EP3134567B1 - Neuartiges verfahren zur herstellung von flammhemmenden garnen - Google Patents
Neuartiges verfahren zur herstellung von flammhemmenden garnen Download PDFInfo
- Publication number
- EP3134567B1 EP3134567B1 EP15725769.2A EP15725769A EP3134567B1 EP 3134567 B1 EP3134567 B1 EP 3134567B1 EP 15725769 A EP15725769 A EP 15725769A EP 3134567 B1 EP3134567 B1 EP 3134567B1
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- EP
- European Patent Office
- Prior art keywords
- polymer
- flame
- sheath
- yarn
- anyone
- 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.)
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Links
- 238000000034 method Methods 0.000 title claims description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003063 flame retardant Substances 0.000 title description 78
- 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 description 44
- 230000008569 process Effects 0.000 title description 19
- 229920000642 polymer Polymers 0.000 claims description 98
- 239000000203 mixture Substances 0.000 claims description 51
- 229920005601 base polymer Polymers 0.000 claims description 42
- 238000002844 melting Methods 0.000 claims description 23
- 230000008018 melting Effects 0.000 claims description 23
- 238000000151 deposition Methods 0.000 claims description 22
- 238000001816 cooling Methods 0.000 claims description 19
- 230000008021 deposition Effects 0.000 claims description 16
- 230000009477 glass transition Effects 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229920002647 polyamide Polymers 0.000 claims description 14
- 239000004952 Polyamide Substances 0.000 claims description 13
- 229920000728 polyester Polymers 0.000 claims description 12
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- 229920000098 polyolefin Polymers 0.000 claims description 9
- -1 styrene ethylene butylene styrene Chemical class 0.000 claims description 9
- 229920001634 Copolyester Polymers 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 239000002174 Styrene-butadiene Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000011115 styrene butadiene Substances 0.000 claims description 4
- 229920001169 thermoplastic Polymers 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 2
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003340 retarding agent Substances 0.000 claims 10
- 229920001971 elastomer Polymers 0.000 claims 2
- 239000000806 elastomer Substances 0.000 claims 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 claims 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims 1
- 239000012757 flame retardant agent Substances 0.000 description 22
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000004753 textile Substances 0.000 description 14
- 239000002131 composite material Substances 0.000 description 12
- 230000007704 transition Effects 0.000 description 12
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- 239000000463 material Substances 0.000 description 11
- 238000001125 extrusion Methods 0.000 description 8
- 229920001944 Plastisol Polymers 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000004999 plastisol Substances 0.000 description 7
- 230000037072 sun protection Effects 0.000 description 7
- 229920002292 Nylon 6 Polymers 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
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- 238000005253 cladding Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 229920002903 fire-safe polymer Polymers 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920004935 Trevira® Polymers 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000004744 fabric Substances 0.000 description 4
- 238000004079 fireproofing Methods 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 239000012943 hotmelt 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
- 125000005395 methacrylic acid group Chemical class 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000013047 polymeric layer Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 229920006098 Vampamid® Polymers 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 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
- 229920006018 co-polyamide Polymers 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
- 230000007613 environmental effect Effects 0.000 description 2
- 230000009970 fire resistant effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 238000009940 knitting Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 229920006249 styrenic copolymer Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- 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 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
- 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 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
- 206010047289 Ventricular extrasystoles Diseases 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
- 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
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001462 antimony Chemical class 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 230000003416 augmentation Effects 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
- 239000012141 concentrate Substances 0.000 description 1
- 238000004320 controlled atmosphere Methods 0.000 description 1
- 230000001419 dependent effect Effects 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
- 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
- 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
- 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 235000020004 porter Nutrition 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
- 150000003384 small molecules Chemical class 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 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
- 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
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Images
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 son adapted to the realization of textile surfaces for sun protection. More specifically, the present invention relates to a new method of manufacturing fireproof son, said son being preferably without halogen.
- Such a technique is, in particular, described in the documents EP 2 562 208 and EP 0 900 294 , wherein a composite yarn is obtained by sheathing a glass core yarn by a plastisol of PVC flame retarded by a ternary mixture comprising an oxygenated antimony compound, a hydrated metal oxide whose metal is selected in the group consisting of aluminum, magnesium, tin, zinc and lead, and zinc borate.
- Flame-retardant properties for halogen-free yarns can also be obtained by the use of halogen-free flame retardant compounds, as has been described in the documents JP 2011-202397 and US 6,150,448 for example.
- Other solutions propose obtaining satisfactory flame retardant properties for halogen-free yarns, sought for environmental reasons, by the use of large amounts of flame retardant fillers, incompatible with obtaining fine yarns (corresponding to an average the order of 80 to 120 tex).
- they are found, in part, near the filaments, and behave as abrasives weakening the final wire obtained.
- halogenated polymers requiring fewer flame retardants are preferred.
- 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.
- one of the objectives of the present invention is to provide a new method of manufacturing small diameter fireproof son that can be used to achieve highly fireproof textile surfaces compatible with applications in the field of sun protection.
- the method according to the invention makes it possible to avoid using halogenated components, recognized as harmful.
- the process according to the invention makes it possible in particular to produce halogen-free yarns.
- the constituent materials of the multi-filament core, the polymeric sheath and the flame retardant or agents present will be chosen to be free of halogen.
- the son produced by the process according to the invention consist of a multi-filament core, said multi-filament core being coated with a polymeric sheath.
- 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 makes it possible 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 yarn whose 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 weight% of 15 to 50% by weight. %, preferably 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 yarns obtained with the process according to the invention have a mean diameter in the range of 150 to 500 ⁇ m, preferably in the range of 200 to 400 ⁇ m.
- the mean diameter is the arithmetic mean of all the diameter measurements made, for example 10 in number, in particular with an MSD type apparatus marketed by ZUMBACH.
- the sheath makes it possible, in a conventional manner, to protect the multi-filament core and to give cohesion to the filaments and, thus, to make the wire usable on industrial transformation machines.
- the sheath made around the multi-filament core also has a dual role: i) to obtain a sheathed wire of circular section and of constant diameter and ii) 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 ZUMBACH.
- the multi-filament core surrounded by the inner zone will have an average diameter of 100 to 400 ⁇ m to more than at least 10%, and preferably from 125 to 300 ⁇ m to more than at least 10%, so obtaining with the outer zone a wire of average total diameter of 150 to 500 microns more than at least 10%, and preferably from 200 to 400 microns to more than at least 10%.
- the high concentration of the flame retardant at the periphery of the yarn is compatible with small diameter yarns and important fireproofing properties.
- the inner zone of the sheath protects the multi-filament core from the aggression that could be caused by the presence of the flame-retardant agent, since in the context of the invention, the latter is mainly located in the outer zone of the flame retardant. sheath.
- the yarn I produced by the process according to the invention comprises a multi-filamentary core 1 surrounded by a sheath comprising two coaxial zones: an inner polymeric zone or layer 2 and an outer polymeric zone or layer 3 in which a flame-retardant agent 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 introduced into the blend deposited will be adjusted to obtain such a percentage.
- the concentration of flame-retardant agent 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 agent in the inner zone, due to the migration involved in the process according to the invention. 'invention.
- the inner zone of the sheath may or may not incorporate a flame retardant, depending in particular on the amount of flame retardant present in the deposited mixture.
- the wire produced by the method according to the invention (both the core and the polymeric sheath) is halogen-free, that is to say that none of its constituents (material constituting the multi-filament core, polymer (s) constituting the sheath, agent (s) flame retardants)) involved in the process comprises 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 currently commercially available.
- a multi-filament core will preferably be used. having a titer of 20 to 150 tex, preferably 30 to 60 tex, depending on the constituent material of the core.
- the multi-filamentary cores will be favored in a weakly combustible material.
- the multi-filament core will be made of a material containing no halogen.
- the multi-filament core is made of an organic material, in particular a thermoplastic polymer, preferably chosen from polyamides, polyesters (such as polyethylene terephthalate-PET), polyurethanes, polyolefins (such as polypropylenes) and vinyl polymers (such as vinyl acetate) as well as other artificial polymers such as cellulose acetate, and mixtures thereof.
- a thermoplastic polymer preferably chosen from polyamides, polyesters (such as polyethylene terephthalate-PET), polyurethanes, polyolefins (such as polypropylenes) and vinyl polymers (such as vinyl acetate) as well as other artificial polymers such as cellulose acetate, and mixtures thereof.
- the core is an inorganic material, and is, for example, consisting of a set of glass filaments. Nevertheless, the invention is particularly suitable for the fireproofing of a core of a combustible material, in particular of the polyester or polyolefin type.
- the multi-filament 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 agent flame retardant on 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 plastisol-based techniques.
- the constituent polymer (s) of the inner and outer 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, erucamides, silicones and acetals.
- each of the two zones of the cladding will, in particular, be dependent on the method used for the constitution of these different zones.
- a miscible mixture of molten polymers is deposited, said mixture comprising at least one flame-retardant agent, and at least two polymers belonging to different chemical families with one of the two polymers (called co-flame retardant polymer) which has on the one hand a vitreous transition temperature significantly lower 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-flame retardant polymer a vitreous transition temperature significantly lower than that of the other polymer
- melting temperature also significantly lower than that of the base polymer.
- significantly lower is meant lower by at least 10 ° C, and preferably on the order of -20 to -30 ° C.
- the difference between the melting temperature of the co-flame retardant polymer and that of the base polymer will be in the range of 15 to 50 ° C, preferably 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. On the other hand, 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 to obtain a miscible mixture.
- co-flame retardant 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 at the same time. melted state, taking with it a part of the flame retardant agent.
- the co-flame retardant polymer preferably behaves as an adhesion promoter, which melt is attached to the surface of the flame retardant.
- the flame retardant agent when the latter is in solid form, will advantageously have a large specific surface, ideally greater than 50 m 2 / g.
- the wetting angle formed by the melt polymer on the flame retardant 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, while 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-flame retardant 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 mixture of polymers, at least one of which in each zone, or all of them, satisfy the conditions set forth in the context of the invention.
- the base polymer (s) constituting the inner zone of the cladding will be chosen from: esters of acrylic or methacrylic acids, non-halogenated vinyl polymers, polyurethanes, polyamides, thermoplastic polyolefins, olefinic elastomer thermoplastics (TPO), styrenic copolymers of styrene-butadiene (SBR) or styrene-ethylene-butylene-styrene (SEBS) type, polyesters and silicones and the polymer matrix of the outer zone of the sheath will be formed of at least one polymer base identical to that present in the inner zone and at least one co-flame retardant polymer chosen from copolyamides, copolyesters, polyurethanes, polyolefins, oleamides, erucamides and copolymers based on styrene.
- the inner zone of the sheath may contain a low concentration of flame retardant but which will always be lower than the concentration of flame retardant in the outer zone.
- 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 ethylene vinyl acetate (EVA) or styrenes and their copolymers, will be preferred, for outdoor applications.
- EVA ethylene vinyl acetate
- the flame-retardant agent (s) present in the process according to the invention are preferably halogen-free.
- one or more agent (s) flame retardant (s) chosen from the agents can be used 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 cladding.
- 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 retarded polymer compositions are commercially available and may be used as a component of the deposited blend.
- Such polyamide-based compositions are especially available from ADDIPLAST, ALBIS, or ULTRAPOLYMERS or ARKEMA, such EVA-based compositions are, for their part, available from ARKEMA, ALPHAGARY or EUROFIND. It is also possible to prepare the deposition compositions using separately sold flame retardant polymer (s) and agent (s) which will be mixed 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 preferably having a small particle size.
- Small particle size means particles whose largest size is less than 50 microns.
- the flame retardant agent will be selected so as to be evenly distributed in the deposit formulation containing it. In particular, if it is one or more liquid compounds, the latter will be soluble or miscible in the molten polymer mixture. If it is one or more solid compounds, their small particle size will allow to obtain a regular dispersion in the molten polymer mixture.
- the process for constituting the yarns according to the invention consists in producing the sheath with a single deposition operation, but in choosing a deposition formulation that makes it possible to migrate the molecules or particles of flame retardant agent into the peripheral portion of the sheath.
- a deposit is, preferably, carried out with implementation of a calibration 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 perform the recovery and calibration of the textile core with any suitable method well known to those skilled in the art for depositing a molten polymer mixture.
- 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 mixture of polymers in the molten state and the selected flame retardant (s) is (are) applied to the multi-filament core wire by any suitable technique which will allow both the coating and the sheathing of the multi-filamentary core.
- the outer zone will therefore be composed of at least 3 components: a base polymer, a co-flame retardant polymer and a flame retardant agent.
- polymer which can be used as base polymer By way of examples of polymer which can be used as base polymer, mention may be made of: esters of acrylic or methacrylic acids, non-halogenated vinyl polymers, polyurethanes, polyamides, thermoplastic polyolefins, olefinic elastomeric thermoplastics ( TPO), styrenic copolymers of styrene butadiene (SBR) or styrene-ethylene / butylene-styrene (SEBS) type, polyesters and silicones.
- esters of acrylic or methacrylic acids non-halogenated vinyl polymers
- polyurethanes polyurethanes
- polyamides thermoplastic polyolefins
- TPO olefinic elastomeric thermoplastics
- SBR styrenic copolymers of styrene butadiene
- SEBS styrene-ethylene / butylene-styren
- a polymer that can be used as a co-flame retardant polymer mention may be made of: copolyamides, copolyesters, polyurethanes, polyolefins, oleamides and erucamides, as well as styrene-based copolymers.
- the cooling step may be carried out by passing the wire into a cooling zone, in particular maintained at a temperature in the range from 3 to 25 ° C.
- a cooling zone in particular maintained at a temperature in the range from 3 to 25 ° C.
- the outer zone will not be obtained by depositing a polymer dispersion in the form of plastisol or in the form of an aqueous dispersion.
- the plastisol route will not be retained because it requires the use of plasticizer (s) which are low molecular weight compounds, which will migrate and exude to the surface of the wires, leading to a greasy feel.
- the aqueous dispersion route 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 of environmental assaults. outside.
- the method according to the invention therefore uses neither plastisol nor plasticizer, so that the sheath contains neither plastisol nor plasticizer.
- the different steps of the process according to the invention can be carried out continuously and lead to long lengths of wire.
- the son obtained at the end of the process according to the invention may be wound in the form of coil, waiting to be used.
- 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 artificial aging with XENOTEST according to the standard NF EN ISO 105B02, a resistance to soiling and a cleaning ability, the mechanical properties necessary for the production of textiles for blinds, and resistance to bad weather, heat and cold, especially 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 M1 according to standard NFP92507 or B1 according to DIN 4102.
- the fire-retardant sheathed 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 constituted at least in 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.
- the yarn 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 aperture factor, in particular of the order of 0 to 15%, and preferably of between 3 and 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 M1 according to the French standard NFP92507 and type B1 according to the German standard DIN 4102.
- the manufacturing process used is schematized Figure 2 the wire 1 constituting the multi-filament core is unwound from a coil 10 , to pass into a preheating zone 20 , before reaching a wrapping extrusion device 30 ending in a die, from which it leaves to be directed to a cooling zone 40 , to obtain a wire I according to the invention which can be stored after winding in the form of a coil 50.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Multicomponent Fibers (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Artificial Filaments (AREA)
Claims (15)
- Verfahren zur Herstellung eines Garns (I), das aus einem Multifilamentkern (1) besteht, der mit einem polymeren Mantel überzogen ist, wobei der Mantel zwei koaxial aufeinander folgende Polymerzonen (2, 3) umfasst, die als innere Zone (2) und äußere Zone (3) bezeichnet werden, wobei die äußere Zone (3) mindestens ein Flammschutzmittel (4) beinhaltet, wobei die Konzentration des Flammschutzmittels (4) in der äußeren Zone (3) höher ist als die Konzentration des Flammschutzmittels (4) in der inneren Zone (2), dadurch gekennzeichnet, dass der Mantel hergestellt wird, indem auf dem Multifilamentkern (1) eine mischbare Mischung von Polymerschmelzen aufgebracht wird, umfassend:- das mindestens eine Flammschutzmittel (4) und- mindestens zwei Polymere, die im geschmolzenen Zustand keine dauerhaften chemischen Bindungen untereinander eingehen, wobei eines der beiden Polymere, das als co-flammhemmendes Polymer bezeichnet wird, einerseits eine Glasübergangstemperatur aufweist, die um mindestens 10°C niedriger ist als die des anderen Polymers, das als Basispolymer bezeichnet wird, und andererseits eine Schmelztemperatur aufweist, die ebenfalls um mindestens 10°C niedriger ist als die des Basispolymers,wobei auf die Aufbringung ein Abkühlungsschritt folgt, bei dem das Basispolymer zuerst erstarrt und das co-flammhemmende Polymer nach außen wandert, wobei es mindestens einen Teil des Flammschutzmittels (4) mit sich führt.
- Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass das hergestellte Garn (I) halogenfrei ist.
- Verfahren gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Abkühlung des Garns (I) mit einem Lager bei einer Temperatur durchgeführt wird, die niedriger als die Glasübergangstemperatur des Basispolymers, aber höher als die des co-flammhemmenden Polymers ist.
- Verfahren gemäß Anspruch 1, 2 oder 3, dadurch gekennzeichnet, dass die Aufbringung mittels eines Kalibrierschrittes durch Extrudieren eines Mantels auf den Kernfaden (1) und Kalibrieren des Mantels durch Führen in eine Düse durchgeführt wird.
- Verfahren gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das oder die Basispolymer(e) ausgewählt wird (werden) aus Acryl- oder Methacrylsäureestern, halogenfreien Vinylpolymeren, Polyurethanen, Polyamiden, thermoplastischen Polyolefinen, thermoplastischen Elastomeren auf Olefinbasis (TPO), Styrolcopolymeren vom Typ Styrol-Butadien oder Styrol-Ethylen/Butylen-Styrol, Polyestern und Silikonen, und das oder die co-flammhemmenden Polymer(e) ausgewählt wird (werden) aus Copolyamiden, Copolyestern, Polyurethanen, Polyolefinen, Oleamiden, Erukamiden und Copolymeren auf Styrolbasis.
- Verfahren gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Differenz zwischen der Schmelztemperatur des co-flammhemmenden Polymers und der des Basispolymers in den Bereich von 15 bis 50 °C, bevorzugt in den Bereich von 30 bis 50 °C, fällt.
- Verfahren gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass der Mantel in dem hergestellten Garn (I) 40 bis 80 Masse-%, bevorzugt 50 bis 70 Masse-%, der Gesamtmasse des Garnes (I) ausmacht.
- Verfahren gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die äußere Zone (3) des hergestellten Garnes (I) eine Menge an Flammschutzmittel (4) umfasst, die einem Masseanteil von 15 bis 50 %, bevorzugt 20 bis 30 %, der Gesamtmasse des Mantels entspricht.
- Verfahren gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass das hergestellte Garn (I) einen mittleren Durchmesser im Bereich von 150 ± 10 % bis 500 ± 10 % µm, bevorzugt im Bereich von 200 ± 10 % bis 400 ± 10 % µm, aufweist.
- Verfahren gemäß einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass das hergestellte Garn (I) einen kreisrunden Querschnitt und einen konstanten Durchmesser über die gesamte Länge des Garnes (I) aufweist, plus/minus ca. 10 %.
- Verfahren gemäß einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass in dem hergestellten Garn (I) mindestens 60 %, bevorzugt mindestens 75 % der Gesamtmasse des im Mantel vorhandenen Flammschutzmittels (4) sich in der äußeren Zone (3) befinden.
- Verfahren gemäß einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass in dem hergestellten Garn (I) das Flammschutzmittel (4) in der die äußere Zone (3) bildenden Polymermatrix gleichmäßig verteilt ist.
- Verfahren gemäß einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass in dem hergestellten Garn (I) die innere Zone (2) des Mantels aus einem oder mehreren Basispolymeren gebildet wird, ausgewählt aus: Acryl- oder Methacrylsäureestern, halogenfreien Vinylpolymeren, Polyurethanen, Polyamiden, thermoplastischen Polyolefinen, thermoplastischen Elastomeren auf Olefinbasis (TPO), Styrolcopolymeren vom Typ Styrol-Butadien oder Styrol-Ethylen/Butylen-Styrol, Polyestern und Silikonen, und die Polymermatrix der äußeren Zone (3) des Mantels aus mindestens einem Basispolymer, das mit dem im inneren Bereich vorhandenen identisch ist, und mindestens einem co-flammhemmenden Polymer gebildet ist, das ausgewählt ist aus Copolyamiden, Copolyestern, Polyurethanen, Polyolefinen, Oleamiden, Erukamiden und Copolymeren auf Styrolbasis.
- Verfahren gemäß einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, das der Multifilamentkern (1) aus einem thermoplastischen Polymer, bevorzugt ausgewählt aus Polyamiden, Polyestern, Polyurethanen, Polyolefinen, Vinylpolymeren und Celluloseacetat, oder einer Mischung solcher Polymere besteht.
- Verfahren gemäß einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, dass das Flammschutzmittel (4) ausgewählt ist aus phosphor- oder stickstoffhaltigen Flammschutzmitteln (4), und insbesondere aus Ammoniumpolyphosphaten, Melaminisocyanurat, Pentaerythritol- und Melaminderivaten sowie Ammoniummolybdaten.
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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 EP3134567A1 (de) | 2017-03-01 |
EP3134567B1 true EP3134567B1 (de) | 2018-06-06 |
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EP15725769.2A Active EP3134567B1 (de) | 2014-04-22 | 2015-04-21 | Neuartiges verfahren zur herstellung von flammhemmenden garnen |
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US (1) | US9920458B2 (de) |
EP (1) | EP3134567B1 (de) |
JP (1) | JP6581995B2 (de) |
KR (1) | KR102239700B1 (de) |
CN (1) | CN106460235B (de) |
AU (1) | AU2015250659B2 (de) |
BR (1) | BR112016024456A2 (de) |
CA (1) | CA2945911C (de) |
DK (1) | DK3134567T3 (de) |
ES (1) | ES2685570T3 (de) |
MX (1) | MX2016013917A (de) |
PL (1) | PL3134567T3 (de) |
WO (1) | WO2015162371A1 (de) |
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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 |
WO2020112363A1 (en) | 2018-11-29 | 2020-06-04 | Eastman Kodak Company | Aqueous composition for making yarns and fabrics |
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 (de) | 2021-07-02 | 2024-02-14 | Eastman Kodak Company | Nicht geschäumte wässrige zusammensetzung, beschichtetes textil und verfahren zur herstellung |
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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 (de) * | 1998-06-19 | 2005-12-14 | Ticona Celstran, Inc. | Beschichtete langfaserige verstärkungsverbundstruktur und verfahren zu deren herstellung |
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 |
EP2922908A2 (de) * | 2012-11-20 | 2015-09-30 | The Procter & Gamble Company | Polymerseifenzusammensetzungen sowie verfahren zur herstellung und verwendung davon |
CN104812548A (zh) * | 2012-11-20 | 2015-07-29 | 艾姆弗勒克斯有限公司 | 模塑包含羟基化类脂的热塑性聚合物组合物的方法 |
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- 2015-04-21 MX MX2016013917A patent/MX2016013917A/es unknown
- 2015-04-21 CA CA2945911A patent/CA2945911C/fr active Active
- 2015-04-21 WO PCT/FR2015/051075 patent/WO2015162371A1/fr active Application Filing
- 2015-04-21 EP EP15725769.2A patent/EP3134567B1/de active Active
- 2015-04-21 AU AU2015250659A patent/AU2015250659B2/en active Active
- 2015-04-21 JP JP2016564083A patent/JP6581995B2/ja active Active
- 2015-04-21 BR BR112016024456A patent/BR112016024456A2/pt not_active Application Discontinuation
- 2015-04-21 ES ES15725769.2T patent/ES2685570T3/es active Active
- 2015-04-21 US US15/305,668 patent/US9920458B2/en active Active
- 2015-04-21 DK DK15725769.2T patent/DK3134567T3/en active
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Also Published As
Publication number | Publication date |
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CA2945911A1 (fr) | 2015-10-29 |
AU2015250659B2 (en) | 2019-03-21 |
AU2015250659A1 (en) | 2016-11-03 |
KR20160143834A (ko) | 2016-12-14 |
DK3134567T3 (en) | 2018-09-03 |
EP3134567A1 (de) | 2017-03-01 |
CA2945911C (fr) | 2022-06-14 |
CN106460235B (zh) | 2019-03-01 |
US20170044694A1 (en) | 2017-02-16 |
KR102239700B1 (ko) | 2021-04-13 |
ES2685570T3 (es) | 2018-10-10 |
CN106460235A (zh) | 2017-02-22 |
US9920458B2 (en) | 2018-03-20 |
BR112016024456A2 (pt) | 2017-08-15 |
MX2016013917A (es) | 2017-05-23 |
WO2015162371A1 (fr) | 2015-10-29 |
JP6581995B2 (ja) | 2019-09-25 |
JP2017514034A (ja) | 2017-06-01 |
PL3134567T3 (pl) | 2018-11-30 |
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