脂溶液に添加してもよい。前記溶媒としては、例えば、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、及びアセトン等の有機溶媒や、ロダン塩水溶液、及び硝酸水溶液等の無機溶媒が挙げられる。湿式紡糸にて得られたアクリル系繊維中の化合物の粒子径は、紡糸原液中の化合物の粒子径と同等であり、湿式紡糸にて得られたアクリル系繊維中の化合物の平均粒子径Ｄ５０は、紡糸原液中の化合物の平均粒子径で示すことができる。 In one or more embodiments of the present invention, the flame-retardant acrylic fiber can be produced by spinning a composition preferably including, but not limited to, an acrylic copolymer and a zinc stannate compound. . Specifically, known methods such as a wet spinning method, a dry spinning method, and a semi-dry semi-wet method can be used. For example, in the case of wet spinning, the method is similar to the case of general acrylic fibers, except that a spinning stock solution obtained by dissolving the acrylic copolymer in a solvent and adding a zinc stannate compound thereto is used. Similarly, it can be produced by coagulating the spinning solution by extruding it into a coagulation bath through a nozzle, followed by stretching, washing with water, drying, heat treatment, and if necessary, crimping and cutting. A solution of a zinc stannate compound dissolved in a solvent may be added to a resin solution containing an acrylic copolymer dissolved in a solvent. Examples of the solvent include organic solvents such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and acetone, and inorganic solvents such as rhodan salt aqueous solution and nitric acid aqueous solution. The particle diameter of the compound in the acrylic fiber obtained by wet spinning is equivalent to the particle diameter of the compound in the spinning dope, and the average particle diameter D50 of the compound in the acrylic fiber obtained by wet spinning is , can be expressed as the average particle diameter of the compound in the spinning dope.
本発明の１以上の実施態様の難燃性布帛は、前記難燃性アクリル系繊維を３０～８０質量％、並びに天然繊維及び化学繊維からなる群から選ばれる一つ以上の他の繊維を２０～７０質量％含む。これにより、難燃性布帛の難燃性を良好にしつつ、他の繊維による特性を付与することができる。前記難燃性布帛は、より好ましくは前記難燃性アクリル系繊維を３５～７５質量％、並びに天然繊維及び化学繊維からなる群から選ばれる他の繊維を２５～６５質量％含み、さらに好ましくは前記難燃性アクリル系繊維を４０～７５質量％、並びに天然繊維及び化学繊維からなる群から選ばれる他の繊維を２５～６０質量％含む。 The flame-retardant fabric according to one or more embodiments of the present invention contains 30 to 80% by mass of the flame-retardant acrylic fibers and 20% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers. Contains ~70% by mass. This makes it possible to improve the flame retardance of the flame-retardant fabric while imparting the characteristics of other fibers. The flame-retardant fabric more preferably contains 35 to 75% by mass of the flame-retardant acrylic fibers and 25 to 65% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers, and even more preferably It contains 40 to 75% by mass of the flame-retardant acrylic fiber and 25 to 60% by mass of other fibers selected from the group consisting of natural fibers and chemical fibers.
前記天然繊維としては、木綿繊維、カポック繊維、亜麻繊維、大麻繊維、ラミー繊維、ジュート繊維、マニラ麻繊維、ケナフ繊維等の天然セルロース繊維；羊毛繊維、モヘア繊維、カシミヤ繊維、ラクダ繊維、アルパカ繊維、アンゴラ繊維、絹繊維等の天然動物繊維等が挙げられる。 The natural fibers include natural cellulose fibers such as cotton fiber, kapok fiber, flax fiber, hemp fiber, ramie fiber, jute fiber, Manila hemp fiber, and kenaf fiber; wool fiber, mohair fiber, cashmere fiber, camel fiber, alpaca fiber, Examples include natural animal fibers such as angora fiber and silk fiber.
前記再生繊維としては、レーヨン、ポリノジック、キュプラ、リヨセル等の再生セルロース繊維、再生コラーゲン繊維、再生タンパク繊維、酢酸セルロース繊維、プロミックス繊維等が挙げられる。 Examples of the regenerated fibers include regenerated cellulose fibers such as rayon, polynosic, cupro, and lyocell, regenerated collagen fibers, regenerated protein fibers, cellulose acetate fibers, and promix fibers.
前記合成繊維としては、ポリエステル繊維、ポリアミド繊維、ポリ乳酸繊維、アクリル繊維、ポリオレフィン繊維（ポリエチレン繊維及びポリプロピレン繊維等）、ポリビニルアルコール繊維、ポリ塩化ビニル繊維、ポリ塩化ビニリデン繊維、ポリクラール繊維、ポリウレタン繊維、ポリオキシメチレン繊維、ポリテトラフルオロエチレン繊維、アラミド繊維、ベンゾエート繊維、ポリフェニレンスルフィド繊維、ポリエーテルエーテルケトン繊維、ポリベンズアゾール繊維、ポリイミド繊維、ポリアミドイミド繊維等が挙げられる。また、前記合成繊維として、難燃ポリエステル、ポリエチレンナフタレート繊維、メラミン繊維、アクリレート繊維、ポリベンズオキサイド繊維等を用いてもよい。その他、酸化アクリル繊維、炭素繊維、ガラス繊維、活性炭素繊維等が挙げられる。 The synthetic fibers include polyester fibers, polyamide fibers, polylactic acid fibers, acrylic fibers, polyolefin fibers (polyethylene fibers, polypropylene fibers, etc.), polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polyclar fibers, polyurethane fibers, Examples include polyoxymethylene fibers, polytetrafluoroethylene fibers, aramid fibers, benzoate fibers, polyphenylene sulfide fibers, polyetheretherketone fibers, polybenzazole fibers, polyimide fibers, polyamideimide fibers, and the like. Further, as the synthetic fiber, flame-retardant polyester, polyethylene naphthalate fiber, melamine fiber, acrylate fiber, polybenzoxide fiber, etc. may be used. Other examples include acrylic oxide fiber, carbon fiber, glass fiber, and activated carbon fiber.
前記他の繊維としては、天然繊維、再生セルロース繊維、ポリエステル繊維、アラミド繊維及びメラミン繊維等が好ましい。 Preferable examples of the other fibers include natural fibers, regenerated cellulose fibers, polyester fibers, aramid fibers, and melamine fibers.
上述した他の繊維は、一つを単独で用いてもよく、二つ以上を組合わせて用いてもよい。 The other fibers mentioned above may be used alone or in combination of two or more.
本発明の１以上の実施態様において、他の繊維は、短繊維でも長繊維でもよく、使用方法において適宜選択することが可能である。単繊維繊度は、使用される布帛、繊維製品の用途により適宜選択されるが、１～５０ｄｔｅｘであってもよく、１．５～３０ｄｔｅｘであってもよく、１．７～１５ｄｔｅｘであってもよい。繊維長は、布帛、繊維製品の用途により適宜選択される。例えば、ショートカットファイバー（繊維長０．１～５ｍｍ）、短繊維（繊維長１５～１７６ｍｍ、２０～１６０ｍｍ、２５～１３８ｍｍ、又は３０～１２８ｍｍ）、及び長繊維（フィラメント）が挙げられる。 In one or more embodiments of the present invention, the other fibers may be short fibers or long fibers, and can be appropriately selected depending on the method of use. The single fiber fineness is appropriately selected depending on the purpose of the fabric and textile product used, but it may be 1 to 50 dtex, 1.5 to 30 dtex, or 1.7 to 15 dtex. good. The fiber length is appropriately selected depending on the use of the fabric or textile product. Examples include short-cut fibers (fiber length 0.1 to 5 mm), short fibers (fiber length 15 to 176 mm, 20 to 160 mm, 25 to 138 mm, or 30 to 128 mm), and long fibers (filaments).
前記難燃性布帛は、織物でもよく、編物でもよい。 The flame-retardant fabric may be a woven fabric or a knitted fabric.
織物としては、平織、斜文織、朱子織、変化平織、変化斜文織、変化朱子織、変わり織、紋織、片重ね織、二重組織、多重組織、経パイル織、緯パイル織、及び絡み織等が挙げられる。平織、朱子織、紋織が、商品としての風合いや強度等に優れる。 Fabrics include plain weave, oblique weave, satin weave, variable plain weave, variable oblique weave, variable satin weave, variable weave, patterned weave, single layer weave, double weave, multiple weave, warp pile weave, weft pile weave, and Examples include twine weave. Plain weave, satin weave, and patterned weave have excellent texture and strength as products.
編物としては、丸編、緯編、経編、パイル編等を含み、平編、天竺編、リブ編、スムース編（両面編）、ゴム編、パール編、デンビー組織、コード組織、アトラス組織、鎖組織、及び挿入組織等が挙げられる。天竺編、リブ編が、商品としての風合いに優れる。 Knitted fabrics include circular knitting, weft knitting, warp knitting, pile knitting, etc., flat knitting, jersey knitting, rib knitting, smooth knitting (double-sided knitting), rubber knitting, pearl knitting, denby knitting, cord knitting, atlas knitting, Examples include chain tissue and intercalated tissue. Tenjiku knitting and ribbed knitting have excellent texture as products.
前記難燃性布帛は、様々な繊維製品（ａｐｐｌｉｃａｔｉｏｎ）に用いることができる、繊維製品としては、例えば、次のようなものが例示される。
（１）衣類及び日用品材料
衣服（上着、下着、セーター、ベスト、ズボン等を含む）、手袋、靴下、マフラー、帽子、寝具、枕、クッション、ぬいぐるみ等
（２）特殊服
防護服及び消防服等の火を取り扱う作業者が着用する作業服、防寒服等
（３）インテリア材料
椅子張り、カーテン、壁紙、カーペット等
（４）産業資材
フィルター、耐炎詰め物、ライニング材等。
The flame-retardant fabric can be used in various textile applications. Examples of textile products include the following.
(1) Clothing and daily necessities Clothing (including jackets, underwear, sweaters, vests, pants, etc.), gloves, socks, mufflers, hats, bedding, pillows, cushions, stuffed animals, etc. (2) Special clothing Protective clothing and firefighting clothing (3) Interior materials: Upholstery, curtains, wallpaper, carpets, etc. (4) Industrial materials: Filters, flame-resistant padding, lining materials, etc.
前記難燃性布帛は、ＩＳＯ１５０２５：２０１６燃焼試験において残炎時間が３０秒以下であればよいが、難燃性（防炎性）により優れる観点から、ＩＳＯ１５０２５：２０１６燃焼試験において残炎時間が１０秒以下であることが好ましく、より好ましくは５秒以下であり、さらに好ましくは３秒以下であり、特に好ましくは２．０秒以下である。これにより、防護服及び消防服等の火を取り扱う作業の難燃性作業服に好適に用いることができる。 The flame retardant fabric may have an afterflame time of 30 seconds or less in the ISO 15025:2016 combustion test, but from the viewpoint of superior flame retardancy (flame resistance), the afterflame time should be 10 seconds or less in the ISO 15025:2016 combustion test. The time is preferably at most seconds, more preferably at most 5 seconds, even more preferably at most 3 seconds, particularly preferably at most 2.0 seconds. As a result, it can be suitably used for flame-retardant work clothes for work involving fire, such as protective clothing and firefighting clothing.
前記難燃性布帛は、特に限定されないが、風合いの観点から、目付が１５０～４００ｇ／ｍ2であることが好ましく、より好ましくは２００～３８０ｇ／ｍ2であり、さらに好ましくは２２０～３５０ｇ／ｍ2である。 The flame retardant fabric is not particularly limited, but from the viewpoint of texture, it is preferable that the fabric weight is 150 to 400 g/m 2 , more preferably 200 to 380 g/m 2 , and still more preferably 220 to 350 g/m 2 . m2 .
防護服及び消防服等の火を取り扱う作業の難燃性作業服用生地としては、下記のような繊維組成の織物及び／又は編物等の布帛を好適に用いることができる。セルロース系繊維を併用することで、布帛や作業服に吸湿性及び快適性を付与することができる。セルロース系繊維の含有量は２０質量％未満の場合、快適性を維持できない恐れがある。
（１）前記難燃性アクリル系繊維３０～８０質量％、及びセルロース系繊維（天然セルロース繊維及び/又は再生セルロース繊維）２０～７０質量％を含む。
（２）前記難燃性アクリル系繊維３５～７５質量％、及びセルロース系繊維（天然セルロース繊維及び/又は再生セルロース繊維）２５～６５質量％を含む。
（３）前記難燃性アクリル系繊維４０～７０質量％、及びセルロース系繊維（天然セルロース繊維及び/又は再生セルロース繊維）３０～６０質量％を含む。
Fabrics such as woven and/or knitted fabrics having the following fiber compositions can be suitably used as flame-retardant workwear fabrics for work involving fire, such as protective clothing and firefighting clothing. By using cellulose fibers in combination, it is possible to impart hygroscopicity and comfort to fabrics and work clothes. If the content of cellulose fibers is less than 20% by mass, comfort may not be maintained.
(1) Contains 30 to 80% by mass of the flame-retardant acrylic fibers and 20 to 70% by mass of cellulose fibers (natural cellulose fibers and/or regenerated cellulose fibers).
(2) Contains 35 to 75% by mass of the flame-retardant acrylic fibers and 25 to 65% by mass of cellulose fibers (natural cellulose fibers and/or regenerated cellulose fibers).
(3) Contains 40 to 70% by mass of the flame-retardant acrylic fibers and 30 to 60% by mass of cellulose fibers (natural cellulose fibers and/or regenerated cellulose fibers).
難燃性をより一層高める観点から、防護服及び消防服等の火を取り扱う作業の難燃性作業服用生地としては、下記のような繊維組成の織物及び／又は編物等の布帛を好適に用いることができる。驚くことに、スズ酸亜鉛化合物を含む難燃性アクリル系繊維とリヨセルを併用することで、難燃性が格段に向上し、特にＩＳＯ１５０２５：２０１６の燃焼試験方法において格段に向上した難燃性を示す。
（１）前記難燃性アクリル系繊維３０～８０質量％、及びリヨセル２０～７０質量％を含む。
（２）前記難燃性アクリル系繊維３５～７５質量％、及びリヨセル２５～６５質量％を含む。
（３）前記難燃性アクリル系繊維４０～７０質量％、及びリヨセル３０～６０質量％を含む。
From the perspective of further increasing flame retardancy, fabrics such as woven and/or knitted fabrics with the following fiber composition are preferably used as flame-retardant workwear fabrics for work that handles fire, such as protective clothing and firefighting clothing. be able to. Surprisingly, the combined use of Lyocell and flame-retardant acrylic fibers containing zinc stannate compounds significantly improved flame retardancy, especially in the ISO 15025:2016 flame test method. show.
(1) Contains 30 to 80% by mass of the flame-retardant acrylic fiber and 20 to 70% by mass of Lyocell.
(2) Contains 35-75% by mass of the flame-retardant acrylic fiber and 25-65% by mass of Lyocell.
(3) Contains 40 to 70% by mass of the flame-retardant acrylic fiber and 30 to 60% by mass of Lyocell.
以下実施例により本発明を更に具体的に説明する。なお、本発明は下記の実施例に限定されるものではない。 The present invention will be explained in more detail with reference to Examples below. Note that the present invention is not limited to the following examples.
実施例及び比較例にて用いた測定・評価方法は下記のとおりである。 The measurement and evaluation methods used in the Examples and Comparative Examples are as follows.
（平均粒子径Ｄ５０）
レーザー回折／散乱式粒子径分布測定装置（株式会社堀場製作所製、粒子径分布測定装置ＬＡ－９５０Ｖ２）を用いてレーザー回折／散乱法でヒドロキシ錫酸亜鉛又はメタスズ酸の分散液におけるヒドロキシ錫酸亜鉛又はメタスズ酸の粒子径分布を測定し、平均粒子径Ｄ５０を求めた。
(Average particle diameter D50)
Zinc hydroxystannate in a dispersion of zinc hydroxystannate or metastannic acid was measured using a laser diffraction/scattering method using a laser diffraction/scattering particle size distribution measuring device (manufactured by Horiba, Ltd., particle size distribution measuring device LA-950V2). Alternatively, the particle size distribution of metastannic acid was measured to determine the average particle size D50.
（難燃性）
ＩＳＯ１５０２５：２０１６（ＰｒｏｃｅｄｕｒｅＡ）に基づく燃焼試験方法にて評価した。ＩＳＯ １５０２５：２０１６（ＰｒｏｃｅｄｕｒｅＡ）に基づく燃焼試験方法は、規定のホルダーにセットした評価用布帛に対して直角に１７±１ｍｍ離れた場所から２５±２ｍｍの炎を１０秒間着炎する方法である。
(Flame retardance)
Evaluation was performed using a combustion test method based on ISO15025:2016 (Procedure A). The combustion test method based on ISO 15025:2016 (Procedure A) is a method in which a flame of 25 ± 2 mm is ignited for 10 seconds from a position 17 ± 1 mm away at right angles to the evaluation fabric set in a specified holder.
（難燃剤の含有量）
アクリル系繊維中の難燃剤（ヒドロキシ錫酸亜鉛又はメタスズ酸）の含有量は蛍光Ｘ線装置（ＳＩＩナノテクノロジー社製「ＳＥＡ２２１０Ａ」）による蛍光Ｘ線分析方法で測定した。予め、スズ含有量が既知の標準試料を用いて、スズの蛍光Ｘ線強度を測定し、検量線を作成した。次に、アクリル系繊維におけるスズの蛍光Ｘ線強度を測定し、検量線と照らし合わせることでアクリル系繊維におけるスズの含有量を測定した。
(Flame retardant content)
The content of the flame retardant (zinc hydroxystannate or metastannic acid) in the acrylic fibers was measured by a fluorescent X-ray analysis method using a fluorescent X-ray device ("SEA2210A" manufactured by SII Nano Technology). Using a standard sample with a known tin content, the fluorescent X-ray intensity of tin was measured in advance to create a calibration curve. Next, the tin content in the acrylic fiber was determined by measuring the fluorescent X-ray intensity of tin in the acrylic fiber and comparing it with a calibration curve.
（製造例１）
アクリロニトリル５１質量％、塩化ビニリデン４８質量％及びｐ－スチレンスルホン酸ナトリウム１質量％からなるアクリル系共重合体をジメチルスルホキシドに樹脂濃度が３０質量％になるように溶解させた。得られたアクリル系共重合体の溶液に、アクリル系共重合体１００質量部に対して４質量部のヒドロキシ錫酸亜鉛（ＺｎＳｎ（ＯＨ）6、ＳＣＬ Ｉｔａｌｉａ． Ｓｐａ社製、品名「Ｚｉｎｆｌａｍ（登録商標）ＺＨＳ」）を添加し、紡糸原液とした。前記ヒドロキシ錫酸亜鉛は、予め、ジメチルスルホキシドに対して３０質量％になるように添加し、均一分散させて調製した分散液として用いた。前記ヒドロキシ錫酸亜鉛の分散液において、レーザー回折／散乱法で測定したヒドロキシ錫酸亜鉛の平均粒子径Ｄ５０は１．２μｍであった。得られた紡糸原液をノズル孔径０．０８ｍｍ及び孔数３００ホールのノズルを用い、５０質量％のジメチルスルホキシド水溶液中へ押し出して凝固させ、次いで水洗した後１２０℃で乾燥し、乾燥後に３倍に延伸してから、さらに１４５℃で５分間熱処理を行うことにより、アクリル系繊維を得た。得られた製造例１のアクリル系繊維は、単繊維繊度１．７ｄｔｅｘ、カット長３８ｍｍであった。
(Manufacturing example 1)
An acrylic copolymer consisting of 51% by mass of acrylonitrile, 48% by mass of vinylidene chloride, and 1% by mass of sodium p-styrene sulfonate was dissolved in dimethyl sulfoxide so that the resin concentration was 30% by mass. To the solution of the obtained acrylic copolymer, 4 parts by mass of zinc hydroxystannate (ZnSn(OH) 6 , manufactured by SCL Italia. Spa, product name "Zinflam (registered) Trademark) ZHS'') was added to prepare a spinning dope. The zinc hydroxystannate was added in advance to dimethyl sulfoxide in an amount of 30% by mass, and was uniformly dispersed for use as a prepared dispersion. In the dispersion of zinc hydroxystannate, the average particle diameter D50 of zinc hydroxystannate measured by a laser diffraction/scattering method was 1.2 μm. Using a nozzle with a nozzle diameter of 0.08 mm and 300 holes, the obtained spinning stock solution was extruded into a 50% by mass dimethyl sulfoxide aqueous solution to solidify it, then washed with water and dried at 120°C, and after drying, it was tripled in size. After the stretching, an acrylic fiber was obtained by further performing a heat treatment at 145° C. for 5 minutes. The obtained acrylic fiber of Production Example 1 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
（製造例２）
ヒドロキシ錫酸亜鉛の添加量をアクリル系共重合体１００質量部に対して５質量部になるようにした以外は、製造例１と同様の方法でアクリル系繊維を作製した。得られた製造例２のアクリル系繊維は、単繊維繊度１．６ｄｔｅｘ、カット長３８ｍｍであった。
(Manufacturing example 2)
Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 5 parts by mass based on 100 parts by mass of the acrylic copolymer. The obtained acrylic fiber of Production Example 2 had a single fiber fineness of 1.6 dtex and a cut length of 38 mm.
（製造例３）
ヒドロキシ錫酸亜鉛の添加量をアクリル系共重合体１００質量部に対して７質量部になるようにした以外は、製造例１と同様の方法でアクリル系繊維を作製した。得られた製造例３のアクリル系繊維は、単繊維繊度１．７ｄｔｅｘ、カット長３８ｍｍであった。
(Manufacturing example 3)
Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 7 parts by mass based on 100 parts by mass of the acrylic copolymer. The obtained acrylic fiber of Production Example 3 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
（製造例４）
ヒドロキシ錫酸亜鉛の添加量をアクリル系共重合体１００質量部に対して１０質量部になるようにした以外は、製造例１と同様の方法でアクリル系繊維を作製した。得られた製造例４のアクリル系繊維は、単繊維繊度１．８ｄｔｅｘ、カット長３８ｍｍであった。
(Manufacturing example 4)
Acrylic fibers were produced in the same manner as in Production Example 1, except that the amount of zinc hydroxystannate added was 10 parts by mass based on 100 parts by mass of the acrylic copolymer. The obtained acrylic fiber of Production Example 4 had a single fiber fineness of 1.8 dtex and a cut length of 38 mm.
（製造例５）
ヒドロキシ錫酸亜鉛に代えてメタスズ酸を用い、メタスズ酸の添加量をアクリル系共重合体１００質量部に対して５質量部になるようにした以外は、製造例１と同様の方法でアクリル系繊維を作製した。得られた製造例５のアクリル系繊維は、単繊維繊度１．７ｄｔｅｘ、カット長３８ｍｍであった。
(Manufacturing example 5)
An acrylic copolymer was prepared in the same manner as in Production Example 1, except that metastannic acid was used instead of zinc hydroxystannate, and the amount of metastannic acid added was 5 parts by mass per 100 parts by mass of the acrylic copolymer. Fibers were produced. The obtained acrylic fiber of Production Example 5 had a single fiber fineness of 1.7 dtex and a cut length of 38 mm.
製造例１～４のアクリル系繊維は、繊維内部にヒドロキシ錫酸亜鉛を含み、製造例５のアクリル系繊維は、繊維内部にメタスズ酸を含む。アクリル系繊維中のヒドロキシ錫酸亜鉛又はメタスズ酸の含有量を上述したとおりに測定し、その結果を下記表１に示した。 The acrylic fibers of Production Examples 1 to 4 contain zinc hydroxystannate inside the fibers, and the acrylic fibers of Production Example 5 contain metastannic acid inside the fibers. The content of zinc hydroxystannate or metastannic acid in the acrylic fibers was measured as described above, and the results are shown in Table 1 below.
（実施例１～８、比較例１～８）
製造例１～５で作製したアクリル系繊維、リヨセル（レンチング社製「テンセル（登録商標）」、単繊維繊度１．３ｄｔｅｘ、繊維長５１ｍｍ）、コットン（カット長３１ｍｍ以下の天然コットン繊維）を下記表２に示す所定の質量割合で混綿し、大和機工(株)製サンプルローラーカードＳＣ－５００にて解繊し、インテック(株)製小型連條機ＴＳＭ－ＤＦＳを用いてスライバーを作製した。次に、このスライバーを用いて豊田自動織機製高速粗紡機ＦＬ２００にて粗紡糸を、豊和工業株式会社製高速精紡機ＵＡ３７にて２０／１番手の紡績糸を作製した。この紡績糸を用い、島精機株式会社製コンピューター横編み機ＳＳＧシリーズ１２２ＦＣにより、下記表２に示す目付を有するシングルニット編地を作製した。なお、下記表２において、ヒドロキシ錫酸亜鉛及びメタスズ酸の量は、アクリル系共重合体１００質量部に対するものである。
(Examples 1 to 8, Comparative Examples 1 to 8)
The acrylic fibers produced in Production Examples 1 to 5, lyocell (“TENCEL (registered trademark)” manufactured by Lenzing, single fiber fineness 1.3 dtex, fiber length 51 mm), and cotton (natural cotton fibers with a cut length of 31 mm or less) are as follows. The cotton was blended at a predetermined mass ratio shown in Table 2, defibrated using a sample roller card SC-500 manufactured by Yamato Kiko Co., Ltd., and a sliver was produced using a small continuous sieve machine TSM-DFS manufactured by Intec Co., Ltd. Next, using this sliver, a roving yarn was produced using a high-speed roving frame FL200 manufactured by Toyota Industries Corporation, and a spun yarn with a count of 20/1 was produced using a high-speed spinning frame UA37 manufactured by Howa Kogyo Co., Ltd. Using this spun yarn, a single knit fabric having a basis weight shown in Table 2 below was produced using a computerized flat knitting machine SSG series 122FC manufactured by Shima Seiki Co., Ltd. In Table 2 below, the amounts of zinc hydroxystannate and metastannic acid are based on 100 parts by mass of the acrylic copolymer.
前記表２から分かるように、実施例の布帛の場合、ＩＳＯ １５０２５：２０１６（ＰｒｏｃｅｄｕｒｅＡ）に基づく燃焼試験方法にて測定した残炎時間が２．０秒以下であり、極めて難燃性（防炎性）が良好であった。 As can be seen from Table 2 above, in the case of the fabric of the example, the afterflame time measured by the combustion test method based on ISO 15025:2016 (Procedure A) is 2.0 seconds or less, and it is extremely flame retardant (flame retardant). performance) was good.
一方、実施例７と同じ難燃性アクリル系繊維を用いているが、該難燃性アクリル系繊維の配合量が３０質量％未満の比較例７の布帛は、ＩＳＯ １５０２５：２０１６（ＰｒｏｃｅｄｕｒｅＡ）に基づく燃焼試験方法にて測定した残炎時間が４０秒であり、難燃性が劣っていた。また、難燃剤としてメタスズ酸を用いた以外は、アクリル系繊維にける難燃剤の配合量、及びアクリル系繊維とセルロース系繊維の配合割合が実施例２と同様である比較例８の布帛は、ＩＳＯ １５０２５：２０１６（ＰｒｏｃｅｄｕｒｅＡ）に基づく燃焼試験方法にて全焼しており、難燃性が極めて劣っていた。 On the other hand, the fabric of Comparative Example 7, which uses the same flame-retardant acrylic fiber as in Example 7, but has a blending amount of the flame-retardant acrylic fiber of less than 30% by mass, conforms to ISO 15025:2016 (Procedure A). The afterflame time measured by the combustion test method based on the standard was 40 seconds, and the flame retardance was poor. In addition, the fabric of Comparative Example 8, which had the same amount of flame retardant in the acrylic fibers and the ratio of acrylic fibers and cellulose fibers as in Example 2, except that metastannic acid was used as the flame retardant, It was completely burnt down by the combustion test method based on ISO 15025:2016 (Procedure A), and its flame retardance was extremely poor.
本発明は、特に限定されないが、例えば、下記の１以上の実施形態を含むことが望ましい。
［１］難燃性アクリル系繊維を３０～８０質量％、並びに天然繊維及び化学繊維からなる群から選ばれる一つ以上の他の繊維を２０～７０質量％含み、
前記難燃性アクリル系繊維は、アクリル系共重合体１００質量部及びスズ酸亜鉛化合物１～１８質量部を含有し、
ＩＳＯ１５０２５燃焼試験において残炎時間が３０秒以下である、難燃性布帛。
［２］前記他の繊維がセルロース系繊維を含む、［１］に記載の難燃性布帛。
［３］前記セルロース系繊維が、リヨセルである、［２］に記載の難燃性布帛。
［４］前記スズ酸亜鉛化合物は、ヒドロキシ錫酸亜鉛である、［１］～［３］のいずれかに記載の難燃性布帛。
［５］前記難燃性布帛は、編物及び織物からなる群から選ばれる一つ以上を含む、［１］～［４］のいずれかに記載の難燃性布帛。
［６］ＩＳＯ１５０２５燃焼試験において残炎時間が３秒以下である、［１］～［５］のいずれかに記載の難燃性布帛。
［７］ 前記アクリル系共重合体は、アクリロニトリル及び塩化ビニリデンを含む、［１］～［６］のいずれかに記載の難燃性布帛。
［８］［１］～［７］のいずれかに記載の難燃性布帛を含む難燃性作業服。
Although the present invention is not particularly limited, it is desirable to include, for example, one or more of the following embodiments.
[1] Contains 30 to 80% by mass of flame-retardant acrylic fibers and 20 to 70% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers,
The flame-retardant acrylic fiber contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound,
A flame-retardant fabric having an afterflame time of 30 seconds or less in an ISO15025 combustion test.
[2] The flame-retardant fabric according to [1], wherein the other fibers include cellulose fibers.
[3] The flame-retardant fabric according to [2], wherein the cellulose fiber is Lyocell.
[4] The flame-retardant fabric according to any one of [1] to [3], wherein the zinc stannate compound is zinc hydroxystannate.
[5] The flame-retardant fabric according to any one of [1] to [4], wherein the flame-retardant fabric includes one or more selected from the group consisting of knitted fabrics and woven fabrics.
[6] The flame-retardant fabric according to any one of [1] to [5], which has an afterflame time of 3 seconds or less in an ISO15025 combustion test.
[7] The flame-retardant fabric according to any one of [1] to [6], wherein the acrylic copolymer contains acrylonitrile and vinylidene chloride.
[8] Flame-retardant work clothes comprising the flame-retardant fabric according to any one of [1] to [7].
Claims (8)
前記難燃性アクリル系繊維は、アクリル系共重合体１００質量部及びスズ酸亜鉛化合物１～１８質量部を含有し、
ＩＳＯ１５０２５燃焼試験において残炎時間が３０秒以下である、難燃性布帛。 Containing 30 to 80% by mass of flame-retardant acrylic fibers and 20 to 70% by mass of one or more other fibers selected from the group consisting of natural fibers and chemical fibers,
The flame-retardant acrylic fiber contains 100 parts by mass of an acrylic copolymer and 1 to 18 parts by mass of a zinc stannate compound,
A flame-retardant fabric having an afterflame time of 30 seconds or less in an ISO15025 combustion test.
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| WO2001032968A1 (en) * | 1999-11-04 | 2001-05-10 | Kaneka Corporation | Flame-retardant union fabric |
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