EP3134567A1 - Nouveau procédé de fabrication de fils ignifugés - Google Patents
Nouveau procédé de fabrication de fils ignifugésInfo
- Publication number
- EP3134567A1 EP3134567A1 EP15725769.2A EP15725769A EP3134567A1 EP 3134567 A1 EP3134567 A1 EP 3134567A1 EP 15725769 A EP15725769 A EP 15725769A EP 3134567 A1 EP3134567 A1 EP 3134567A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer
- flame retardant
- sheath
- polymers
- process 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 239000003063 flame retardant Substances 0.000 title claims description 79
- 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 description 55
- 229920000642 polymer Polymers 0.000 claims abstract description 96
- 229920005601 base polymer Polymers 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000012757 flame retardant agent Substances 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 19
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 12
- 229920002647 polyamide Polymers 0.000 claims description 12
- 229920002635 polyurethane Polymers 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 12
- 239000004952 Polyamide Substances 0.000 claims description 11
- 229920000728 polyester Polymers 0.000 claims description 11
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 229920002903 fire-safe polymer Polymers 0.000 claims description 6
- 229920001169 thermoplastic Polymers 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 229920001634 Copolyester Polymers 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 239000002174 Styrene-butadiene Substances 0.000 claims description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 125000005395 methacrylic acid group Chemical class 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 239000011115 styrene butadiene Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 229920002397 thermoplastic olefin Polymers 0.000 claims description 4
- 239000004416 thermosoftening plastic Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920006249 styrenic copolymer Polymers 0.000 claims description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical group C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 claims 2
- 150000001253 acrylic acids Chemical class 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims 1
- 230000009477 glass transition Effects 0.000 abstract description 15
- 239000000155 melt Substances 0.000 abstract description 3
- 239000003340 retarding agent Substances 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- 239000011162 core material Substances 0.000 description 36
- 239000004753 textile Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000945 filler Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 229920002959 polymer blend Polymers 0.000 description 6
- 230000037072 sun protection Effects 0.000 description 6
- 238000005253 cladding Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 238000004079 fireproofing Methods 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 229920001944 Plastisol Polymers 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011133 lead Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000004999 plastisol Substances 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 239000013047 polymeric layer Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 229920002292 Nylon 6 Polymers 0.000 description 2
- 239000002318 adhesion promoter Substances 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 238000009941 weaving Methods 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-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
- 206010001488 Aggression Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 229920006098 Vampamid® Polymers 0.000 description 1
- 206010047289 Ventricular extrasystoles Diseases 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003082 abrasive agent Substances 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- QLVHFTGKDGTJDH-UHFFFAOYSA-N acetic acid;ethenyl acetate Chemical compound CC(O)=O.CC(=O)OC=C QLVHFTGKDGTJDH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000016571 aggressive behavior Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920006018 co-polyamide Polymers 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 239000004815 dispersion polymer Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000013529 heat transfer fluid Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920006285 olefinic elastomer Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 230000000475 sunscreen effect Effects 0.000 description 1
- 239000000516 sunscreening agent Substances 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 1
- ATCJTYORYKLVIA-SRXJVYAUSA-N vamp regimen Chemical compound O=C1C=C[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1.C=1N=C2N=C(N)N=C(N)C2=NC=1CN(C)C1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1.O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1.C([C@H](C[C@]1(C(=O)OC)C=2C(=CC3=C(C45[C@H]([C@@]([C@H](OC(C)=O)[C@]6(CC)C=CCN([C@H]56)CC4)(O)C(=O)OC)N3C=O)C=2)OC)C[C@@](C2)(O)CC)N2CCC2=C1NC1=CC=CC=C21 ATCJTYORYKLVIA-SRXJVYAUSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- D02G3/22—Yarns or threads characterised by constructional features, e.g. blending, filament/fibre
- D02G3/40—Yarns in which fibres are united by adhesives; Impregnated yarns or threads
- D02G3/404—Yarns or threads coated with polymeric solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D11/00—Other features of manufacture
- D01D11/06—Coating with spinning solutions or melts
-
- 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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
-
- 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
Definitions
- the present invention relates to the technical field of fiis adapted to the production of textile surfaces for sun protection. More specifically, the present invention relates to a novel process for the production of flame-retardant yarns, wherein the ends are preferably halogen-free.
- halogenated flame retardants such as, for example, deca bromo diphenyl ether or deca bromo diphenyl ethane or chlorinated paraffins, which are particularly effective and can therefore be used at lower concentrations, alone. or in synergy with antimony salts, such as antimony trioxide.
- antimony salts such as antimony trioxide.
- the resulting fabrics have excellent flame retardant properties, and with some eontextures they can get Mi type classifications according to French standard FP 2.507.
- the bromine content present in these tissues is about 4.5%.
- most brominated flame retardants are suspected of being toxic and that deca bromo diphenyl ether, which remains to this day one of the most successful brominated flame retardants, is included in the SVHC list of substances in the regulation. European REACH,
- one of the objectives of the present invention is: a new process for the production of small diameter flame retardants which can be used to produce highly flame retardant textile surfaces compatible with applications in the field of sun protection,
- the method according to the invention avoids the use of halogen components, which are recognized as harmful.
- the invention relates to a method for manufacturing a wire consisting of a multi-filament core coated with a poformic sheath, said sheath comprising two successive coaxial zones, called internal zone and external zone.
- external material incorporating at least one flameproofing agent, the concentration of flame retardant in the external zone being greater than the concentration of flameproofing agent in the internal zone, characterized in that the sheath is made by depositing, on the muiti-filamentary core, a miscible mixture of molten polymers comprising i
- polymer which do not establish in the molten state, permanent chemical bonds between them.
- polymer named co ⁇ f flame that present on the one hand a glass transition temperature slgnlchaircativement lower than that of the other polymer, named base polymer, and secondly a melting temperature also significantly lower than that of the base polymer,
- the process according to The invention makes it possible, in particular, to produce halogen-free wires.
- the materials constituting the core material, the polymeric sheath and the flame retardants present will be selected to be free of halogen.
- the son products by the method according to the invention consist of a core UiTi m-Fi lamentai ref said multi-filament core being coated with a sheath polymérlque.
- said sheath comprises two successive coaxial polymeric zones, called internal zone and external zone, the external zone incorporating at least one flame-retardant agent, the concentration of flame-retardant agent in the external zone being greater than the concentration in flame retardant agent in the internal area.
- the multi-filamentary core is of organic nature.
- the method according to the invention makes it possible, thanks to a single deposition step made from a particular mixture of miscible polymers when they are in the fused state, to obtain, in the end, a multi-filament core which is protected. by the inner zone of the sheath obtained, said inner zone being free or weakly loaded with flame retardant, the concentration of flame retardant in the outer zone of the sheath allows to concentrate its action on the peripheral zone of the wire thus leading to obtaining excellent properties of fire resistance.
- the amounts of polymers introduced will be chosen so as to obtain a sheath of which the sheath is 40 to 80% by weight, and preferably 50 to 70% by weight, of the total weight of the yarn.
- the amounts of flame-retardant agent (s) introduced will be chosen so as to obtain a yarn whose external zone comprises a quantity of flame-retardant agent corresponding to a mass% of 15 to 50%. preferably from 20 to 30%, of the total weight of the sheath. This mass percentage corresponds to the mass of flame retardant agent on the total mass of sheath 100 times.
- the son obtained with the process according to the invention have an average diameter belonging to the range of 150 to 500 um f preferably in the range of 2 ⁇ 0 400 m,
- the average diameter is the arithmetic average of all diameter measurements made, for example 10 in number, in particular with equipment of the type SD 25 marketed by ZUMBACH.
- the method according to the invention comprising a single deposition step also makes it possible to have continuity of the polymeric layer with the same material present in the entire volume, so there is a reduction in the number of interfaces in the material and thus increase in its cohesion.
- FIG. 1 is a diagrammatic representation of a cross section of a wire obtained by means of a process according to the invention
- FIG. 2 is a diagrammatic representation of an example installation of implementation of a method according to the invention with a single depositing operation
- the sheath allows ,, conventionally., Protect the soul malti-fllamentaire and give cohesion to the filaments and ,, as well, to make it usable wire transformations machines
- the sheath made around multi-filamentous file also has a dual role i) to obtain a sheathed wire of circular section and constant diameter and it) to give its flame retardancy to the wire.
- the yarn made by the process according to the invention has a circular section which has a constant diameter over the entire length of the yarn at plus or minus 10%. That is, each measured diameter value belongs to the range. : average value plus or minus 10%, the average value is the arithmetical average of all diameter measurements made, in particular with an MSD25 type apparatus marketed by ZUHS ⁇ CH.
- the multi-filament core surrounded by the inner zone will have an average diameter of from .1.00 to 400 ⁇ m more than or equal to at least 10%, and preferably from 125 to 300 ⁇ m to more than at least 10%, whereby with the outer zone a yarn having a total average diameter of from 150 to 500 ⁇ m is obtained with at least 10%, and preferably from 200 to 400 ⁇ m by at least 10%.
- the wire I produced by the method according to the invention comprises a multi-filament core i surrounded by a sheath comprising two coaxial zones: an inner polymeric zone or layer 2 and an outer polymeric zone or layer 3 wherein a flame retardant 4 is distributed.
- Each of the two zones of the sheath (inner and outer zone) will preferably be uniform in size and in composition.
- the flame retardant will be regularly distributed in the polymeric matrix forming the outer zone.
- the internal polymeric zone is a minority in the composition of the sheath. It preferably represents from 6 to 26% of the total mass of the composite yarn (ie core-sheath) and the amounts of base polymer and co-flame retardant polymer and flame retardant agent introduced into the deposited mixture will be adjusted to obtain such a percentage,
- the concentration of flame retardant in the outer zone of the polymeric sheath surrounding the filament yarn consisting of a set of filaments is greater than the concentration of flame retardant in the inner zone, due to the migration involved in the process according to the invention.
- the inner zone of the cladding may or may not incorporate a flameproofing agent, depending in particular on the amount of flame retardant present in the deposited mixture.
- the yarn made by the process according to the invention (both the core and the polymeric sheath) is halogen-free, that is to say that none of its constituents (constituent material of the core multi- filamentary, polymer (s) constituting the sheath, agent (s) fireproofing)) involved in the procedure involves a halogen atom,
- the core of the wire made according to the invention is in the form of a set of filaments extending in a preferred direction.
- Such multi-filament cores correspond to multi-filament yarns commonly available commercially.
- a multi-filament core will preferably be used. having a titer of 20 to 150 tex, preferably 30 to 50 tex, depending on the constituent material of the core.
- multi-filament cores will be preferred to a low-fuel material.
- the multi-filament core will be of non-halogen-containing material.
- multi-fllameniaire core is an organic material, especially a thermoplastic polymer ,, preferably selected from polyamides, polyesters (such as polyethylene terephthalate - PET).
- a thermoplastic polymer preferably selected from polyamides, polyesters (such as polyethylene terephthalate - PET).
- the invention is particularly suitable for the core fireproofing of a combustible material, in particular polyester type or pdyolifine.
- the multi-filamentary core is covered with a composition comprising a mixture of molten polymers and at least one flame-retardant agent which will allow the sheathing of the yarn and which is formulated to obtain, during cooling a migration of the flame retardant agent at the periphery of the wire,
- the constituent polymer (s) of the sheath will be halogen-free, which therefore excludes, in particular, the family of PVCs used in the prior piastlsol-based techniques.
- the constituent polymer (s) of the internal and external zones are, for example, chosen from esters of acrylic or methacrylic acids, non-halogenated vinyl polymers, ethylene / vinyl acetate copolymers, polyolefins, styrene copolymers, polyurethanes, polyamides, polyesters, copolyamides, copolyesters, oleamides, erueamides, slcones and acetals,
- the nature of the polymer (s) constituting each of the two zones of the cladding will, in particular, depend on the method used for the constitution of these different zones.
- it is a miscible blend of polymers which melt is introduced, said mixture comprising at least one flame retardant, and at least two polymers belonging to different chemical families with one of the two polymers ( named co-fire retardant polymer) which has on the one hand a vitreously lower glass transition temperature than that of the other polymer (named base polymer) and on the other hand a melting temperature also significantly lower than that of the base polymer .
- co-fire retardant polymer a vitreously lower glass transition temperature than that of the other polymer
- base polymer a melting temperature also significantly lower than that of the base polymer .
- significantly lower is meant, preferably, less than at least 10 ° C, and preferably of the order of -20 to -30 ° C.
- the difference between the melting temperature of the co-polymer is flame retardant and that of the base polymer will belong to the range of 15 to 5D to C ; preferably from 30 to 50 ° C.
- the difference will be determined by taking the arithmetic averages of the measurements, for example on the basis of 5 measurements, for each temperature to be compared.
- the co-flame retardant polymer having the lowest melting temperature will be chosen not to degrade to the melting temperature of the base polymer.
- the deposited polymer blend is referred to as a miscible blend of melt polymers, i.e. the blend is homogeneous, and does not demix or separate the different polymers.
- this does not necessarily mean that the base polymer and the co-fire retardant polymer are miscible in a mixture of these two only molten polymers. It may be necessary to add another polymer which makes it possible to obtain a miscible mixture,
- the other polymer referred to as a co-lubricating polymer, which although miscible in the melt with the base polymer, will then migrate outward due to the absence of permanent chemical bonds between the two polymers.
- a molten state which carries with it a portion of the flame retardant, the co-flame retardant polymer, preferably behaves as an adhesion promoter, which, in the molten state, attaches to the surface of the flame retardant agent.
- the flame retardant when the latter is in solid form, will advantageously present a large specific surface area, ideally greater than 511 m 2 / g.
- the wetting angle formed by the polymer in the molten state on the flameproofing agent will be less than 90 °
- the base polymer in the final sheath will be in crystallized or partially crystallized form.
- the base polymer will have a number-average molecular weight Mn of between 10,000 and 30000 g / mol, whereas the co-fire-retardant polymer will have a number-average molecular weight Mn of between 300 and 1000 g / mol.
- the base polymer will form the inner zone and the co-inhibiting polymer in admixture with the polymer of the invention.
- the base will form the polymeric matrix of the outer zone of the sheath. It is of course possible that each of the zones is formed of a polymer blend including at least one in each of the zones or all satisfy the requirements in the context of the invention.
- the base polymer (s) constituting the internal zone of the cladding will be chosen from: esters of acrylic or methacrylic acids, non-halogenated vinyl polymers, polyurethanes, polyamides, thermoplastic polyolefins, thermoplastic elastomers (Styrene-butadiene (SB) or styrene-ethylene / butylene-styrene (SE8S) styrenic copolymers, polyesters and silicones and the polymeric matrix of the outer zone of the sheath will be formed of at least one base polymer identical to that present in the inner zone and at least one eo-flame retardant polymer chosen from copolyamides, copolyesters, polyurethanes, polyolefins, oleamoys, erucamides and copolymers based on styrene.
- the inner zone of the sheath may contain a low concentration of flame retardant agent but which will always be lower than the concentration of flame retardant in the outer zone.
- the inner zone comprises a quantity of flame retardant agent, usually at least 60% of the total weight of flame retardant agent present in the sheath, preferably at least 75%, will be in the external area,
- polymers (s) used for forming the sheath will also be adapted, depending on the final application envisaged for the wire.
- polymers having a high moisture uptake such as polyamides
- non-hydrolyzable polymers such as vinyl acetate acetate (EVA) or styrenes and their copolymers will be preferred, for outdoor applications.
- EVA vinyl acetate acetate
- the flame-retardant agent (s) present in the process according to the invention are preferably halogen-free.
- one or more flame-retardant agent (s) chosen from the agents may be used.
- AX phosphorus or nitrogen-containing flame retardants such as ammonium polyphosphates, melamine isocyanurate, pentaerythritol and melamine derivatives and ammonium molybdates, depending on the nature of the polymer (s) present in the outer zone of the sheath .
- the flame-retardant agent (s) present may therefore be of a mineral or organic nature. In known manner, they will be chosen, depending on the nature of the polymer or polymers that will (will) constitute the outer zone of the sheath.
- the outer zone will be formed of a polyamide
- nitrogen-containing flame retardants such as melamine isocyanurates.
- Many already flame retardant polymer compositions are commercially available and may be used as a component of the deposited blend. .
- Such polyamide-based compositions are especially available from ADDIPIAST ,, ALBiS, or ULTRAPOLYMERS or AR EMA, such EYA-based compositions are, for their part, available from ARKEMA, ALPHAGARY or EUROFI D. It is also possible to prepare the solder compositions using polymer (s) and flame retardant (s) sold separately which will be blended or compounded.
- the flameproofing agent (s) may be in the form of one or more liquid compounds and / or of one or more solid compounds having, preferably, a small particle size.
- Small particle size means particles whose largest size is less than 50 microns.
- the flame retardant agent will be chosen so as to be uniformly distributed in the depot formulation containing the same, In particular, sil is one or more liquid compounds, they will be soluble or miscible in the mixture of molten polymers. IF! This is one or more solid compounds, their low particle size will allow to obtain a regular dispersion in the mixture of molten polymers.
- the process for forming the son seioo the invention consists in making the sheath with a single deposition operation, but to choose a deposition formulation that allows to migrate the molecules or particles of flame retardant agent in the peripheral portion of the sheath .
- a deposit is, Preferably, carried out with implementation of a caiibration step by extrusion of a sheath on the core wire and calibration of the sheath by passage through a die. Nevertheless, it is possible to achieve the recovery and caiibration of the textile core with any suitable method well known to those skilled in the art for depositing a molten polymer mixture.
- This method consists in placing, during the production of the coating which also constitutes the sponging of the yarn, the flameproofing agents at the periphery of the composite yarn.
- the formulation used being in the form of a miscible mixture of molten polymers comprises the following elements:
- one or more base polymers intended to impart the mechanical properties and to guarantee the durability of the sheath
- one or more flameproofing agents formed from one or more liquid compounds and / or from one or more solid compounds having, preferably, a small particle size
- one or more co-nitrogenizing polymers having a glass transition temperature and a melting temperature significantly lower respectively than the glass transition temperature and the melting temperature of the base polymer which will cause at least one part of the flame retardant at the periphery of the sheath, during cooling,
- the flame retardant will be evenly distributed in the molten polymer mixture. This homogeneous distribution can be obtained by a mixing operation, for example with mechanical stirring.
- the formulation comprising the melt polymer blend and the selected flame retardant (s) is applied to the core yarn by any suitable technique which will allow both the coating and the sheathing of the core. In particular, a technique that leads to obtaining a sheath of circular section and constant diameter, such as the extrusion-cladding technique, will be used. It is possible to preheat the core before the deposition operation, The cooling operation of the coating thus obtained will allow the positioning of the flame retardant fillers or molecules at the periphery of the latter, that is to say in the outer zone of the fine wire ; got.
- the co-flame retardant polymer behaves as an adhesion promoter and will melt in the surface of the fillers or molecules constituting the flame retardant system.
- the base polymer which has the highest melting temperature, will freeze first.
- the co-flame retardant polymer which has no permanent chemical bonds with the base polymer in the molten state, will therefore not be retained by chemical bonds and migrate outwardly, bringing with it the flame retardant fillers it coated.
- the temperature of the composite yarn is lower than the glass transition temperature of the base polymer or the melting temperature of the co-flame retardant polymer, the migration of the co-flame retardant polymer can no longer continue and the structure will be frozen.
- the wire obtained will then be in accordance with Figure 1.
- the cooling of the wire will be carried out with a bearing at a temperature lower than the glass transition temperature of the base polymer but greater than that of the co-flame retardant polymer.
- this step will take place rapidly as soon as the cooling starts, in particular less than 20 s f preferably less than 10 s f and more preferably less than s seconds after the start of cooling; and / or last from 1 to 10 s, for this, the following two procedures may, for example. , to be retained:
- the first tray makes it possible to quench the extruded wire and to bring back, in a few seconds (ideally ⁇ 5s), its temperature to a temperature below the glass transition temperature of the base polymer but greater than that of the co-flame retardant polymer,
- the second tank allows to maintain this temperature for a few seconds (ideally> 10s), there is then migration of the co-flame retardant polymer on the peripheral zone of the composite yarn. This solution is to be retained when the base polymer and the co-flame retardant polymer have melting and relatively glass transition temperatures. close (difference less than 2o ° Q
- the external zone will be composed of at least 3 components; a base polymer, a co-flame retardant polymer and a flame retardant agent,
- esters of acrylic or methacrylic acids include esters of acrylic or methacrylic acids, non-halogenated vinyl polymers, polyurethanes, polyamides, thermoplastic polyols, thermoplastics olefinic elastomers (TPG), styrene-butadiene (SBR) or styrene-ethylene-butylene-styrene (SEBS) type copolymers, polyesters and silicones,
- a polymer which can be used as a co-flame retardant polymer there may be mentioned: oopalyamides, copolyesters, polyurethanes, polyolefins, oleamides and erucamides, as well as styrene-based copolymers.
- the pair of base polymer / co-flame retardant polymer will be chosen so as to meet the following conditions: -They must be able to melt to form a miscible mixture, optionally by combination with another polymer. Indeed, if when they are only the base polymer and the polymer co ⁇ flame retardant in the molten state are immiscible, a miscible mixture can be obtained by adding another miscible polymer independently with both. It is thus possible to render the polyamide / polyester blends melt-miscible by using copolyamide hot melts as a compatibilizer of these two polymers. Similarly, it is conceivable to use ssanlsés polymers to make compatible mixtures of polyamides and polyurethanes;
- the ce-flame retardant polymer must have a glass transition temperature signifcantly lower than that of the base polymer, and also a melting temperature significantly lower than that of the base polymer.
- nt Copolyester (30 parts by weight)
- o Compatibilizer co-polyamide (10 parts by weight).
- Co-freezing polymer styrene / butadiene / styrene copolymer (20 parts by weight),
- the cooling step may be carried out by passing the wire through a cooling zone, especially maintained at a temperature in the range from 3 to 25.degree. cooling used in any coating process. Ex rusion, hot melt deposit, and also also implemented after the two deposition operations of the two-step process, may be used.
- the outer zone will not be obtained by depositing a polymer dispersion in the form of plastlsol or in the form of an aqueous dispersion.
- Plastisol will not be retained because it requires the use of plasticizer (s) which are compounds of low molecular weight, which will migrate and exude to the surface of the yarns, leading to a greasy feel ".
- plasticizer s
- the aqueous dispersion path will not be retained either, because it does not allow to obtain a continuous sheath at the outer zone which is the guarantor of the protection of the core wire attacks of the external environment.
- the method according to the invention therefore uses neither plastisol nor plastifian so that the sheath contains neither plastisol nor plasticizer,
- the various steps of the process according to the invention may be carried out continuously and lead to long lengths of yarn
- the yarns obtained at the end of the process according to the invention may be wound in the form of a spool. to be used.
- the proposed composite yarn may be halogen-free and is obtained by sheathing a multi-fllamentalre web yarn with a coating comprising at least two successive zones of different composition:
- an outer zone consisting of a uniform fireproof envelope in composition and in thickness deposited on the inner zone.
- the various components used to make the yarns according to the invention will be chosen to possess all the technical characteristics of the products intended for this purpose. use, and in particular UV resistance as measured by XE OTEST artificial aging according to the MF E ISO 5BB2 standard, a dirt resistance and a cleaning ability, the mechanical properties necessary for the production of awning textiles, and resistance to bad weather, heat and cold in particular when the wire is intended for outdoor applications.
- the method according to the invention may lead to son having a high level of fireproofing type Hl according to standard NFP925 ⁇ 7 or Bl according to DIN 4102.
- the sheathed fireproofed yarns obtained by the process according to the invention may be used for the constitution of textiles intended for sun protection, chosen from woven fabrics, woven and nonwoven grids and knits made up of at least part or even totally of son according to the invention.
- the flame retardant wire obtained by the process according to the invention can be used for the constitution of textiles adapted to sun protection, in particular for the manufacture of blinds.
- wire obtained by the process according to the invention will be woven, crisscrossed, knitted, or glued according to the selected architecture, by any appropriate technique well known to those skilled in the art.
- Fabrics, grids or knits, made with yarns obtained by means of the process of the invention and having a low opening factor, in particular of the order of from 6 to 15%, and preferably from 3 to 10%, will have the following characteristics: properties required, especially in terms of sun protection and fire resistance.
- Such textiles may be intended to be positioned indoors or outdoors.
- the yarns according to the invention make it possible to produce textiles whose fireproofing performance corresponds to a classification of type H1 according to the French standard NFP92507 and type 81 according to the German standard DIN 4102.
- - Multilamentous core PET 2x18 thread? dtex S12 ⁇ (average diameter: 210 ⁇ m) treated with fire, (commercial reference: TREV1RA 691 G from T EVÎRA);
- co-inhibiting polymer co-polyester (commercial reference, GRILTEX 2132 E from EHS division GRILTEX) - represents 20% by weight of the sheath (melting temperature: 110-124 ° C. -Tg: -1.8 ⁇ 20 ° C. );
- FIG. 2 the wire i constituting a multi-leafless core is unwound from a coil 10, to pass into a preheating zone 20, before reaching a cladding exfruslon device 38 ending in a die, from which it leaves to be directed to a cooling zone 40, to obtain a fiber according to the invention which can be stored after winding in the form of a coil 50.
- flame-retarded type ethylene-vinyl acetate copolymer (EVA) type V0 (commercial reference: Alphagary's MEGOLON HF1876) represents 60% by weight of the sheath, (melting temperature 165 ° C. to 175 ° C.) ° C ⁇ Tg: 80-90 ° C),
- SEBS co-lubricating polymer (commercial reference: Lifoflex 50 from HEXPOL) represents 20% by weight of the sheath (melting temperature: 125-160 ° C. - Tg of the blocks: -40 -G ⁇ C 0 ,
- the polymer used to obtain a mixture of poly (ethylene-maleic anhydride) and acrylic acid represents 20% by weight of the sheath (melting temperature). 100 - 115 ° C - Tg: 40 - 60 o C).
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
Claims
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PL15725769T PL3134567T3 (pl) | 2014-04-22 | 2015-04-21 | Nowy proces produkcji ogniotrwałych nici |
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FR1453617 | 2014-04-22 | ||
PCT/FR2015/051075 WO2015162371A1 (fr) | 2014-04-22 | 2015-04-21 | Nouveau procédé de fabrication de fils ignifugés |
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EP3134567A1 true EP3134567A1 (fr) | 2017-03-01 |
EP3134567B1 EP3134567B1 (fr) | 2018-06-06 |
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EP15725769.2A Active EP3134567B1 (fr) | 2014-04-22 | 2015-04-21 | Nouveau procédé de fabrication de fils ignifugés |
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US (1) | US9920458B2 (fr) |
EP (1) | EP3134567B1 (fr) |
JP (1) | JP6581995B2 (fr) |
KR (1) | KR102239700B1 (fr) |
CN (1) | CN106460235B (fr) |
AU (1) | AU2015250659B2 (fr) |
BR (1) | BR112016024456A2 (fr) |
CA (1) | CA2945911C (fr) |
DK (1) | DK3134567T3 (fr) |
ES (1) | ES2685570T3 (fr) |
MX (1) | MX2016013917A (fr) |
PL (1) | PL3134567T3 (fr) |
WO (1) | WO2015162371A1 (fr) |
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FR3080387B1 (fr) * | 2018-04-20 | 2020-11-13 | Mermet | Fil composite renforce, procede de preparation et textile comprenant un tel fil |
EP3887456A1 (fr) | 2018-11-29 | 2021-10-06 | Eastman Kodak Company | Composition aqueuse pour la fabrication de fils et de tissus |
CN111455477A (zh) * | 2020-04-07 | 2020-07-28 | 山东宏业纺织股份有限公司 | 一种阻燃纱线生产方法 |
KR102190365B1 (ko) * | 2020-08-11 | 2020-12-11 | 주식회사 대웅에프엔티 (F.N.T) | 폴리올레핀계 난연사 |
EP4320307A1 (fr) | 2021-07-02 | 2024-02-14 | Eastman Kodak Company | Composition aqueuse non expansée, textile enduit et procédé de préparation |
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JPH09144329A (ja) * | 1995-11-20 | 1997-06-03 | Hagiwara Kogyo Kk | 建築工事用メッシュシート |
US5985193A (en) * | 1996-03-29 | 1999-11-16 | Fiberco., Inc. | Process of making polypropylene fibers |
FR2748496B1 (fr) | 1996-05-07 | 1998-06-26 | Chavanoz Ind | Fil composite |
NL1010837C2 (nl) | 1997-12-18 | 1999-07-13 | Kyowa Kk | Vlamvertrager voor netten en niet-ontvlambaar netmateriaal dat deze bevat. |
EP1105277B1 (fr) | 1998-06-19 | 2005-12-14 | Ticona Celstran, Inc. | Structure composite enduite de renfort a longues fibres et son procede de fabrication |
JP2000119961A (ja) * | 1998-10-13 | 2000-04-25 | Nitto Boseki Co Ltd | ガラス繊維ヤーン被覆用難燃性樹脂組成物及びその製品 |
JP2003105635A (ja) * | 2001-09-27 | 2003-04-09 | Mitsubishi Engineering Plastics Corp | 難燃性ポリアミド複層フィラメント及びメッシュシート |
FR2834302B1 (fr) * | 2001-12-28 | 2005-05-06 | Chavanoz Ind | Fil composite, procede d'obtention et structure textile obtenue |
JP4585748B2 (ja) * | 2003-08-05 | 2010-11-24 | 日本ユニカー株式会社 | 難燃性オレフィン系樹脂被覆金属線及びその製造方法 |
KR100918462B1 (ko) | 2008-08-19 | 2009-09-24 | (재)한국섬유기계연구소 | 차광막용 이형 단면 코팅사 및 그 제조 방법 및 그 직물 |
JP5432019B2 (ja) * | 2010-03-25 | 2014-03-05 | 宇部エクシモ株式会社 | 難燃性ネット状物、網糸用未硬化状線状物の製造方法、及び難燃性frpネット本体の製造方法 |
US8795561B2 (en) * | 2010-09-29 | 2014-08-05 | Milliken & Company | Process of forming a nanofiber non-woven containing particles |
KR101286628B1 (ko) | 2011-08-25 | 2013-07-22 | 주식회사 알켄즈 | 친환경성 코팅사, 이의 제조방법, 이의 직물 및 이에 사용되는 코팅 조성물 |
CN104955887A (zh) * | 2012-11-20 | 2015-09-30 | 宝洁公司 | 聚合物-皂组合物及其制备和使用方法 |
BR112015011201A2 (pt) * | 2012-11-20 | 2017-07-11 | Imflux Inc | métodos de moldagem de composições de polímero termoplástico que compreendem lipídios hidroxilados |
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2015
- 2015-04-21 WO PCT/FR2015/051075 patent/WO2015162371A1/fr active Application Filing
- 2015-04-21 KR KR1020167031878A patent/KR102239700B1/ko active IP Right Grant
- 2015-04-21 PL PL15725769T patent/PL3134567T3/pl unknown
- 2015-04-21 AU AU2015250659A patent/AU2015250659B2/en active Active
- 2015-04-21 CA CA2945911A patent/CA2945911C/fr active Active
- 2015-04-21 BR BR112016024456A patent/BR112016024456A2/pt not_active Application Discontinuation
- 2015-04-21 JP JP2016564083A patent/JP6581995B2/ja active Active
- 2015-04-21 DK DK15725769.2T patent/DK3134567T3/en active
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- 2015-04-21 CN CN201580020919.XA patent/CN106460235B/zh active Active
- 2015-04-21 ES ES15725769.2T patent/ES2685570T3/es active Active
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Publication number | Publication date |
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JP6581995B2 (ja) | 2019-09-25 |
AU2015250659B2 (en) | 2019-03-21 |
US9920458B2 (en) | 2018-03-20 |
MX2016013917A (es) | 2017-05-23 |
CA2945911A1 (fr) | 2015-10-29 |
CA2945911C (fr) | 2022-06-14 |
KR102239700B1 (ko) | 2021-04-13 |
US20170044694A1 (en) | 2017-02-16 |
DK3134567T3 (en) | 2018-09-03 |
PL3134567T3 (pl) | 2018-11-30 |
WO2015162371A1 (fr) | 2015-10-29 |
KR20160143834A (ko) | 2016-12-14 |
CN106460235A (zh) | 2017-02-22 |
AU2015250659A1 (en) | 2016-11-03 |
BR112016024456A2 (pt) | 2017-08-15 |
ES2685570T3 (es) | 2018-10-10 |
EP3134567B1 (fr) | 2018-06-06 |
JP2017514034A (ja) | 2017-06-01 |
CN106460235B (zh) | 2019-03-01 |
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