FR2834302A1 - COMPOSITE WIRE, PROCESS FOR OBTAINING AND TEXTILE STRUCTURE OBTAINED - Google Patents

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

inner guide (3) and said anode roller (31).

  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 suitable textile plies, to meet any particular application or specification, for example for the manufacture of blinds or rain curtains. More particularly, the invention relates to

  flame retardant composites obtainable by coating.

  In general, we already know, and the Applicant manufactures and sells technical composite yarns, comprising: - a core comprising a continuous yarn, in particular of inorganic material such as glass, or organic such as polyester, polyamide, I ' polyvinyl alcohol, and - a sheath or envelope comprising a matrix, constituse by at least one chlorinated polymer material, for example a polyvinyl chloride (PVC), a fireproof mineral filler incorporated and distributed

  in said matrix, and a plasticizer.

  Preferably, but not exclusively, such a yarn is obtained by coating in one or two layers, the core with a plastisol comprising the chlorinated polymer material, for example polyvinyl chloride.

  vinyl, and the plasticizer, then by gelling the plastisol around the soul.

  The technical fabrics obtained with such yarns, and when they are used in different environments, in particular for interior and exterior development of buildings or constructions, for example as blinds, are subject to the requirements of fire behavior, delinquency by regulations and / or procedures

  approval or authorization, national or international.

  Thus, the regulations applicable to such fabrics in the Federal Republic of Germany delineat different classifications, characterized in particular by the length of the sample destroyed by the 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 define, as for it, also different classifications according to standards NF 1601 and NF P 92503, on the one hand characterized in particular by the emission of fumoes and identified by the letters FO to F5, F3 being the best behavior accessible by a material containing a halogenated polymer, and secondly characterized in particular by the residual ignition temperature of the fabric, and identified by the letters MO to M4, the letter M 1 identifying the best fire behavior generally accessible by a material

  comprising organic materials.

  Various attempts have been made to inherently improve the fire performance of such composite yarns, for example by using special peat- izers, such as organic powders. Unfortunately, the use of such plasticizers deteriorates the characteristics of implementation (flexibility, sliding power, etc ...) of these son, which affects their posterior weaving, and makes the latter more difficult. Moreover, the incorporation of such plasticizers increases the smoke index. As regards the performance of the flame retardant itself, various documents have proposed various compounds or various compositions that can improve the fire behavior of plastic matrices in which the fire-retardant filler is incorporated, without the application or implementation of form of matter

  flame-retarded plastic, for example in the form of wire, is specified.

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

of zinc.

  And according to FR-A-2 448 554, again for a polyvinyl chloride-based matrix, which also incorporates a stabilizer, a plasticizer consisting of a phosphoric ester, and a charge of alumina hydroxide, it has been proposed a flame retardant filler comprising an antimony oxide, optionally combined with a zirconium borate. None of the flame retardant fillers previously proposed is suitable for improving in the desired proportions the fire behavior of a composite yarn as previously considered, and without

  degrade its other properties, for example mechanical.

  Nor is it possible to significantly increase the proportion by weight of the flame retardant filler, except to deteriorate as before the characteristics of implementation of the flame retardant

composite yarn.

  The subject of the present invention is a coated flame-retardant composite yarn having overall and intrinsically improved fire behavior, by promoting the dissipation of heat and by greatly reducing the random phenomenon of flame spread measured by fire tests according to the invention. NF P 92 503 standard on any fabric obtained from the composite yarn according to the invention, using less flame retardant filler. These properties are obtained by using, as the core of the fireproof composite yarn coated, a composite yarn consisting of distributed fibers.

  uniformly in a polymeric material.

  The present invention relates to a composite yarn consisting of a continuous yarn, obtained by spinning fibers made of an organic or inorganic material or natural fibers such as linen or cotton, and a polymer material, characterized in that the constituent fibers of said continuous wire are distributed uniformly in said polymeric material of such

  whereby each of said fibers is coated with said polymeric material.

  This composite yarn can then be used as a core for the production of flame retarded composite yarns obtained by coating with

  polymers with flame retardant fillers.

  The subject of the present invention is also the coated fire-resistant composite yarn that can be obtained by a coating process with a polymer material comprising a fire-retardant filler, characterized in that it comprises a core constituted by a composite yarn as defined above. and in that the polymeric material formed around

  the soul and the constituent polymeric material of the soul are of the same nature.

  According to the invention, said coating can be carried out with a liquid monomer or polymer preparation, for example a liquid polymer preparation 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 UV irradiation. The invention also relates to the method of manufacturing a 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 method of mechanical opening of the yarn allowing the separation of said fibers, simultaneously or in advance with its

  coating with a polymer material.

  It also relates to the method of manufacturing a fireproof composite yarn characterized in that subject a continuous yarn, obtained by spinning fibers of an organic or inorganic material or natural fibers, to a method 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 a flame-retardant filler, and in that the composite yarn obtained is subjected to a second coating with a liquid monomer or liquid-form polymer preparation comprising

a fireproof charge.

  By mechanical opening is meant any process which simultaneously or before the coating allows the opening of fibers such as the derating, by the application of an air jet, a jet of water, a treatment by ultrasound, the application of machanic pressure, for example a crushing of the wire or any method of separating the fibers to allow penetration of the polymeric material within the

constituent fibers of said yarn.

  The yarn according to the invention has none of the phenomena of

  stripping and shading observed with the son of the prior art.

  These results are obtained without affecting the characteristics of implementation 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 elements, by suppressing or reducing capillary rise, and easier to remove.

  cut out by delibrillation phenomena at the cut.

  By liquid preparation of monomers or polymers,

  means 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 split-state polymer preparation comprising additives in an organic liquid.

or not.

  By "plastisol" is meant a dispersion of polymers, fillers and other additives, in a finely divided state, in a plasticizer. As the polymer material, it is possible to use chlorinated polymers, silicones, polyurethanes, acrylics, ethylene-vinyl acetate-EVA copolymers, ethylene-propylene-diene terpolymers.

monomer, EPDM.

  As a chlorinated polymer material, it is possible to use, in accordance with the invention, any PVC resin that can be plasticized, and in particular that can therefore be used in the form of plastisol. By chlorinated polymer material is meant, or 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 that can be copolymerized with vinyl chloride, there may be mentioned olefins such as 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.

  Examples of chlorinated polymers that may be mentioned are 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 weight content of

  halogen between 40 and 70%.

  As a silicone polymer material, it is possible to use according to the invention the organopolysiloxanes and more particularly the resins and

  polysiloxane elastomers with or without a diluent.

  As polyurethane polymer material, any material consisting of a hydrocarbon chain comprising

the urethane or -NHCOO- unit.

  Regarding the continuous wire it is itself constituted by one or more continuous filaments or fibers. Its chemical nature can be organic, for example polyester, polyamide, polyvinyl, acrylic, of natural origin such as linen or cotton, or inorganic, for example S glass or silica, it being understood that its melting temperature must be higher the flame retardant filler is selected from the group consisting of zinc borate, aluminum hydroxide, antimony trioxide and zinc hydroxystannate, molybdenum compounds, derivatives thereof. halogenated compounds, active halogen compounds, phosphorus compounds and

intumescent systems.

  Other fillers may be incorporated and dispensed into the liquid preparation of monomers or polymers, in addition to the flame retardant filler, for example a pigment filler, silica, talc, glass beads and / or a stabilizing filler. In such a case, the total weight composition of the composite yarn, in inorganic materials, 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 properties of implementation of the wire, vis-à-vis his

subsequent weaving.

  The invention also makes it possible to limit the fire-retardant load by weight, in proportions not exceeding 50% of the plastic matrix. Beyond, we are witnessing an alteration of the properties in particular

mechanical composite wire.

  All the technical characteristics of the wire are improved. Particularly noteworthy include the homogeneous distribution of the polymeric material formed around the core, the resistance to capillarity, the homogeneity of the colors and the attachment of the sheath on the core. In the case of the use of PVC plastisol, the addition of agent

  Isocyanate bonding is not necessary.

  FIG. 1 is a sectional drawing of a flame retardant composite yarn of

the prior art.

  Figure 2 shows in section a fireproof composite yarn according to the invention. The homogeneous distribution of the fibers 1 is observed in the preparation of monomer or polymer 2 applied to the liquid state and cooled or polymerized after application. Secondary coating 3 is

  also regularly distributed in the composite yarn according to the invention.

  The following comparative table makes it possible to illustrate all of these characteristics, in comparison with a conventionally coated wire, in the particular case of using a material

chlorinated polymer, PVC.

  Standard Coating Coating according to the inven1ion> -m # l -s <turns the enducuon FsEsol PVC ignig 1500 PsUsol 350 mPa.s = 1 - rdse PVC = JOOpor - rdse PVC = 100 charge carriers OgnTgeants) = 15 - chsrge rate = 0 p - plesEsn1 rate = 30 50 pcr - plasdEan1 rate = 00 70 pcr

- _ 0 - ^ _ 0

  : _ = PlstisoI PVC fireproof identical Plastisoi PVC lgnifug 1500 mPa. s 26me enduchon the first endo Rate of empo = 30 50 - i = 1 - ux of chse (ignlgeants) = 1 pcr - rate of plasdDnt = 30-50 pcr

- _ 0

  Proprid1As of the ILO = 30.7 ILO = 30 Bl plaster - ger nuangage - no nuangage - ger dgaage - no dgaage - ug fgngeant = 8 15 - ux @ngeant the # of envimn = ^ - no and cheminde 16 layer: + 45 PVC i67 layer: + 41 PVC 28th layer: + 24 PVC 2nd layer: + 30 PVC - 1 B1 - 1 homogenous property - slightly nuncA - B] nssu Some of the drains (breakages of duct propdats during mechanized solilcittions under constraints (non-mechanics) glass defects) - No nuangage - No dgasge - No defflatlon - anticapll [aritd The take-off rate is the rate of impregnation of the ffl is defined by the following formula : Coated Wire Density - FlL x 1 OQ Wt. Weight of IL Coated Wire Represents Flndlce OxvgAne Limit, It Is dAtermlnd 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 have been used: Resins: a. Vinnolit P4472 PVC resin, Vinnolit P70, Vinnolit P70 PS (VINNOLIT), SELIN 372 No (SELVAN) b. Lacovyl B 1050 filler resin (ATOFINA), Vinnolit C65V (VINNOLIT), Vinnolit

C66 (VINNOLIT), C66W.

  Plastifiers: DINP (Jayflex DINP, Palatinol N (BASF), Vestinol 9 (OXENO)), TXIB (Eastman TXIB), DIDP (Jayflex DIDP (EXXON), Palatinol Z (BASF)), BBP (Santicizer 206) (FERRO) Stabilizers : at. Thermal Stabilizer based on Pb (Baerostab V 220) (BAERLOCHER) based on Organic Salts of Barium Zinc (Lastab DC 261 GL (LAGOR), Mark BZ 561 (WITCO)) based on Thio Etain (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 Trooxide (Antimony Oxide / Timonox) (SICA,

CAMPINE, PLC)

  Zinc Hydroxystannate (StormFlam ZHS (JOSEPH STOREY) Additives: Viscosity Modifiers / Rheological Agents: Viscobyk 4013, CAB-OSIL, Exxsol D80 (BYK-CHEMIE, CABOT, EXXON)

  Wetting agents: disperplast-1142 (BYK-CHEMIE).

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

fries.

  This optimization of the dissipation overall makes it possible to lower the rate of fire-retardant fillers in the coated fire-resistant composite wire. The following example illustrates the invention in the case

  particular of the use of a silicone polymer material.

  By coating according to the method of the invention a mineral / continuous glass fiber / silionne wire, that is to say by subjecting the wire to a mechanical opening by derogating simultaneously or prior to coating with a liquid preparation of polymer based on silicone polymer is obtained a fireproof composite wire coated according to the invention without halogen. The coating formulation is defined by a viscosity of between 1000 and 5000 mPa.s, measured at 25.degree.

  Brookfield RVT viscometer at 20 rpm, spindle 4.

  The primary coating is carried out with a formulation comprising the following products: Silicone 100 pcr Solvent / water O to 50 pcr Zinc borate O to 10 pcr Adhesion promoter O to 5 pcr Flame retardant O to 5 pcr Crosslinking agent 2 to 6 pcr Hydrophobic O to 5 pcr Additives O to 5 pcr The second coating is carried out with a formulation comprising the following products: Silicone 1 0 0 pcr Solvent / water 0 to 50 pcr r Zinc borate 0 to 10 pcr Flame retardant 0 to 5 pcr Reticulant 2 to 6 pcr Alumina hydrate 0 to 50 pcr Pigment 0 to 5 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).

  The diluents arechosis among toluene, xylene, white

spirit or water.

  The fillers consist, for example, of Firebreak ZB zinc borate, aluminum hydroxide (OMYA), SH5n promoter alumina Elastosil 45568 VP or HF86 (WACKER), retarder HTV-SB5WACKER), water repellent WS60E (WACKER) or marbles

glass (SOVITEC).

  Tissues obtained with a composite yarn according to the invention do not need a posterior treatment to improve their fire behavior. A flame-retarded composite yarn according to the invention has no defibrillation at the cut, it is more hydrophobic, its feel is more "soft",

  and the textiles obtained by weaving are antifouling.

  A composite yarn according to the present invention can be intagré in all textile structures, or assembled according to any textile structures required, two-dimensional (tablecloths, fabrics, etc.) or three-dimensional

(braids for example).

  The composite yarn can first be cut and divided into elementary yarns, which can be interwoven and fixed to one another in the form of non-woven textile structures, eg mats. The fixing of the intermingled elementary son can be obtained by impregnation with an appropriate adhesive substance, or by thermo-fusion of the material

polymer sheath.

  The composite yarn can then be assembled on itself, in any suitable knitted textile structures. but it can be assembled with other son, according to the present invention or not, to constitute different two-dimensional or three-dimensional structures; in the latter case, they may be grids in which the yarns according to the present invention are crisscrossed and fixed with other yarns, according to the present invention or not, and of fabrics, in which the composite yarns according to the invention are woven with other warp yarns and / or weft, also

according to the invention or not.

  A very particular application of the present invention relates to obtaining technical fabrics intended for the production or

  manufacture of blinds or curtains both inside and outside.

  After fire tests, all these fabrics showed that they satisfied, and to the German regulations with the classification B1, and to

  the French regulations with the classification M 1 and F3.

Claims (11)

  1. Composite yarn consisting of a continuous yarn, obtained by spinning fibers of an organic or inorganic material or natural fibers, and a polymeric material, characterized in that the constituent fibers of said continuous yarn are distributed uniformly in said material polymer such that each of said fibers is coated with said polymeric material. 2. fire-resistant composite yarn obtainable by a coating process with a monomer or polymer liquid preparation comprising a polymeric material and a fire-retardant filler, characterized in that it comprises a core constituted by a composite yarn according to the claim 1 and in that the material formed around the soul   and the constituent polymeric material of the core are of the same nature.   Composite yarn according to any one of claims 1   or 2, characterized in that the inorganic or organic material constituting the fibers of the yarn is selected from the group consisting of polyester, glass or silica.   4. Composite yarn according to any one of claims 1   or 2, characterized in that the polymeric material is selected from chlorinated polymers.   5. Composite yarn according to claim 4, characterized in that the chlorinated polymer material is selected from the group consisting of polyvinyl chloride, superchlorinated PVC, polyvinylidene chloride and chlorinated polyolefins.   Composite yarn according to one of claims 1   or 2, characterized in that the polymeric material is selected from organopolysiloxanes.   Composite yarn according to any one of claims 1   or 2, characterized in that the polymeric material is selected from polyurethanes.   8. Composite yarn according to any one of claims 1   or 2, characterized in that the flame retardant filler is selected from the group consisting of zinc borate, aluminum hydroxide, trioxide   of antimony and zinc hydroxystannate.   9. A method of manufacturing a composite yarn characterized in that subject a continuous thread, obtained by spinning fibers of an organic or inorganic material, to a macanese opening process of the yarn allowing the separation of the fibers, simultaneously or prior to   its coating with a polymer material.   10. A method of manufacturing a fireproof composite yarn characterized in that subject a continuous yarn, obtained by spinning fibers of an organic or inorganic material, to a macanese opening process of the yarn allowing the separation of said fibers, previously at a primary coating by a monomer or polymer liquid preparation having no flame retardant filler, and in that the composite yarn obtained is subjected to a second coating with a monomer or polymer liquid preparation comprising a flame-retardant filler. 11. 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 2 to 9.