WO2004101872A1

WO2004101872A1 - Basalt containing fabric

Info

Publication number: WO2004101872A1
Application number: PCT/BE2003/000085
Authority: WO
Inventors: Jean-Marie Nolf
Original assignee: Groep Masureel Veredeling
Priority date: 2003-05-16
Filing date: 2003-05-16
Publication date: 2004-11-25
Also published as: AU2003229147A1; EP1625248A1

Abstract

Product comprising at least a structure made of at least: yarns containing basalt fibers, a metallic reinforcing element, whereby said yarns and reinforcing element are linked together, whereby the metallic reinforcing element is adapted for ensuring a resistance to cuts and tears.

Description

Basalt containing fabric

The state of the art

Basalt fibers are well known in the art. They were developed starting in the sixties and seventies - mainly in the ex-USR , with noted activities in the USA and to a lesser degree in Italy, UK, France, Germany - initially as wool, later on the basis of continuous extruded filaments.

Basalt fibers are sized at the filament extrusion step in order to improve some of their properties, like smoothening of the filament surface (i.e. filling possible surface micro cracks and hiding surface defects) to reduce the probability of filament breakage and decreasing the fiber friction coefficient to facilitate further processing steps as weaving, knitting, braiding, etc.

US 4778844 teaches for example polyurethane flame retardant products consisting of polyurethane foam, possibly combined with basalt fibers or wool.

The reinforcement of polymers, such as epoxy, with basalt fibers, i.e. composite material, has already been taught by Subramanian et al in Sampe Quarterly, July

1977, pages 1 to 11.

It is also known to manufacture fabrics (knitted, woven, braided, non woven, combinations of these, etc.) from basalt yarns (made of basalt continuous filaments or fibers). The problems of these fabrics are :

- instability of the weave or fabric and vulnerability to defects during transportation and handling. These instability and vulnerability are mainly due to the low friction coefficient of the sized basalt fibers ; instability of the sewn fabric at the seam ; breakage problem when submitted to a sufficiently small curvature, with the consequence that the fabrics cannot be folded ; instability of the fabric due to its high friction coefficient and therefor for its non stitchability (low strength at the seam) ; high stiffness of basalt ; naked basalt fabric may irritate the skin when handled, due to the small diameter of the basalt filament ends and their stiffness ;

Etc.

Notwithstanding the good fire resistance of basalt fibers, basalt fabrics have not been widely used due to the above mentioned problems, for making clothes, especially fire protection clothes, curtains, etc. Indeed, if the fabric is not stable, cannot be stitched, is irritating and can be broken by folding, such a fabric can not provide a safe fire protection.

It has been proposed by Applicant (WO- A- 02 086213) to provide a thin polyester polyurethane coating on at least a face of a basalt fabric (advantageously on both of its faces), so as to obtain a flexible and stable fabric solving the problems of the known and marketed basalt fabrics. When bending and pinching the fabric of the invention, no or at least substantially no filament breakage appears. -Due to its stability, flexibility and resistance to breakage when folded and pinched, the coated fabric of the invention has various possible applications, for example in fire protection, especially in the manufacture of fire protecting product, such as for example clothes or parts thereof.

Said product is however not suitable for some application due to the formation of smoke. Furthermore, the product as disclosed in said document, while ensuring a sufficient drapeability, has an abrasion resistance, which is often not considered as sufficient for special applications. The PUR layer has an abrasion resistance of less than 20,000 cycles, according to the Martindale test BS 5690; 1991. Applicant has also proposed in unpublished PCT/BE 03/00061 a flexible and stable fabric having a low flammability (less than Ml, preferably M0 according to the norm NF P92-503 : 1995 ; NF P92-507 : 1997) and a low smoke generation (less than FI, preferably F0 according to the norm NF XI 0-702-1 : 1995 and NF X 10- 702-3 : 1994, toxicity in accordance with NF X 70-100 : 1986), said fabric having advantageously furthermore an excellent abrasion resistance of more than 10,000 cycles, advantageously more than 20,000 cycles, preferably more than 40,000 cycles, most preferably more than 50,000 cycles, while maintaining good flexibility and advantageously good resistance to aging.

Even if the products proposed by applicant are a good solution for fire protection, said products require further anti vandalism protection.

Anti vandalism products, such as product having cut resistance, are known. For example, EP 190 064 discloses a vandal-proof seat covering consisting of at least three layers one above another, the intermediate layer being a layer in the form of a steel wire network.

WO 02/090644 and WO 02/089617 disclose a fabric comprising at least two layers of individual elements differing from 90°. Product according to said patent applications are commercialized under the name "Locktex" by Dynatex, Mouscron (Belgium).

However, these known products do not have a sufficient fire resistance, fire blocking capability and fire stopping capability.

EP 323763 discloses a textile barrier for protection against mechanical and/or thermal attack, such as attack by fire, explosion, projectiles, bullets, vandalism, etc. The textile is a non woven fabric made of aramide fibers. The textile can be provided with a woven or netted metallic fabric. Aramide fibers are expensive and provide a limited fire resistance. The invention has thus for subject matter a product combining anti vandalism properties and fire resistance properties with a flammability of Ml or MO according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702- 3 : 1994 and NF X 70-100 : 1986.

Brief description of the invention

The invention relates to a product comprising at least a structure made of at least:

- yarns containing basalt fibers,

- a metallic reinforcing element, whereby said yarns and reinforcing element are linked together, whereby the metallic reinforcing element is adapted for ensuring a resistance to cuts and tears in a cutting or tearing direction, advantageously preventing tears and/or cuts, by means of a cardboard box cutter, said cutter being pushed into the structure and with application of a force in said cutting direction of more than 300 N, advantageously of more than 500 N, preferably of more than 600 N , such as more than 1000N or even more than 1500N and whereby said structure is at least provided with a coating layer covering at least partly the yarns containing basalt fibers, said coating being selected from the group consisting of polyester containing coating, polyurethane containing coating, silicone containing coating and mixture thereof, whereby the coated yarns containing basalt fibers are selected so as to ensure a flammability of Ml or M0 according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 for said yarns.

Advantageously, the metallic reinforcing element is adapted for ensuring a resistance to cuts and tears in two orthogonal cutting or tearing directions, as well as any combinations thereof (i.e. intermediate directions), advantageously preventing tears and/or cuts, by means of a cardboard box cutter, said cutter being pushed into the structure and with application of a force in anyone of the cutting direction (selected from the group consisting of orthogonal tearing/cut directions and directions intermediate to said two orthogonal directions) of more than 300 N, advantageously of more than 500 N, preferably of more than 600 N, such as more than 1000N, or even more than 1500N.

The metallic reinforcement element can be made of metallic wire having sufficient mechanical properties for providing anti vandalism resistance, such as cut resistance to a knife. Such metallic reinforcement element is for example an intermediate layer in the form of a steel wire network as disclosed in EP 190 064, a fabric comprising at least two layers of individual elements (advantageously differing from 90°) as disclosed in WO 02/090644 and WO 02/089617. Advantageously the metallic reinforcement combines at least one steel wire network as disclosed in EP 190 064 with one or more fabrics with two layers of individual elements as disclosed in WO 02/090644 and/or WO 02/089617. The content of these documents EP 190 064, WO 02/090644 and WO 02/089617 is incorporated in the present specification by reference. The metallic reinforcement wires and the yams containing basalt fibers can be combined together so as to form yams comprising metallic reinforcement wire(s) and basalt containing fibers, such as yams comprising a core comprising metallic reinforcement wire and a protection layer surrounding the core, said protection layer comprising basalt containing fibers. The yams can possibly comprise several metallic wires. According to an embodiment, the metallic wires and the basalt fibers are combined together so as to form the yams. Possibly the metallic wire(s) extend at the periphery of the yams or adjacent to said periphery. The metallic reinforcement wires and the yams containing basalt fibers can also be combined together so as to form a fabric, such as a woven fabric (with bindings such as satin, sateen, plain, etc.), a non woven fabric, knitted fabric, a braided fabric, a three axial (plane) fabric, a three directional or three dimensional fabric, etc. and combinations thereof. Such fabric are made of at least of yams containing at least basalt fibers, preferably basalt continuous filament fibers or BCF fibers, said fabric having a basalt weight comprised between 70 g/m² and 4000 g/m², advantageously from 100 to 3500g/m², preferably less than 2500g/m². Basalt weight means the weight of basalt present in the fabric. When the fabric is a tridimensional fabric or has a tridimensional stmcture, such as a closed stmcture, such as cylindrical stmcture, the weight per surface is determined after developing the tridimensional fabric in a plane.

However, advantageously in the basalt fabric and the metallic reinforcement element do not form a single fabric, but are bound or connected together by means of one or more connecting or binding means, such as by sewing, by adhesion, by gluing, etc. or by combinations of such means. The binding can be made by dot coating or dot sewing, so as to form local binding points.

According to an advantageous embodiment, the product comprises : - a fabric (woven such as satin, plain, etc., non woven, knitted, braided, , three dimensional, three axial (plane), etc. and combinations thereof) made at least of yams containing at least basalt fibers (preferably basalt continuous filament fibers or BCF fibers), said fabric having a weight comprised between 70 g/m² and 4000 g/m², advantageously from 100 to 3500g/m², preferably less than 2500g/m² ; advantageously a primer coating at least partly said yams or fibers of said fabric, said primer being suitable for the coating layer(s), the dry weight of primer being comprised between 10 and 200 g/m², advantageously between 20 and 100 g/m², preferably between 25 and 50 g/m² ; - at least a coating layer selected from the group consisting of polyester containing coating, polyurethane containing coating, silicone containing coating and mixture thereof, said layer coating at least partly a face of the fabric advantageously provided with a primer coating, said coating layer having a dry weight comprised between 20 and 500 g/m², advantageously between 40 and 400 g/m², preferably between 50 and 200 g/m², said weight being calculated on basis of the weight of polyester, polyurethane and silicone present in said coating layer (i.e. without taking into consideration additives, solid particles, colouring agents, powders , etc possibly present in the layer) (The total weight of the layer, i.e. with additives, solid particles, etc. is advantageously comprised between 50 and 1000g/m²). When the fabric is a tridimensional fabric or has a tridimensional stmcture, such as a closed stmcture, such as cylindrical stmcture, the weight per surface is determined after developing the tridimensional fabric in a plane. The presence of a primer coating is preferred as it ensures a better binding of polyester, polyurethane, polyester polyurethane, silicone on the yams containing basalt fibers. Polyester polyurethane and silicone are most preferred. Silicone is especially preferred.

According to a preferred embodiment, the fabric containing basalt fibers and coated with at least a coating layer is adapted for providing a fire resistance with a flammability of Ml or M0 according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 .

Most preferably, the stmcture comprising yams containing basalt fibers (especially in the form of a fabric), the metallic reinforcing element and the coating layer is adapted (by selection of the metallic reinforcing element, the yams, the coating layer and the possible binding means) for ensuring a fire resistance with a flammability of Ml or M0 (preferably M0) according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 (preferably F0) according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70- 100 : 1986 . When stitching wires or sewing wires are used, said wires are selected to be M0 or Ml, preferably M0, and F0 or FI, preferably F0.

Preferably, the fabric containing basalt fibers and coated with at least a coating layer is adapted for providing a fire resistance with a flammability of M0 according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 .

While the primer layer when used is advantageously free or substantially free of any additives, the coating layer comprises advantageously less than 25% by weight of solid particles and possible additives. The additives and solid particles, when present, are advantageously selected so as to be unapt to generate smoke (FI or preferably F0 according to norm NF XI 0-702-1 : 1995 and NF X 10-702-3 : 1994 (toxicity in accordance with NF X 70-100 : 1986)).

Advantageously the weight ratio weight of the coating layer/weight of primer layer is comprised between 3 and 30, preferably between 5 and 20, most preferably between 10 and 20.

The primer layer when applied is advantageously a layer obtained from one or more silane esters, said layer contacting preferably directly the basalt fibers, so that said primer layer is bound to silicon atoms present in the basalt fibers. Examples of preferred silane esters are ethenyl triacetate silane with trimethoxyl-3- propylester or vinyl triacetate silane with trimethoxy-3-propyl ester or allyl triacetate silane with trimethoxy-3-propyl ester or isopropenyl triacetate silane with trimetoxy-3-propylester or ethenyl triacetate silane with tri ethoxyl-3- propylester or vinyl triacetate silane with triethoxy-3-propyl ester or allyl triacetate silane with triethoxy-3-propyl ester or isopropenyl triacetate silane with trietoxy-3 -propylester or combinations thereof. Said ester can be applied on the basalt fibers as a solution or as a dispersion, for example in a solvent, such as an organic solvent suitable for the silane ester, but preferably as an aqueous dispersion, such as an aqueous dispersion containing less than 10% by weight, preferably less than 5% by weight silane ester.

According to a preferred embodiment, the coating layer on the basalt fibers or yams has an abrasion resistance of more than 10,000 cycles, advantageously more than 20,000 cycles, preferably more than 25,000 cycles, according to the Martindale test BS 5690; 1991. Most preferably, the coating layer on the basalt fibers or yams has an abrasion resistance of more than 40,000 cycles, preferably more than 50,000 cycles, according to the Martindale test BS 5690; 1991.

The basalt fabric used in the product of the invention has advantageously a flexibility (flexibility of the fabric without the metallic reinforcement) such that the coated face can be folded and pinched (pressing the folded face between fingers along the folding line), whereby two portions of the coated faces contact each other. The folding is carried out with a radius of curvature of less than 2mm, advantageously of less than 1mm, substantially without visible breakage of basalt fibers or filaments on the coated face. When only a face of the fabric is coated, the folding of the fabric does not form visible broken basalt fibers or filament on the coated side of the fabric, while some broken fibers or filaments are visible along the folding line on the uncoated side. The ratio number of visible broken fibers or filaments on the coated side along the folding line / number of visible broken fibers on the uncoated face along the folding line is advantageously less than 0.1, preferably less than 0.05, most preferably less than 0.01, especially less than 0.001, or even more. The number of visible broken fibers or filaments even on the uncoated face along the folding line is in any case low due to the passage of some coating agent between adjacent filaments or fibers.

When the two opposite faces of the fabric are coated with a primer layer and with a silicone elastomer layer, substantially no broken basalt fibers are visible on both sides along the bending line (radius of curvature of less than 1mm).

The basalt fiber comprises advantageously more than 43 % by weight, preferably at least 46% by weight of SiO₂, more preferably more than 50%, specifically more than 55%> by weight SiO₂. The basalt fibers are advantageously acid type basalt fibers. The basalt fibers have also advantageously a high Al₂O₃ content, for example a Al₂O₃ content higher than 18% by weight (for example a content comprised between 18% and 24%), and a low (CaO,MgO) content, for example a (CaO + MgO) content of less than 8% by weight (for example comprised between 5% and 8%).

According to an embodiment, the portion of the face of the fabric coated with a coating layer has a coating weight distribution such that for each cm² of the portion of the coated fabric, the weight of coating layer varies between 60%> and 250% of the average coating weight, advantageously between 70% and 150%, preferably between 80% and 130%.

While the yams can comprise a high percentage of materials other than basalt (such as glass fibers, silicate fibers, etc.) according to a detail of preferred embodiment, the yams comprise at least 50% by weight, such as more than 60% by weight, or even more than 75% by weight, advantageously more than 85% by weight, preferably more than 95% by weight of basalt fibers.

According to a specific embodiment, the two opposite faces of the fabric are coated with a primer layer and with a coating layer. The two faces can be coated with a same coating composition or with different coating compositions. However, preferably the two faces are coated with a same coating composition.

According to a preferred embodiment, the product comprises a basalt containing fabric coated with an elastomer silicone containing coating, said silicone elastomer having preferably a density after curing of at least 1.3, a shore A hardness of at least 45, and an acidity index of more than 30.

Preferably, the coating layer, especially the silicone elastomer layer, covers at least substantially uniformly a portion of a face of the fabric provided with a primer layer. According to an embodiment, a first face of the fabric is substantially completely coated with a polyester polyurethane layer, said coating being substantially uniform. The other face of the fabric (i.e. the face opposite to said first face) is possibly uncoated, but is advantageously also coated with a polymer layer, preferably with a silicone elastomer layer.

According to a possible embodiment, different silicone elastomers can be used for coating the two opposite faces of the fabric. However, preferably the same silicone elastomer is used for coating the two opposite faces of the fabric.

According to a specific embodiment, the portion of the coated face of the fabric (for example coated with a silicone elastomer coating ) has a coating weight distribution such that for each cm² of the portion of the coated fabric, the weight of coating layer varies between 60% and 250% of the average coating weight, advantageously between 10% and 150%, preferably between 80% and 130%. A uniform distribution of the coating is advantageous for ensuring substantially uniform properties of the coated fabric (stability, resistance to breakage, flexibility, etc.).

The yams can comprise some fibers not made from basalt, for example steel fibers, glass fibers (such ass E glass fibers, AR glass fibers, R glass fibers, S glass fibers, HT glass fibers, etc., and combinations thereof), carbon fibers, etc. However, advantageously the yams comprise more than 50% by weight, such as at least 75% by weight, advantageously more than 85% by weight, preferably more than 95% by weight of basalt fibers. For example, the yams comprise more than 99% basalt fibers, or is made substantially completely from basalt fibers or filaments.

According to a detail of an embodiment, the layer coating a face of the fabric has a maximum coating weight (wet stage) of 100g/m², advantageously a maximum coating weight of 80g/m², preferably a maximum coating weight of 70g/m². Possibly the said maximum coating weight at the wet stage can be higher than 100g/m², such as 200g/m² or even more.

According to a detail of another embodiment, the coating layer, especially a silicone elastomer coating layer coating a face of the fabric has a maximum coating weight of 100g/m², advantageously a maximum coating weight of 80g/m², preferably a maximum coating weight of 70g/m². Possibly the said maximum coating weight can be higher than 100g/m².

Preferably, the layer comprises at least 50% by weight of silicone elastomer and or polyester polyurethane. Most preferably, the silicone elastomer/polyester polyurethane layer comprises more than 75%> by weight silicone elastomer and/or polyester polyurethane, for example more than 90% or even more than 95%. According to an embodiment, the coating layer comprises substantially only silicone elastomer or polyester polyurethane.

According to a detail of a preferred embodiment, the basalt fibers comprises a large number (such as more than 100, for example from 100 to 1000) of continuous basalt filaments having each a diameter comprised between 5 μm and 25μm, preferably between 7μm and 24μm. The yams have a linear weight comprised between 50 tex and 4000 tex (ltex= lg for a length of 1000m), advantageously between 50 tex and 3000 tex, such as between 80 and lOOOtex, most preferably lower than 500 tex, preferably from 80 to 150 tex for weaving yams and from 150 to 600tex roving yams. The yams have for example an average equivalent diameter [equivalent diameter = 4 x ( surface of the cross section of a yam defined by the outer filaments)/(outer length of the cross section surface defined by the outer filaments)] comprised between 50 and lOOOμm, advantageously between 100 and 500μm, for example between 200 and 400μm, such as about 250μm, about 300μm, about 350 μm.

Possibly, at least a portion of a coated face with a coating layer, especially a silicone elastomer layer and/or with a polyester polyurethane, is provided with one or more further layers, such as by calendering, etc.. Said further layer can be a further silicone layer and/or a polyester polyurethane layer or a layer having various properties, such as a heat insulating layer, for example needle felt layer, basalt continuous filament fibers layer, etc. According to a possible embodiment, the fabric is provided with successive silicone elastomer layers, preferably applied the one on another, for example by applying a new silicone elastomer layer after a at least partial curing of the previous silicone elastomer. Said further layer(s) are advantageously selected so as to be Ml or MO, preferably MO, and FI or F0, preferably FO.

Preferably, the portion of the fabric coated with a coating layer, especially a polyester polyurethane layer or with a silicone layer has a porosity made of pores of less than 50μm, advantageously of less than 25 μm, preferably of less than lOμm. Said portion is most preferably substantially impermeable to liquids. Most of the times in clothing, some gas permeability is desired and/or even required. According to a possible embodiment, at least a portion of a coating layer comprises at least one, for example one or more, pigments and/or coloring pigments and/or metallic pigments (such as aluminum powders, metallic microfibers, etc.) and/or luminescent compounds (such as fluorescent compound(s) and/or a phosphorescent compound(s)) and/or mixtures thereof.

According to still another possible embodiment, at least a face of the coated fabric (which can be for example a plain fabric or a satin fabric) is associated with a heat insulating layer and/or with a heat insulating layer on its both sides.

According to still another possible embodiment, the coated fabric of the invention is used for covering one or both faces of a substrate, such as a non woven substrate.

The invention relates also to an element comprising at least a product of the invention. Preferably, a portion of the product is sewn with another portion of the product or with another product of anyone of the preceding claims or with another fabrics or layer or sheet. Advantageously, at least a portion of the product of the invention is sewn with another portion of the product of the invention or with another product of the invention or with one or more other fabrics or layers or sheets. According to a specific embodiment, the product comprises at least 3 layers which are connected the one with the other, a first layer and a second layer being each a basalt containing fabric as disclosed here above [advantageously provided with a primer coating, and with at least a coating layer selected from the group consisting of polyester containing coating, polyurethane containing coating, silicone containing coating and mixture thereof, said layer coating at least partly a face of the fabric advantageously provided with a primer coating, said coating layer having a dry weight comprised between 20 and 500 g/m², advantageously between 40 and 400 g/m², preferably between 50 and 200 g/m², said weight being calculated on basis of the weight of polyester, polyurethane and silicone present in said coating layer (i.e. without taking into consideration additives, solid particles, colouring agents, powders, etc. possibly present in the layer) (The total weight of the layer, i.e. with additives, solid particles, etc. is advantageously comprised between 50 and 1000g/m²), while an intermediate layer is a metallic reinforcing element adapted for ensuring a resistance to cuts and tears in a cutting or tearing direction (advantageously in two orthogonal directions, as well as in any combinations thereof), advantageously preventing tears and/or cuts, by means of a cardboard box cutter, said cutter being pushed into the stmcture and with application of a force in said cutting direction of more than 300 N, advantageously of more than 500 N, preferably of more than 600 N Connecting elements form bounds between the layer, such bounds can be connection created by chemical (glue, etc.), plastics, rubber, connection elements (sewing points, sewing lines, local connecting points, connection elements which are weaker than the reinforced layer, preferably weaker than at least one basalt containing fabric.

The product of the invention has various uses, such as for making inner layers, outer layers, intermediate layers, interliners in wall, floor, ceiling panels, fire resistance panels, covering laminates, such as for floor, seats, cushions, fire resistant mattresses, protective clothing, such as gloves, pancho's for forest fire fighters, tapes, canisters, tubes, heat protection envelopes (such as for pipes, valves, cables, electrical cables). These possible uses are given here above as non limiting examples.

The product of the invention finds thus possible uses in various sectors, such as construction, transport (transport of persons, transport of goods), car industry, trains, furniture, protective clothes, plant, machinery and equipment, air plane and train seating, fire proof electrical cables or wires, telecommunication wires and cables (for example copper wires, copper cables, coaxial cables, etc.), signal transmission wires or cables, optical fiber optical fiber cables, truck tarpaulins, car soft tops or covers, canopies, tents, car covers, seat covers, tapes, etc.

In order to improve specific uses of the product of the invention, additional finishing coatings are possible, such as coating for soft and continuous contact with the skin (for example obtained by flocking), further silicone coatings (for heat, weather and small impacts protection, elasticity),elastic layer, intumescent layer (for fire-heat insulation), etc.

Preferred silicone elastomers are silicone having a high density after curing, said density being measured for the cured silicone elastomer as such (i.e. free of charges or additives). Preferred silicone elastomers are elastomers having a density after curing of at least 1.3 (g/cm³), most preferably of at least 1.35, such as 1.4, 1.5 or even more. The density is measured at 23 °C in water according to the norm DIN

53479A - ISO 2781.

The silicone elastomer has moreover advantageously one or more further properties selected from the group consisting of : - Shore A hardness (DIN 53 505 - ISO 868) of at least 45, preferably of at least 50, most preferably of at least about 55 ;

- An elongation at break of at least 200%o, preferably at least 250%, most preferably from 300 to 400% (DIN 53504-S 1 - ISO 37) ;

- A tensile strength (DIN 53 504-S 1 - ISO 37) comprised between 5 and 6.5 N/mm²; - A tear resistance (ASTM D 624 B) comprised between 10 and 20 N/mm, preferably about 15 N/mm;

- A heat conductivity of about 0 W/m°K ;

- An acidity index of more than 30% ; - abrasion resistance of more than 25,000 cycles, advantageously more than

40,000 cycles, preferably more than 50,000 cycles according to the Martindale test BS 5690; 1991,

- a resistance to aging through immersion in acid, alkalis, solvents, etc., and mixture thereof. - high resistance to hydrolysis and water(for example resistance of at least 15 minutes in a boiling solution containing 4% by weight NaOH), i.e. a high resistance to aging; etc.

The invention relates also to a process for the preparation of a product of the invention, in which a basalt containing fabric is advantageously coated at least partly with a primer composition, whereby the fabric advantageously coated with the primer composition (possibly after a curing step of the primer coating) is coated at least partly with an aqueous dispersion of polyester and/or polyurethane and/or silicone elastomer, said aqueous dispersion containing at least 10% by weight of compound selected from the group consisting of polyester, polyurethane, silicone elastomer and mixture thereof, advantageously from 20 to 70% by weight, preferably from 30 to 50% by weight of said compound, whereby before and/or after the coating with an aqueous dispersion containing the compound, the basalt containing fabric is provided with a metallic reinforcement or comprises a metallic reinforcement.

In said process, advantageously no organic solvents are used, so as to avoid safety problems (fire risks), as well as environmental problems. Preferably, the aqueous dispersion is free or substantially free of emulgators. Therefore, mineral pigments or particles, such as mineral powder, can be added to the coating dispersion before its application on the basalt fabric. Said pigments or other solid additives have advantageously a particle size of less than 2μm, preferably of less than lμm, most preferably less than O.lμm.

The invention relates also to the use of a product according to the invention, as fire protection layer with anti vandalism properties, such as for interliner for mattress or seats, mattress covering, seat covering. The basalt fabric can be in direct contact with the skin.

More specifically, objects of the invention are fire protection clothes, fingers, boots, mittens, gloves, cowls, helmets, pancho's, overcoats, etc., curtains, seat interliners, panel constructions, fire proof electrical cables or wires, communication wires, truck tarpaulins, car soft tops or covers, canopies, tents, car covers, seat covers, tapes, etc. comprising at least a product or an element of the invention. Tapes can be used for wrapping, with partial overlapping (for example overlapping between 10 and 90%> of the width, advantageously between 10 and 50% of the width), around a tube, a container, a cable, an electrical cable, a telecommunication cable, a parcel, signal transmission wire or cable, etc. so as to form an armored tube, cable, container, etc. , and/or an abrasion resistant layer. Such a tape can be provided with adhesion means such as gluing means, so as to ensure a good adhesion of the tape on the tube, cable, container, etc. For example a silicone or polyurethane glue can be used.

Details and characteristics of the invention will appear from the following description, in which reference is made to the attached drawings.

Brief Description of the Drawings

Figure 1 is an upper (enlarged) view of a portion of an upper face of a fire resistant and anti vandalism structure of the invention; Figure 2 is a downside view of the stmcture of Figure 1 ;

Figure 3 is a cross section view of the structure of Figure 1 along the line III-III ; Figure 4 is a cross section view of a stmcture provided with a coated fabric on both of its faces ;

Figure 5 is an upper view of a specific embodiment similar to the embodiment of

Figure 1 ; Figure 6 is schematic view of a yam combining fire resistance and anti vandalism resistance ;

Figure 7 is a schematic view of a process for manufacturing a coated stmcture of the invention ;

Figures 8 to 10 are schematic views of other processes for manufacturing a coated fabric of the invention;

Figure 11 is an exploded view of a further stmcture of the invention;

Figure 12 is an upper view of the stmcture of figure 11 ;

Figure 13 is a schematic view showing a stmcture with a dot coating for obtaing dot connecting points ; Figure 14 is a schematic view of a portion of a possible embodiment of a structure of the invention, and

Figure 15 is a schematic view of a film stmcture having a plurality of various adjacent cushion like elements .

Description of Embodiments

Fig 1 is a schematic view of the upper face of a stmcture of the invention having fire resistance and anti vandalism properties. Said upper face consists of a coated basalt fabric. The basalt fabric 1 has a weight of about 200g/m² to 400g/m² and is made of warp yams 1A and weft yams IB, said weft yams being crossed with respect to the warp yams for example so as to pass once above and once under said warp yams (plain binding). The density of yams is 10 yams/centimeter for the warp yams and 8 yams/centimeter for the weft yams. The thickness E of the fabric before its coating is about 190μm. The yams are made from continuous basalt filament with a diameter comprised between 7 and 2 lμm, for example about 9μm, about 13μm, about 20μm, and combinations thereof, said yams weigh about 117 tex and comprise about 100 to 1500 filaments, for example about 500 filaments. The basalt filaments are made from acid type basalt, with a SiO₂ content higher than 43%, advantageously higher than 46%>, for example higher than 50% by weight. A torsion is carried out on the yams so as improve the cohesion of the filaments the one with respect to the other, for example, the torsion is such that the yam is submitted to a torsion from 5 to 150 times per meter, for example from 70 to 120 times per meter, preferably about 100 times.

A primer coating P made from silane esters with a density of about 1.1 (density at 23°C, in water - DIN 53479A - ISO 2781) is applied on the acid basalt fibers. The primer coating quantity represents about 25 g/m² of fabric. The primer forms a thin continuous or not continuous layer (preferably substantially continuous) on the face of the yams directed towards the face to be provided with the silicone elastomer coating. The silane ester used is ethenyl triacetate silane with trimethoxyl-3-propyl ester.

A coating 2 is provided on the upper face of the fabric 1, face which is provided with the primer coating, as well as on its downside face. Said coating is a silicone elastomer coating, for example a coating prepared from Elastosil ® Liquid rubber sold by Wacker Chemie. The coating 2 is applied on the fabric as an aqueous dispersion at a silicone elastomer rate of about 300g/m² (on dry basis), meaning that the thickness of the coating 2 is less than about 220μm, as part of the coating dispersion flows in between filaments of yams. The coated fabric has a total thickness of about 400-500μm. The coating layer is regularly applied so that the thickness of the coating layer varies between 50% and 200%>, advantageously from 80%) to 130% of the average coating thickness. The thickness of the coating layer is higher in the valley portions of the fabric.

The face 3 of the fabric of Fig 1 is coated so as to form a protection for the metallic reinforcement element 50, as well as partly connecting means between the reinforcement element 50 and the coated fabric 1. The reinforcement element is a knitted fabric of thin steel wire 51,51 A, etc. as disclosed in figure 4 of EP 190 064. The knitting is operated so that the distance L between the base of two adjacent wires 51, 51A is comprised between 1mm and 20mm, advantageously between 2mm and 12mm, such as 3mm, 4mm, 5mm, 6mm and 8mm. The number of connections or links between two adjacent wires is for example comprised between 1 to 20 for a length of 3cm of adjacent wires. This number is for example substantially adapted so that the distance H between two adjacent connections or links corresponds substantially to the distance L. The pitch of the knitted fabric is for example comprised between 5 and 9mm.

While in EP 190 064, the knitted fabric is not coated, in the present example, the knitted fabric 50 is coated with a primer PI and with a silicone composition 2C, advantageously compatible with the composition used for coating the fabric 1 , preferably substantially the same composition as used for coating the fabric. The fabric 1 and the knitted fabric 50 are bound together by silicone bindings or links

The knitted fabric has the form of a textile with a slidable binding. Advantageously, the knitted metallic fabric is prepared from metallic wires coated with a silicone layer prior the knitting operation.

The manufacture of the stmcture of figure 1 can for example be operated as follows.

The basalt fabric is coated on his both faces with a primer layer P. After curing of said primer layer, one of its faces is coated with a silicone composition, so as to obtain after curing a thin silicone coating on said coated face.

The knitted fabric is treated with a primer composition, cured, and thereafter coated with a silicone containing composition. After curing, the wire of the knitted fabric is provided with a silicone layer. The metallic wire has for example a diameter comprised between 50μm and 500μm, while the primer coating has a thickness for example comprised between lOμm and 75μm. The silicone coating has for example a thickness comprised between 50μm and 300μm.

The silicone coated metallic fabric is applied on the face of the basalt fabric not coated with a silicone layer. A silicone composition is then applied so as to coat the face of the basalt fabric in contact with the coated knitted metallic fabric, whereby forming after curing, silicone binds or links between the knitted fabric and the basalt fabric.

Advantageously a same silicone composition is used for coated the metallic fabric and the basalt fabric.

According to another process, the two opposite faces of the basalt fabric are coated with a silicone layer, before being contacted with the silicone coated metallic knitted fabric.

Figure 4 is a view of a structure similar to that shown in figures 1 to 3.

Said figure 4 is cross section view. The stmcture comprises three layers LA1,LA2 and L A3.

The layer LAlis a basalt fabric 1 (yams 1A,1B) provided with a primer coating P and with a silicone coating 2A,2B on its both opposite faces.

The layer LA3 is similar to the layer LAI.

The layer LA2, an intermediate layer located between the layer LAI and LA3, comprises a metallic reinforcement element, such as a metallic knitted fabric as disclosed for the embodiment of figures 1 to 3. Said knitted fabric is coated with a primer coating, before being embedded in a silicone layer 54 forming a link between the two basalt fabrics and the knitted fabric 50.

As the knitted metallic fabric is embedded in a silicone layer forming a connection between the two basalt fabrics, the knitted metallic fabric 50 can be not be coated with a primer coating.

Figure 5 is an upper view of an embodiment similar to the embodiment of figure 1. The basalt fabric 1 is a knitted fabric instead of being a woven fabric. The use of a knitted fabric 1 is advantageous for increasing the flexibility of the stmcture. The pitch of the knitted basalt fabric is for example comprised between 0.5mm and 5mm.

Figure 13 is an exploded view of a stmcture similar to that shown in figure 1. In said embodiment, the basalt fabric 1 is provided on its both faces with a silicone layer 2, said silicone layer being cured.

The metallic reinforcing element 50 is provided with a primer coating suitable for creating binds with silicone. The cured basalt fabric is provided with a pattern of uncured silicone points or dots or local area. After placement of said local silicone area, the metallic reinforcing element is pressed against the face of the basalt fabric provided with local uncured silicone points 59. The assembly consisting of basalt fabric and metallic reinforcing element is then passed through a chamber for curing the silicone points 59.

The so obtained structure comprises local binding points between the basalt fabric and the metallic reinforcing element 50, which enables a higher flexibility between the basalt fabric and the metallic reinforcing element. In this embodiment the metallic wires are connected only on their face directed towards the basalt fabric by local silicone bindings.

The silicone used for the local binding points can be a silicone having a specific properties, such as properties enabling a breakage of a local point when a force higher than a predetermined force is exerted. For example, in order to weaken the breakage properties of one or more local binding points, the silicone used for said binding points comprises one or more fillers, the breakage ability being adapted in function of the amount of filler(s) and/or the form of the filler(s) present in the silicone. Examples of possible fillers are clay, glass particles, glass fibers, metallic fibers, etc. The type and amount of filler(s) is advantageously appropriate for enabling a sufficient flexibility to the fabric or stmcture.

Figure 6 is a view of a metallic wire 60 with a diameter comprised between 25 μm and 500μm, said metallic wire being surrounded with a layer 61 comprising basalt filaments with a diameter comprised between 5μm and 25 μm, said layer 61 having for example a thickness comprised between lOOμm and 500μm. A primer coating layer P is applied on the outer face of the layer 61, while a silicone layer 62 is applied on the primer layer P.

The wire shown in figure 6 can then be used for forming a fabric, a woven fabric, a knitted fabric, a braided fabric, etc. possibly with basalt fibers not associated to a metallic wire. The wire of figure 6 can advantageously be used for preparing woven fabric having slidable binding and/or bindings suitable to be easily broken for enabling a slidability of wires the one with respect to others.

The structure of figure 1, of figure 4, of figure 5 or prepared with wire as shown in figure 6 has also the following properties :

- stable (relative movement between yams is prevented, and even at least some relative movement between filaments are prevented) ; - the coating is stable and is resistant to UN aging, as well as to temperature aging ;

- excellent adhesion of the coating on the basalt fabric ;

- the coating does not degrade the basalt fibers or filaments, nor their properties, during the application of the coating, as well as during its burning ; - the coating does not catch fire with propagating flame, nor produces toxic fumes (coated fabric classified as M0 in accordance to the norm ΝF P92-503: 1995 and NF P92-507 : 1997), the coating disappears when burning in non toxic fumes (coated fabric classified as F0 in accordance to the norm NF X10- 702-1 : 1995, NF X10-702-3 : 1994 and NF X 70-100 : 1986); r the coated face is non irritating (for example due to the absence of naked basalt filament ends) ; excellent resistance to flames after the disappearance of the coating without degradation of the basalt fabric due to the coating process;

- economical coating ;

- excellent flexibility properties and drapeability, whereby the coated fabric can conform to complex or variable form of substrates, such as seats, etc. ;

- possibility of sewing with excellent stability at the seam ;

- possibility to change, without any problem, the color of the fabric by simple addition of pigments to the polyester polyurethane dispersion (possibility to dissimulate without problem the natural color of basalt) ; - high drapeability ( according to the drape test BS 5058 : 1973) ;

- high tearing resistance ( according to the norm BS 2576 : 1986) ;

- high resistance to abrasion (an abrasion resistance of more than 50,000 cycles for the silicone elastomer coating, according to the Martindale test BS 5690; 1991.) ; - high resistance to heat, UN

- high resistance to aging through immersion in water, acids, alkalis, solvents, etc.

- anti vandalism properties

Instead of using a plain woven fabric as in example 1, a satin woven fabric or a knitted fabric can also be used for the preparation of a product according to the invention.

For example, the satin fabric (with a satin binding = 5/3) has a weight of 345g/m², a thickness of 270μm, number of weft yams per cm : 13 and a number of warp yams per cm : 22. The yams have a weight corresponding to about 100 tex and are made from about 500 continuous basalt filaments having a diameter of about lOμm. The filaments assembled for forming a yam are submitted to a torsion for example about 100 torsions for a length of lm.

Figure 7 is a schematic view of a process for manufacturing a coated fabric of Figure 1.

A knitted metallic fabric 50 is provided from a roll W and is moved towards the roll B.

The naked basalt fabric 1 is provided from a roll A, is applied on the metallic fabric 50, and is pulled by a stenter in the dryer 16 and taken by the roll B on which the coated basalt fabric attached to the metallic fabric is enrolled. The naked basalt fabric placed on the metallic fabric 50 passes through a pair of brake rollers 10 with a torque motor regulated so as to exert a low braking (for example torque motor regulated to less than 15%, advantageously less than 10%_> of the full braking capacity). The naked fabric 1 passes then in a knife over air system 11 comprising two support rollers 12,13 between which the fabric 1 extends substantially horizontally. A knife 14 contacts a portion of the fabric located between the two rollers 12,13, said knife 14 distributing an aqueous dispersion of silicone elastomer 15. After the coating operation (which can be carried out at a temperature for example from 0°C up to 100°C, advantageously from 10°C up to 65°C, preferably from 15°C up to 40°C), the wet coated fabric Ibis enters in a dryer 16. Said heater 16 comprises the stenter 17 exerting a force on the lateral edges of the fabric so as to limit the lateral or transversal stretching of the basalt fabric to less than 10%), advantageously to less than 2%o, preferably so as to avoid or to prevent substantially any transversal stretching during the drying, most preferably so as to exert a kind of negative stretching during the drying. The fabric 1 is moved with a speed for example lower than 40m/minute, such as a speed comprised between 10 and 25m/minute. The dryer 16 is advantageously using a direct gas heating or steam heating or oil heating, for example heated gas with a temperature comprised between 120°C and 250°C, preferably with a temperature of about 160°C when contacting the fabric to be dried (water evaporation and curing). The heated gas is for example combustion gas, but can also be heated air.

Possibly, before the coating operation, the fabric is prewetted with an aqueous medium or with water.

Possibly, also, the coating is made in a vacuum chamber.

The silicone elastomer coating is applied on the basalt fabric after a pretreatment step, namely the formation of a primer layer directly applied on the basalt fiber. The primer is advantageously applied as an aqueous dispersion and is at least partly cured (preferably only partly cured) before the application of the silicone elastomer liquid dispersion.

Before the application of the primer, the basalt fabric can for example be treated with an acid and/or solvent system and/or with heat.

Possibly, the coating operation and/or the drying operation are carried out in a controlled atmosphere, such as in an inert atmosphere (nitrogen).

When the two sides or faces of the fabric 1 have to be provided with a coating layer, the device disclosed in figure 7 is provided with a further coating system, preferably a coating system similar to the system 11. In this case, rollers are provided so as to turn the lower face of the fabric upwards so as to enable the coating thereof with a system similar to the system 11.

Possibly the coating of the other face of the fabric can be operated after the drying of the first coating layer. Advantageously, the drying temperature of the first layer is lower than the curing temperature. Various silicone dispersions can be used in the process shown in Figure 5 or for the preparation of the stmcture of anyone of the structures of the figures. Said dispersion have advantageously a low viscosity for example a viscosity lower than 100 mPa.s at 23°C and a pH comprised between 5 and 8, preferably from 6 to 7.5.

Examples of possible silicone elastomer dispersions are given hereafter, said dispersions being used at room temperature for the coating.

Dispersion 1 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A B with a platinum catalyst ) with a silicone elastomer content of 40%)

Dispersion 2 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 45%

Dispersion 3 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A B with a platinum catalyst) with a silicone elastomer content of 20%

Dispersion 4 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 20% and with pigment content of 10% (for example kaolin, etc.)

Dispersion 5 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A/B with a platinum catalyst ) with a silicone elastomer content of 20% and with pigment content of 20% (for example kaolin, etc.)

Dispersion 6 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 20% and with a fluorescent pigment content of 5% Dispersion 7 : aqueous dispersion silicone elastomer ( Elastosil Liquid Rubber® 3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 5% and with a fluorescent pigment content of 5%>

Dispersion 8 : aqueous dispersion silicone elastomer (Elastosil Liquid rubber

3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 10%> by weight with fume glass (SiO2) particles with a particle size lower than 50μm (such as a particle size between 0.5μm and lOμm) (SiO2 content of 5% by weight)

Dispersion 9 : aqueous dispersion silicone elastomer (Elastosil Liquid rubber

3001/55 A/B with a platinum catalyst) with a silicone elastomer content of 10% by weight with fume glass (SiO2) particles with a particle size lower than 50μm (such as a particle size between 0.5μm and lOμm) (SiO2 content of 5% by weight) and with a biocide content of 0.1% by weight (the presence of one or more biocide in the silicone coating is advantageous for preventing problems with insects).

For the precoating (precoating of the naked basalt fabric with a primer), various primer dispersions can be used, such as : - aqueous dispersion containing 5%> silane ester (ethenyl triacetate silane with trimethoxyl-3-propyl ester);

- aqueous dispersion containing 10%> silane ester (ethenyl triacetate silane with trimethoxyl-3-propyl ester);

- aqueous dispersion containing 20 %> by weight silane ester (ethenyl triacetate silane with trimethoxyl-3-propyl ester)

- aqueous dispersion containing 2%> by weight silane ester (ethenyl triacetate silane with trimethoxyl-3-propyl ester)

The various fabrics coated on one or both faces with one or more of the above dispersion can be sewn without any problem or breaking risks. Figure 8 shows a specific process for the manufacture of a double coated basalt fabric.

In this figure, the naked basalt fabric 1 enters in a bath 20 containing a primer solution or a primer dispersion. The naked fabric provided with a primer coating is then passing between nip rolls 21 so as to remove excess primer composition. The naked fabric can then be moved, if necessary, in a dryer 22 or a system for accelerating the curing of the primer on the naked fabric. Possibly, before said treatment, the basalt fabric is submitted to a treatment for removing at least partly the sizing agent (such as silane and/or paraffin) possibly used for coating the basalt filament

The drying or curing of the primer is for example made by hot air, IR heating, heat nitrogen gas, CO gas, microwave, etc., the primer being for example heated or cured at a temperature from 50°C up to 200°C.

In order to avoid an excessive reaction rate, the fabric provided with a primer coating is submitted to a cooling step 23, so as to reduce the temperature of the fabric to less than 25°C.

The fabric 1 with a primer coating is then passing through the bath 24 containing an aqueous dispersion of silicone elastomer. Before its passage in the bath 24, the coated fabric is associated with a metallic reinforcement element 50. The basalt fabric and the element 50 are then moved together in the bath 24 (containing a silicone dispersion), before passing through nip rolls 25 for removing excess silicone elastomer. A knife coater, such as a knife over air enduction ,26 is then used for coating the upper face of the fabric with a sufficient and regular amount of silicone elastomer. Said coater distributes silicone elastomer on the upper face of the fabric. The so^" coated fabric is then moved in a heating chamber or in a curing chamber 27 for enabling a quick cure of the silicone elastomer. The drying or curing of the silicone elastomer is for example made by hot air, IR heating, heat nitrogen gas, CO₂ gas, microwave, etc., the primer being for example heated or cured at a temperature from 50°C up to 250°C.

The nip-rolls are for example adapted for admitting a controlled pressure between the rolls, for example a pressure comprised between 2 10⁵Pa and 10 10⁵ Pa. Said nipp-rolls are moved in relation to the movement of the fabric.

The so obtained fabric is provided with a thick upper silicone elastomer layer and with lower silicone elastomer layer with a thickness which can vary.

In the method of figure 9, the reinforcement element 50 is added to the basalt fabric, so that the element lays on the upper face of the basalt fabric, the air knife system ensuring a control of the thickness. According to a possible embodiment, the thickness is adapted so that the reinforcement element 50 is embedded in a silicone layer bound to the basalt fabric.

If the fabric has to be provided with two thick silicone elastomer layers, one on its lower face and another on its upper face, it is possible to use a system for reversing the fabric after coating the upper face of the fabric with a silicone elastomer with a knife coater, whereby the lower face becomes the upper face which can then be further treated with a knife coater for distributing uniformly a silicone elastomer.

In the process of figures 7 to 9, aqueous primer dispersion and aqueous silicone elastomer dispersion are preferably used, especially for safety purposes, for environmental purposes, etc. and as it seems that the presence of water in both dispersions seems to be adequate for increasing the possible hydrolysis and/or curing of the primer and/or silicone elastomer.

According to still a possible method, the basalt fabric and the reinforcement element are separately treated with a silicone dispersion or with different silicone dispersions, the treated basalt fabric and the treated reinforcement element being thereafter contacted together and pressed together, before being cured together. Said method is exemplified in figure 10, in which the same reference have been used as in the methods of figures 7 and 8.

The silicone elastomer used in said process is preferably halogen free.

In the embodiments shown in figures 1 to 10, it is also possible to use a "Locktex" product (sold by Dynatex Project, Mouscron, Belgium) or a product as disclosed in WO 02/090644 and in WO 02/089617, especially a product as disclosed in anyone of the figures 1 to 10. of said patent applications, said "locktex" product being provided with two thin films sewn together, whereby the metallic wires are located between the two films.

The invention has also for subject matter a product as disclosed in WO 02/090644 and in WO 02/089617, in which the metallic wires are connected to at least a basalt fabric, preferably coated with a polyester polyurethane and/or with a silicone.

The invention has thus also for subject matter : - a fabric comprising at least two layers and/or two directions of individual elements of which at least one individual element is a reinforcing element comprising a metal component, preferably a steel component, which elements are not interwoven or interwoven, but have only an indirect connection created by chemicals, plastics, bbers or by a connection elements which are weaker than the individual reinforcing element(s), in which the individual elements are connected by means of a fabric layer, said fabric layer being a basalt containing fabric, the yams of which are coated with a polyester polyurethane and/or with a silicone; fabric as disclosed hereabove having one or more characteristics mentioned in anyone of the claims 2 to 23 of WO 02/089617. Figure 11 is a schematic exploded view of a stmcture comprising such a layer of individual elements, while figure 12 is an upper view of said stmcture.

The stmcture comprises : - an upper basalt fabric 70 made of basalt containing yams, both faces of said fabric being coated with a silicone and/or polyester polyurethane layer; an lower basalt fabric 71 made of basalt containing yams, both faces of said fabric being coated with a silicone and/or polyester polyurethane layer;

- an intermediate layer 72 comprising three series of metallic reinforcement wires (carbon steel wire with a diameter of 150μm) 73,74,75, the wires of the first series extending in a first direction, while the wires of the second series extend in a second direction, the wires of the third series extending in a third direction, said second direction forming an angle of +30° with respect to the first direction, while the third direction forms an angle of -30° with respect to the first direction (an angle of 60° being defined between the second and third directions), the wires of the three series crossing each other at crossing points CP, the number of reinforcement wires being two or three per cm in each direction,

- connecting lines CL making links at least at some crossing points with the upper and lower basalt fabrics, said connecting lines being for example made by knitting or stitching or sewing with one or more 167 dtex polyester yams and/or 70 dtex polyester yams.

The yams used for said connecting lines CL can be made in various materials, advantageously materials which do not emit toxic fumes, preferably materials having a good fire resistance, materials not suitable for propagating fire, etc. The yams can be glass containing yams, basalt containing yams, aramide yams, etc. The yams forms connecting points between wires of different series, said connecting points being weaker than the reinforcing wires, so that when a cutter is moved onto the stmcture, connecting points can be broken, whereby giving a slidability to reinforcing wires therebetween. According to an advantageous embodiment, the wire can also be made in a material resistant to a high temperature, such as at temperature higher than 300°C, advantageously higher than 400°C, preferably greater than 500°C, so as to ensure a good connection between the basalt fabric and the metallic reinforcing element. In the special embodiment in which sews are used for connecting the basalt fabric and the metallic reinforcing element, said sews being resistant to a high temperature, it has been observed that the metallic reinforcing element enables a cooling effect, as when submitted to fire, the metallic fabric and the basalt fabric remains in contact.

One or more wires are connected to a electrical power source so as to emit a signal when one or more wires are contacted together due to the action of the knife or cutter, especially a cardboard box cutter, i.e. a cutter used for opening cardboard box.

Figure 14 is a view in cross-section of a portion of a layered stmcture comprising :

- a upper basalt fabric 1 provided with silicone on its both faces ;

- a lower basalt fabric 1 provided with silicone on its both faces ; - an intermediate metallic reinforcing element (such as a fabric) 50 :

- a first insulating layer 60, for example made of basalt fibers, such as a mat of basalt fibers, said insulating layer being located between the upper basalt fabric 1 and the intermediate metallic reinforcing element 50;

- a second insulating layer 61, for example made of basalt fibers, such as a mat of basalt fibers, said insulating layer being located between the lower basalt fabric

1 and the intermediate metallic reinforcing element 50 ;

- connecting elements 62 forming bonds along edges of the stmcture, said bonds being for example sewing points connecting the upper basalt fabric, the lower basalt fabric and the intermediate metallic reinforcing element 50. Such a stmcture is advantageous as it enables great movement of the metallic reinforcing element 50 with respect to the basalt fabrics.

The lower insulating layer 61 is associated to one or more distinct electrically conductive elements, such as an aluminum film 63. Said film 63 is for example connected to the ground or to a terminal of an electrical power source, while the wires of the metallic reinforcing elements are connected to one or several electrical power source, whereby when the end of a blade of a cutter traverse the upper layer, the metallic reinforcing element and partly the lower insulating layer, an electrical contact is made between the wire and the aluminum film, whereby an alarm signal can be emitted.

An assembly can be obtained (see figure 15) with a pattern combining adjacent cushions with a stmcture similar to the structure shown in figure 14, except that the insulating layer is a compressible insulating layer and that the insulating layers are also sewn with the basalt fabrics and the metallic reinforcing element.

Instead of using silicone, while silicone is preferred, it is possible to use polyester polyurethane, such as IMPRANIL DLN aqueous dispersion.

Example of possible polyester polyurethane dispersions are given hereafter, said dispersions being used at room temperature for the coating.

Dispersion 1 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 40%

Dispersion 2 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 45%) Dispersion 3 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 20%>

Dispersion 4 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 20%> and with pigment content of 10%> (for example kaolin, etc.)

Dispersion 5 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 20% and with pigment content of 20%> (for example kaolin, etc.)

Dispersion 6 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 20%> and with a fluorescent pigment content of 5%

Dispersion 7 : aqueous dispersion polyester polyurethane ( Impranil DLN ®) with a polyester polyurethane content of 5% and with a fluorescent pigment content of 5%

It is further possible to use a combination of polyester polyurethane / silicone aqueous dispersions, as well to use silicone dispersion for coating one face of the basalt containing fabric and a polyester polyurethane dispersion for coating the other face of the basalt containing fabric.

Examples of possible fabrics are : woven fabric with binding such as plain, sateen, twill, etc., knitted flat fabric, three dimensional fabrics, etc., such as knitted tubes, braided fabrics such as in tubes, non woven fabric, needlefelt fabrics, etc.

The product of the invention can have various uses, such as for making inner layers in wall, floor, ceiling panels, fire resistance panels, covering laminates, such as for car floor, seats, cushions, fire resistant mattresses, protective clothing, such as gloves, pancho's for forest fire fighters, tapes, canisters, tubes, heat protection envelope (such as for pipe, valves, cables, electrical cables, cutting resistant luggage, cutting resistant parcel or package, cutting resistant upholstery fabric, for seats, chairs, etc.

Specific application fields are :

• construction : wall, floor and ceiling paneling for building-in fire resistance, fire curtains such as automatically falling down to segment buildings, manufacturing halls, storage areas, tunnel, electrical wire insulation, fire blocking interliners with a thermal insulation function, etc. in case of fire ;

• transportation : flexible rolls of floor covering laminates, fire resistance covering for seats, cushions, etc.

• furniture : fire resistant mattresses, fire blocking interliners in mattresses, plane seats, train seats, bus seats, etc.

• protective clothes, especially sewn protective clothes : overcoats, gloves, boots, etc. for example for fire fighter, forest fire fighter ;

• plant, machinery and equipment construction : fire protection of valves, pipes, cables, telecommunication cables, power cables, etc. • stretchable, vandalism proof fire blocking interliners

In the process of figure 6, the coating with the silicone elastomer is advantageously carried out substantially just after the treatment of the basalt fabric with the primer composition. For example, the silicone elastomer coating is carried out less than 30minutes, advantageously less than 15 minutes, most preferably less than 5 minutes after the end of the treatment of the basalt fabric with the primer composition.

Claims

What I claim is :

1. Product comprising at least a stmcture made of at least:

- yams containing basalt fibers,

- a metallic reinforcing element, whereby said yams and reinforcing element are linked together, whereby the metallic reinforcing element is adapted for ensuring a resistance to cuts and tears, in a cutting or tearing direction, advantageously preventing tears and/or cuts, by means of a cardboard box cutter, said cutter being pushed into the stmcture and with application of a force in said cutting direction of more than 300 N, advantageously of more than 500 N, preferably of more than 600 N , and whereby said stmcture is at least provided with a coating layer covering at least partly the yams containing basalt fibers, said coating being selected from the group consisting of polyester containing coating, polyurethane containing coating, silicone containing coating and mixture thereof, whereby the coated yams containing basalt fibers are selected so as to ensure a flammability of Ml or M0 according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702- 3 : 1994 and NF X 70-100 : 1986 for said yams.

2. The product of claim 1, which comprises : - a fabric made at least of yams containing at least basalt fibers, preferably basalt continuous filament fibers, said fabric having a weight comprised between 70 g/m² and 4000 g/m² ;

- advantageously a primer coating at least partly said yams or fibers ;

- at least a coating layer selected from the group consisting of polyester containing coating, polyurethane containing coating, silicone containing coating and mixture thereof, said layer coating at least partly a face of the fabric advantageously provided with a primer coating, said coating layer having a dry weight comprised between 20 and 500 g/m², advantageously between 40 and 400 g/m², preferably between 50 and 200 g/m², said weight being calculated on basis of the weight of polyester, polyurethane and silicone present in said coating layer.

3. The product of claim 1 or 2, in which the fabric containing basalt fibers and coated with at least a coating layer is adapted for providing a fire resistance with a flammability of Ml or M0 according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 .

4. The product of claim 1 or 2, in which the fabric containing basalt fibers and coated with at least a coating layer is adapted for providing a fire resistance with a flammability of M0 according to the norm NF P 92-503 : 1995, NF P 92-507 :

1997 and a smoke generation of F0 according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 .

5. The product of anyone of the preceding claims, in which the complete stmcture has a flammability of Ml or M0, preferably M0, according to the norm NF P 92-

503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0, preferably F0, according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70-100 : 1986 .

6. The product of anyone of the preceding claims, in which the binding means for linking the basalt containing fabric and the metallic reinforcing element has a flammability of Ml or M0, preferably M0, according to the norm NF P 92-503 : 1995, NF P 92-507 : 1997 and a smoke generation of FI or F0, preferably F0, according to the norm NF X 10-702-1 : 1995; NF X 10-702-3 : 1994 and NF X 70- 100 : 1986

7. The product of claim 1 or 2, characterized in that the coating layer on the basalt fibers or yams has an abrasion resistance of more than 10,000 cycles, advantageously more than 20,000 cycles, preferably more than 25,000 cycles, according to the Martindale test BS 5690; 1991.

8. The product of claim 1 or 2, characterized in that the coating layer on the basalt fibers or yams has an abrasion resistance of more than 40,000 cycles, preferably more than 50,000 cycles, according to the Martindale test BS 5690; 1991.

9. Product of anyone of the preceding claims, characterized in that the basalt fiber comprises at least 43%) by weight of SiO₂, advantageously more than 46%, preferably more than 50%> by weight SiO₂.

10. Product of anyone of the claims 1 to 9, characterized in that the portion of the face of the fabric coated with a coating layer has a coating weight distribution such that for each cm² of the portion of the coated fabric, the weight of coating layer varies between 60% and 250% of the average coating weight, advantageously between 70% and 150%, preferably between 80% and 130%.

11. Product according to anyone of the preceding claims, characterized in that the yams comprise at least 50% by weight, advantageously more than 85% by weight, preferably more than 95%> by weight of basalt fibers.

12. Product according to anyone of the preceding claims, characterized in that the two opposite faces of the fabric are coated with a primer layer and with a coating layer.

13. Product according to anyone of the preceding claims, characterized in that the layer coating a face of the fabric has a maximum coating weight of 100g/m², advantageously a coating weight lower than 80g/m².

14. Product according to anyone of the preceding claims, characterized in that the basalt fibers comprises continuous basalt filaments having a diameter comprised between 5 μm and 25 μm, preferably between 7μm and 24μm, and in that the yams have a weight comprised between 50 and 4000 tex, advantageously comprised between 100 and 2500tex, preferably lower than 500 tex.

15. Product according to anyone of the preceding claims, characterized in that at least a portion of the basalt containing fabric, especially a face of the basalt containing fabric coated with the coating layer is provided with one or more further layers.

16. Product according to anyone of the preceding claims, characterized in that the portion of the fabric coated with a coating layer has a porosity made of pores of less than 50μm, advantageously of less than 25μm, preferably of less than lOμm.

17. Product according to anyone of the preceding claims, characterized in that at least a portion of a coating layer comprises at least one or more compounds selected from the group consisting of luminescent compounds, fluorescent compounds, phosphorescent compounds, pigments, metallic pigments, coloring pigments, biocide and mixtures thereof.

18. Product of anyone of the preceding claims, characterized in that at least a face of the coated fabric is associated with a heat insulating layer.

19. The product of anyone of the preceding claims, characterized in that the primer coating of the basalt containing yams and/or metallic reinforcing element is a layer obtained from one or more silane esters.

20. The product of anyone of the preceding claims, characterized in that the primer has a dry weight comprised between 10 and 200 g/m²

21. The product of anyone of the preceding claims, characterized in that it comprises a basalt containing fabric coated with an elastomer silicone containing coating.

22. The product of claim 21, characterized in that the silicone elastomer has a density after curing of at least 1.3, a shore A hardness of at least 45, and an acidity index of more than 30.

23. The product according to claim 21 or 22, characterized in that the silicone elastomer coating layer comprises at least 50% by weight of silicone elastomer, advantageously at least 75%, preferably at least 85%>.

24. The product of anyone of the preceding claims, which comprises at least 3 layers which are connected the one with the other, a first layer and a second layer being each a basalt containing fabric as disclosed in anyone of the preceding claims, while an intermediate layer is a metallic reinforcing element adapted for ensuring a resistance to cuts and tears in a cutting or tearing direction, advantageously preventing tears and/or cuts, by means of a cardboard box cutter, said cutter being pushed into the stmcture and with application of a force in said cutting direction of more than 300 N, advantageously of more than 500 N, preferably of more than 600 N

25. Element comprising at least a product according to anyone of the preceding claims, in which advantageously at least a portion of the product is sewn with another portion of the product or with another product of anyone of the preceding claims or with another fabrics or layer or sheet.

26. A process for the preparation of a product according to anyone of the claims 1 to 25, characterized in that a basalt containing fabric is advantageously coated at least partly with a primer composition, whereby the fabric coated with the primer composition is overcoated with an aqueous dispersion of polyester and/or polyurethane and/or silicone elastomer, said aqueous dispersion containing at least 10%) by weight of compound selected from the group consisting of polyester, polyurethane, silicone elastomer and mixture thereof, advantageously from 20 to 70%) by weight, preferably from 30 to 50% by weight of said compound, whereby before and/or after the coating with an aqueous dispersion containing the compound, the basalt containing fabric is provided with a metallic reinforcement or comprises a metallic reinforcement.

27. Use of a product according to anyone of the claims 1 to 25, as fire protection layer.

28. Fire protection clothes, fingers, boots, mittens, gloves, cowls, helmets,interliners, truck tarpaulins, car soft covers, electrical cables, telecommunication cables comprising at least a product of anyone of the claims 1 to 25.

29. Mattress provided with at least a product of anyone of the claims 1 to 25.