EP1458910A2

EP1458910A2 - Composite yarn, method for obtaining same and resulting textile structure

Info

Publication number: EP1458910A2
Application number: EP02799125A
Authority: EP
Inventors: Isabelle Conesa; Philippe Berge; Laurence Pollet
Original assignee: Chavanoz Industrie SARL
Current assignee: Chavanoz Industrie SARL
Priority date: 2001-12-28
Filing date: 2002-12-27
Publication date: 2004-09-22
Anticipated expiration: 2022-12-27
Also published as: DE60221707T2; DE60221707D1; DK1458910T3; KR20040071760A; WO2003056082A3; BR0215350A; US20050042447A1; EP1458910B1; HK1072280A1; JP2005513299A; AU2002364347B2; ES2291533T3; BR0215350B1; FR2834302B1; JP4272530B2; CN1608153B; CA2470453A1; CN1608153A; WO2003056082A2; ATE369448T1

Abstract

The invention concerns a composite yarn consisting of a continuous yarn, obtained by spinning fibers made of organic or inorganic material or natural fibers, and a polymer material. The invention is characterized in that the consecutive fibers said yarn are uniformly distributed in said polymer material such that each of said fibers is coated by said polymer material. The invention also concerns a method for making such a composite yarn and a textile structure obtainable from at least a composite yarn of the invention.

Description

COMPOSITE YARN, PROCESS FOR OBTAINING SAME, AND TEXTILE STRUCTURE OBTAINED

The present invention relates to a composite yarn for technical or industrial use, which can be assembled into all types of textile structures, in particular appropriate textile tablecloths, to meet any particular application or specification, for example for the manufacture of blinds or curtains. More particularly, the invention relates to composite yarns capable of being obtained by coating.

In general, we already know, and the Applicant manufactures and sells technical composite yarns, comprising:

a core comprising a continuous wire, in particular in inorganic material such as glass, or organic material such as polyester, polyamide, polyvinyl alcohol, and

- A sheath or envelope comprising a matrix, consisting of at least one chlorinated polymeric material, for example a polyvinyl chloride (PVC), a flame retardant mineral filler incorporated and distributed in said matrix, and a plasticizer. Preferably, but not exclusively, such a wire is obtained by coating in one or two layers, the core with a plastisol comprising the chlorinated polymeric material, for example polyvinyl chloride, and the plasticizer, then by gelation of the plastisol. around the soul.

The technical fabrics obtained with such threads, and when they are used in different environments, in particular for the interior and exterior fittings of buildings or constructions, for example as blinds, are subject to fire behavior, defined by national or international regulations and / or approval or authorization procedures. Thus, the regulations applicable to such fabrics in the Republic

Federal Republic of Germany defines different classifications, characterized in particular by the length of the sample destroyed by fire, and by the temperature of the combustion fumes, and identified by the letters B1 to B3, the letter B1 characterizing the best accessible fire behavior by a material comprising organic materials. And the regulations applicable in France, meanwhile, also define different classifications according to standards NF 1601 and NF P 92503, on the one hand characterized in particular by the emission of smoke and identified by the letters FO to F5, F3 being the best behavior. accessible by a material containing a halogenated polymer, and on the other hand characterized in particular by the residual ignition temperature of the fabric, and identified by the letters MO to M4, the letter M1 identifying the best behavior in fire generally accessible by a material comprising organic matter. Various attempts have been made to intrinsically improve the fire behavior of these composite yarns, for example by using specific plasticizers, such as organic phosphates. Unfortunately, the use of such plasticizers deteriorates the processing characteristics (flexibility, sliding power, etc.) of these threads, which harms their posterior weaving, and makes the latter more difficult. Furthermore, the incorporation of such plasticizers increases the smoke index.

As regards the performance of the flame retardant filler proper, various documents have proposed various compounds or various compositions, capable of improving the fire behavior of the plastic matrices in which the flame retardant filler is incorporated, without the application or setting form of the flame-retardant plastic, for example in the form of a wire, is specified.

Thus, according to document JP-A-58185637, for a matrix based on polyvinyl chloride, a flame retardant filler has been proposed comprising a chlorinated polyethylene, a compound chosen from in particular the oxides and / or hydroxides of antimony, and of aluminum, and preferably another compound chosen from certain zinc salts, including zinc borate; products based on tin, for example zinc stannate.

And in accordance with document FR-A-2 448 554, still for a matrix based on polyvinyl chloride, incorporating moreover a stabilizer, a plasticizer constituted by a phosphoric ester, and a filler of aluminum hydroxide, we have proposed a flame retardant filler comprising an antimony oxide, optionally combined with a zinc borate.

None of the flame retardants previously proposed is suitable for improving the desired behavior in the desired proportions. fire of a composite wire as previously considered, and this without degrading its other properties, for example mechanical.

It is not possible, either, to significantly increase the weight proportion of the flame-retardant filler, except to deteriorate, as before, the processing characteristics of the composite yarn.

The subject of the present invention is a coated composite wire, having an overall and intrinsically improved fire behavior, promoting heat dissipation and making it possible to greatly reduce the random phenomenon of flame propagation measured by fire tests according to the standard. NF P 92 503 on any fabric obtained from the composite yarn according to the invention.

The temperature resistance properties are improved due to the regular distribution of the fibers in the polymer coating material which allows heat dissipation, in fact when the fibers are grouped together they constitute a preferential conduction path which promotes the propagation of the heat.

The subject of the present invention is a composite yarn consisting of a continuous yarn, obtained by spinning fibers of an organic or inorganic material or of natural fibers such as linen or cotton, and of a polymer material, characterized in that the constituent fibers of said continuous yarn are distributed uniformly in said polymeric material so that each of said fibers is coated by said polymeric material.

This composite wire can be used alone or as a core for the manufacture of composite wires obtained by a second coating with a polymeric material.

The present invention also relates to a coated composite yarn capable of being obtained by a coating process with a polymeric material, characterized in that it comprises a core constituted by a composite yarn as defined above and in that the polymer material formed around the core and the polymer material constituting the core are of the same nature.

Depending on the required fire behavior characteristics, this composite yarn can be used as a core for the manufacture of flame retardant composite yarns obtained by coating with polymers containing flame retardant fillers. Yarns are thus obtained which, overall and intrinsically, exhibit improved fire behavior by using less flame retardant filler.

The present invention also relates to a coated flame retardant composite yarn capable of being obtained by a coating process with a polymer material comprising a flame retardant filler, characterized in that it comprises a core constituted by a composite yarn as defined above and in that the polymer material constituted around the core and the polymer material constituting the core are of the same nature.

According to the invention, said coating is capable of being carried out with a liquid preparation of monomer or of polymer, for example a liquid preparation of polymer is obtained by melting a polymer or by dispersion, for example in the form of plastisol, and for example a liquid monomer preparation consists of a liquid monomer which will polymerize under the effect of heat or by irradiation, for example UN irradiation.

The invention also relates to the process for manufacturing a composite thread, characterized in that a continuous thread, obtained by spinning fibers of an organic or inorganic material or of natural fibers, is subjected to a process of mechanical opening of the thread allowing the separation of said fibers, simultaneously or prior to its coating with a polymeric material.

It also relates to the process for manufacturing a composite thread, characterized in that a continuous thread, obtained by spinning fibers of an organic or inorganic material or of natural fibers, is subjected to a process of mechanical opening of the thread allowing the separation of said fibers, simultaneously or prior to a primary coating with a liquid preparation of monomer or polymer in the liquid state, and in that the composite yarn obtained is subjected to a second coating with a liquid preparation of monomer or polymer.

Preferably, the monomer or polymer of the second coating is of the same nature as the monomer or polymer of the first coating.

It further relates to the process for manufacturing a fireproof composite yarn, characterized in that a continuous yarn, obtained by spinning fibers of an organic or inorganic material or of natural fibers, is subjected to a process of mechanical opening of the yarn. allowing the separation of said fibers, simultaneously or prior to a primary coating with a liquid preparation of monomer or polymer in the liquid state not comprising no flame retardant filler, and in that the composite yarn obtained is subjected to a second coating with a liquid preparation of monomer or polymer in the liquid state comprising a flame retardant filler.

By mechanical opening is meant any process allowing the fibers to be opened simultaneously or prior to coating, such as coding, by the application of an air jet, a water jet, a treatment by ultrasound, the application of mechanical pressure, for example a crushing of the wire or any process making it possible to spread the fibers to allow the penetration of the polymeric material inside the fibers constituting said wire. The yarn according to the invention does not exhibit any of the stripping and shading phenomena observed with the yarns of the prior art.

These results are obtained without harming the processing characteristics of the same yarn, required for weaving, and these characteristics are even improved. Thus, the fabrics obtained by weaving these composite yarns are better protected from the weather, by suppressing or reducing capillary lifts, and easier to cut by eliminating defibrillation phenomena during cutting.

By liquid preparation of monomers or polymers is meant any liquid formulation based on monomers or polymers. By formulation is meant any mixture comprising at least one product, for example dispersion, solution, mixture of monomers and / or oligomers.

By polymer dispersion is meant any preparation of polymer in the divided state comprising additives in an organic or non-organic liquid.

By “plastisol” is meant a dispersion of polymers, fillers and other additives, in the finely divided state, in a plasticizer.

As polymeric material, use may be made of chlorinated polymers, silicones, polyurethanes, acrylics, ethylene-vinyl acetate EVA copolymers, terpolymers of ethylene propylene diene monomer, EPDM.

As chlorinated polymeric material, it is possible to use, in accordance with the invention, any PVC resin capable of being plasticized, and in particular able therefore to be used in the form of plastisol. By chlorinated polymeric material is meant either a pure chlorinated polymer or a copolymer of vinyl chloride copolymerized with other monomers, or a chlorinated polymer which is alloyed with other polymers.

Among the monomers which can be copolymerized with vinyl chloride, mention will be made in particular of olefins such as, for example, ethylene, vinyl esters of saturated carboxylic acids, such as vinyl acetate, vinyl butyrate or maleates; halogenated vinyl derivatives such as, for example, vinylidene chloride, esters of acrylic or methacrylic acid such as butyl acrylate.

By way of chlorinated polymer, mention may, for example, be made of polyvinyl chloride but also superchlorinated PVCs, polyvinylidene chlorides and chlorinated polyolefins.

Preferably, but not exclusively, the chlorinated polymer material according to the present invention has a halogen content by weight of between 40 and 70%. As silicone polymer material, organopolysiloxanes and more particularly resins and elastomers of polysiloxane with or without diluent can be used according to the invention.

As polyurethane polymer material, one can use according to the invention any material consisting of a hydrocarbon chain comprising the urethane or -NHCOO- unit.

As regards the continuous thread, it is itself constituted by one or more continuous filaments or fibers. Its chemical nature may be organic, for example polyester, polyamide, polyvinyl, acrylic, of natural origin such as linen or cotton, or inorganic, for example of glass or silica, it being understood that its melting temperature must be higher than that of implementation of the polymer material

The flame-retardant filler is chosen from the group consisting of zinc borate, aluminum hydroxide, antimony trioxide and zinc hydroxystannate, molybdenum compounds, halogen derivatives, active halogen compounds, phosphorus compounds and intumescent systems.

Other fillers can be incorporated and distributed in the liquid preparation of monomers or polymers, in addition to the flame-retardant filler, for example a pigmentary filler, silica, talc, glass beads and / or a stabilizing filler. In such a case, the composition total weight of the composite yarn, in inorganic matter, is obviously modified or affected.

In the case of the use of plastisol, thanks to the invention, it remains possible to use traditional plasticizers, for example comprising at least one phthalate, and therefore not to compromise the processing properties of the wire, with regard to its subsequent weaving.

The invention also makes it possible to limit the flame-retardant charge by weight, in proportions not exceeding 50% of the plastic matrix. Beyond this there is an alteration in the properties, in particular mechanical properties, of the composite wire.

All the technical characteristics of the wire are improved. More particularly, the homogeneous distribution of the polymer material formed around the core, the resistance to capillarity, the uniformity of the colors and the attachment of the sheath to the core will be noted.

When using PVC plastisol, the addition of isocyanate-type bonding agent is not necessary.

Figure 1 shows in section a flame retardant composite wire of the prior art. Figure 2 shows in section a flame retardant composite wire according to the invention.

The homogeneous distribution of the fibers 1 is observed in the preparation of monomer or polymer 2 applied in the liquid state and cooled or polymerized after application. The secondary coating 3 is also regularly distributed in the composite yarn according to the invention.

The following comparative table illustrates all of these characteristics, in comparison with a wire coated in a conventional manner, in the particular case of the use of a chlorinated polymer material, PVC.

The take-up rate is the rate of impregnation of the wire, it is defined by the following formula: weight of the coated wire - weight of the wire x 100 weight of the coated wire

ILO represents the Oxygen Limit Index, it is determined according to standard NF G 07128. For the preparation of formulations according to the invention, based on chlorinated polymer such as PVC, by way of example the following ingredients were used: Resins: a. pvc resin

Vinnolit P4472, Vinnolit P70, Vinnolit P70 PS (VINNOLIT), SELIN 372 No (SELVAN) b. resin filler Lacovyl B 1050 (ATOFINA), Vinnolit C65V (VINNOLIT), Vinnolit

C66 (VINNOLIT), C66W. Plasticizers:

DINP (Jayflex DINP, Palatinol N (BASF), Vestinol 9 (OXENO)), TXIB (Eastman TXIB), DIDP (Jayflex DIDP (EXXON), Palatinol Z (BASF)), BBP (Santicizer 206) (FERRO)

Stabilizers: a. Pb-based thermal stabilizer (Baerostab V 220) (BAERLOCHER) based on Organic Barium Salts Zinc (Lastab DC 261 GL (LAGOR), Mark BZ 561 (WITCO)) based on Thio Tin (Baerostab M62 A (BAERLOCHER) ) b. UV stabilizer

Benzotriazole or benzophenone (Tinuvin 320, Tinuvin 571, Tinuvin P (WITCO)) Charges:

Opacifying fillers: Zinc sulfide, ZnS (sachtolit L (SACHTLEBEN)), Titanium dioxide (KRONOS) Flame retardants:

Zinc Borate (Firebreak ZB (USBORAX)) Aluminum hydroxide (Alumina SH 5) (OMYA)

Antimony hydroxide (Antimony oxide / Timonox) (SICA, CAMPINE, PLC)

Zinc Hydroxystannate (StormFlam ZHS (JOSEPH STOREY) Additives: Viscosity modifiers / rheological agents: Viscobyk-4013,

CAB-O-SIL, Exxsol D80 (BYK-CHEMIE, CABOT.EXXON) Wetting agents: disperplast-1142 (BYK-CHEMIE).

The glass promoting heat dissipation, the phenomenon of flame propagation encountered during fire tests according to standard NF 92503 on fabric, is with a fabric obtained by weaving a flame retardant wire according to the invention, greatly reduced because the polymer material is better distributed in the core of the fibers and the stored heat is then better dissipated by the fibers.

This optimization of the dissipation makes it possible overall to lower the rate of flame retardant charges in the coated flame retardant composite wire.

The following examples illustrate the invention in the particular case of the use of a silicone-based polymer material.

By coating according to the method of the invention of a mineral wire / continuous glass fiber / silionne, that is to say by subjecting the wire to a mechanical opening by tamping simultaneously or prior to coating with a liquid polymer preparation based on silicone polymer, a flame retardant composite yarn coated according to the invention without halogen is obtained.

The coating formulation is defined by a viscosity of between 500 and 10,000 mPa.s and preferably between 1,000 and 5,000 mPa.s, measured at 25 ° C with a Brookfield RVT viscometer at 20 rpm, pin 4.

The coating is carried out with a formulation comprising the following products:

Silicone 100 pcr

Solvent / water 0 to 50 pcr Fillers (pigment, flame retardant ..) 0 to 20 pcr

Crosslinker 2 to 6 pcr

Additives 0 to 5 pcr

The silicones used are for example:

Elastosil RD6635, RD 3151 or 45539 WP (WACKER), Rhodosil

RTV 1519 (RHODIA), Dow FC227TS (DOW CORNING), 9050 / 30P de DOW

CORNING, 6600 F by WACKER, SILASTIC LPX by DOW CORNING,

Silicolease UV Poly 200 and UV cata 211 from RHODIA. The diluents are chosen from toluene, xylene, white spirit or water. The fillers consist for example of zinc borate

Firebreak ZB, aluminum hydroxide (OMYA), alumina SH5n promoter comm Elastosil 45568 VP or HF86 (WACKER), retarder HTV-SB

WACKER), water repellant WS60E (WACKER) or glass beads (SOVITEC), RAL pigment paste from WACKER.

The following formulations were carried out and composite yarns according to the invention obtained by coating.

Example 1:

First coating Carrying rate 30%

9050 / 30P of DOW CORNING 100 pcr

(viscosity 3000 cPo)

Second coating Carrying rate 30% 9050/30 P 100 pcr

Silastic (DOW CORNING) 2pcr

Example 2:

First coating 15% take-off rate 9050 / 30P from DOW CORNING

Second coating Carrying rate 15%

RD3151 (WACKER) 100 pcr

HTV-SB batch 2 (WACKER) 0.5 pcr

ZNFirebreak Borate 5 pcr RAL pigment paste (WACKER) .. 2 pcr

Crosslinker Elastosil W (WACKER) .. 3 pcr

Example 3:

A single coating Carrying rate 18% 6600 F (WACKER) 100 pcr

HTV-SB batch 2 (WACKER) 1 pcr

ATH (ALCAN) 20 pcr

Crosslinker Elastosil W (WACKER) .. 5 pcr Toluene 20 pcr Example 4:

The silicones used are crosslinkable to UV.

First coating

Silicolease UV Poly 200 (RHODIA). 100 parts Silicolease UV Cata 211 (RHODIA) 2 to 5 parts

Second coating

Silicolease UV Poly 200 (RHODIA). 100 shares

Silicolease UV Cata 211 (RHODIA) 2 to 5 parts

Fire Retardant Fillers Pigment

The fabrics obtained with a composite yarn according to the invention do not need a subsequent treatment to improve their fire behavior.

A composite yarn according to the invention has no defibrillation when cut, it is more hydrophobic, its feel is "softer", and the textiles obtained by weaving are anti-fouling.

A composite yarn according to the present invention can be integrated into any textile structure, or assembled according to any required textile structure, two-dimensional (tablecloths, fabrics, etc.) or three-dimensional (braids for example).

The composite yarn can firstly be cut and divided into elementary yarns, which can be intertwined and fixed to each other, in the form of non-woven textile structures, for example matt. The fixing of the intermingled elementary wires can be obtained by impregnation with an appropriate adhesive substance, or by thermofusion of the polymer material of the sheath.

The composite yarn can then be assembled on itself, in any suitable knitted textile structure, but it can be assembled with other yarns, according to the present invention or not, to constitute different two-dimensional or three-dimensional structures; in the latter case, it may be grids in which the threads according to the present invention are intertwined and fixed with other threads, according to the present invention or not, and fabrics, in which the composite threads according to the invention are woven with other warp and / or weft threads, also according to the invention or not. A very particular application of the present invention relates to obtaining technical fabrics, intended for the realization or manufacture of blinds or curtains both inside and outside.

After fire tests, all of these fabrics showed that they satisfied both the German regulations with the B1 classification and the French regulations with the M1 and F3 classification.

Claims

1. Composite yarn consisting of a continuous yarn, obtained by spinning fibers of an organic or inorganic material or of natural fibers, and of a polymer material, characterized in that the fibers constituting said continuous yarn are distributed uniformly in said material polymer such that each of said fibers is coated with said polymeric material.

2. Composite wire capable of being obtained by a coating process with a liquid preparation of monomer or of polymer comprising a polymer material, characterized in that it comprises a core constituted by a composite wire according to claim 1 and in that that the material formed around the core and the polymer material constituting the core are of the same nature.

3. Flame retardant composite wire capable of being obtained by a coating process with a liquid preparation of monomer or polymer comprising a polymer material and a flame retardant filler, characterized in that it comprises a core constituted by a composite wire according to the claim 1 and in that the material formed around the core and the polymer material constituting the core are of the same nature.

4. Composite yarn according to any one of claims 1 to 3, characterized in that the inorganic or organic material constituting the fibers of the yarn is chosen from the group consisting of polyester, glass or silica.

5. Composite wire according to any one of claims 1 to 3, characterized in that the polymeric material is chosen from chlorinated polymers.

6. Composite yarn according to claim 5, characterized in that the chlorinated polymer material is chosen from the group consisting of polyvinyl chloride, superchlorinated PVCs, polyvinylidene chlorides and chlorinated polyolefins.

7. Composite wire according to any one of claims 1 to 3, characterized in that the polymeric material is chosen from organopolysiloxanes.

8. Composite wire according to any one of claims 1 to 3, characterized in that the polymeric material is chosen from polyurethanes.

9. Composite wire according to claim 3, characterized in that the flame retardant filler is chosen from the group consisting of zinc borate, aluminum hydroxide, antimony trioxide and zinc hydroxystannate.

10. A method of manufacturing a composite yarn characterized in that a continuous yarn, obtained by spinning fibers of an organic or inorganic material, is subjected to a process of mechanical opening of the yarn allowing the separation of said fibers, simultaneously or prior to its coating with a polymeric material.

11. A method of manufacturing a composite yarn characterized in that a continuous yarn, obtained by spinning fibers of an organic or inorganic material, is subjected to a process of mechanical opening of the yarn allowing the separation of said fibers, prior to a primary coating with a liquid preparation of monomer or polymer, and in that the composite yarn obtained is subjected to a second coating with a liquid preparation of monomer or polymer.

12. A method of manufacturing a fireproof composite yarn characterized in that a continuous yarn, obtained by spinning fibers of an organic or inorganic material, is subjected to a process of mechanical opening of the yarn allowing the separation of said fibers, beforehand to a primary coating with a liquid preparation of monomer or of polymer not comprising a flame retardant filler, and in that the composite yarn obtained is subjected to a second coating with a liquid preparation of monomer or of polymer comprising a flame retardant filler.

13. Method according to any one of claims 11 or 12, characterized in that the monomer or polymer of the second coating is of the same nature as the monomer or polymer of the first coating.

14. Textile structure, for example fabric, characterized in that it is capable of being obtained from at least one composite yarn according to any one of claims 1 to 10.