EP1300506A2 - Textiles Substrat mit verbesserter Feuerbeständigkeit - Google Patents

Textiles Substrat mit verbesserter Feuerbeständigkeit Download PDF

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Publication number
EP1300506A2
EP1300506A2 EP02370038A EP02370038A EP1300506A2 EP 1300506 A2 EP1300506 A2 EP 1300506A2 EP 02370038 A EP02370038 A EP 02370038A EP 02370038 A EP02370038 A EP 02370038A EP 1300506 A2 EP1300506 A2 EP 1300506A2
Authority
EP
European Patent Office
Prior art keywords
aluminum hydroxide
substrate according
retardant coating
flame
polymeric binder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02370038A
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English (en)
French (fr)
Other versions
EP1300506A3 (de
Inventor
Carole Annick Myriam Magniez
René Delobel
Franck Poutch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centre De Recherche Et D'etude Pour Les Procedes D'ignifugation Des Materiaux
Institut Francais Textile et Habillement
Original Assignee
Centre De Recherche Et D'etude Pour Les Procedes D'ignifugation Des Materiaux
Institut Francais Textile et Habillement
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Centre De Recherche Et D'etude Pour Les Procedes D'ignifugation Des Materiaux, Institut Francais Textile et Habillement filed Critical Centre De Recherche Et D'etude Pour Les Procedes D'ignifugation Des Materiaux
Publication of EP1300506A2 publication Critical patent/EP1300506A2/de
Publication of EP1300506A3 publication Critical patent/EP1300506A3/de
Withdrawn legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/72—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with metaphosphoric acids or their salts; with polyphosphoric acids or their salts; with perphosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Definitions

  • the present invention relates to a textile substrate, formed from synthetic yarns or fibers and having a flame retardant coating comprising agents developing an intumescent structure, intended to provide said substrate with improved performance as to its resistance to heat and fire.
  • WO 98/22555 relates to a flame-retardant composition applicable to a substrate, including a textile structure.
  • This flame-retardant composition includes a polymeric binder and an intumescent agent which is consisting at least of an acid source agent and of a source agent of carbon (polyhydric carbon compound).
  • the acid must be able to dehydrate the polyol. This dehydration should not have place only from a certain temperature or in the presence of a flame, this is why the acid salts are preferably used.
  • the release of acid should take place below the temperature of decomposition of polyhydric material.
  • the relative effectiveness of the different acids will depend on the strength of the acid character. Acid salts most often used are compounds which have a volatile cation, so that the acid can be released in areas of temperature close to the ignition temperature of the material.
  • the carbonaceous polyhydric compound is generally a compound chosen from different classes of carbohydrates and which has a quantity relatively high carbon and many hydroxile sites.
  • the carbonaceous polyhydric compound has the function of developing, in combination with the strong thermodegradable acidic compound, one layer alveolar carbonaceous, capable of forming, when the substrate is subjected to a heat source, a shield for protecting said substrate. It is the principle of indirect fireproofing.
  • the strong acid compound thermodegradable is preferably chosen from the group consisting in phosphoric acids, boric acids, or a salt of these the latter having a volatile cation and in particular polyphosphate ammonium.
  • the carbon-containing polyhydric compound it is same document of a starch or polyhydric alcohol and more preferably pentaerythritol.
  • the relatively high amount of carbon and hydroxile sites contained by said agents promotes the formation of a large alveolar or expanded carbon layer. This are the gases released by the reaction of the strong acid compound thermodegradable with the polyhydric carbon compound which allow the expansion of the carbon layer.
  • the polymeric binder As regards the polymeric binder, according to document WO 98/22555, its choice is not limited to a particular polymer, as long as it fulfills the function of binder of the flame-retardant composition. However, when the polymeric binder is a polyurethane or an acrylic polymer, it necessarily add a fire retardant adjuvant, in particular an inorganic phosphorus compound.
  • the composition flame retardant of the aforementioned document consists of 35 to 45% by weight an acrylic polymer, from 15 to 35% of ammonium polyphosphate, 10 to 15% pentaerythritol and 10 to 30% a flame retardant adjuvant which can be an alumina hydroxide or an organophosphorus compound, this adjuvant always being different and distinct from the constituent compounds the intumescent agent and in particular of the strong acid compound thermally degradable.
  • a flame retardant composition comprising a binder fraction with a binder polymer and an intumescent composition, allowing to keep or improve the properties of the intumescent agent without altering the basic properties of the binding fraction, for example its thermosolvency and / or its resistance to moisture uptake so as to ability to apply to substrates such as textile structures including technical fabrics and obtaining fire resistance improved of these substrates.
  • substrates can be either threads of mineral or organic material, of natural origin or synthetic or textile structures, woven, non-woven or knitted fabrics, of the technical fabric type used for example to make blinds, curtains and the like.
  • the aim that the applicants have set themselves is to propose a textile substrate having improved performance in terms of resistance to heat and fire thanks to a special intumescent system.
  • the textile substrate of the invention which, in known manner, includes a flame retardant coating, which comprises a polymeric binder and an intumescent composition.
  • the coating flame retardant further comprises a small amount of at least one synergy, chosen from aluminum hydroxide, magnesium, bauhemite, titanium oxide, sodium silicate, zeolites, low melting point glass, clay nanoparticles, borosilicate product, nanocomposites of polyamide, polypropylene and polyester so to obtain, under the action of a heat source, a double layer carbonaceous, namely a uniform thin layer on the surface and a layer alveolar in depth.
  • synergy chosen from aluminum hydroxide, magnesium, bauhemite, titanium oxide, sodium silicate, zeolites, low melting point glass, clay nanoparticles, borosilicate product, nanocomposites of polyamide, polypropylene and polyester so to obtain, under the action of a heat source, a double layer carbonaceous, namely a uniform thin layer on the surface and a layer alveolar in depth.
  • the quantity of synergy, implemented, according to the present invention is in quantity reduced, for example between 0.2 and 3% by weight relative to the polymeric binder. This amount is so small that the improvement in performance cannot be explained by the water release caused by the degradation of this synergistic agent.
  • the synergistic agent containing a metal atom an X-ray analysis of the elements constituting the carbon layer following the thermal degradation of the sample showed a very high concentration of the metal at level of the uniform surface thin layer, which strengthens the cohesion of the intumescent system.
  • the synergistic agent in small quantities allows to lead to a ceramic structure on the surface of the carbon layer.
  • the hydroxide alumina or aluminum, titanium oxide, sodium silicate, zeolites, low melting point glasses, clay nanoparticles, borosilicate product, polyamide nanocomposites, polypropylene and polyester acting as a ceramising agent improve the mechanical properties of the carbonaceous residue, while the charges minerals play the role of cement by improving the cohesion of the layer carbon.
  • the textile substrate is formed from polypropylene yarns or fibers or polyester.
  • polyamide is not at all suitable with the use of an acrylic polymer as a polymeric binder.
  • the intumescent composition includes an ammonium polyphosphate as the acid salt.
  • the overall preferred proportion of ammonium polyphosphate and the synergistic agent relative to the polymeric binder is between 10 and 20%, the percentage of 15% being an optimum compromise in terms of outcome and cost.
  • the proportion by weight of the flame retardant coating by relative to the entire textile substrate it can be between 20 and 70%, a proportion of the order of 40% being preferred.
  • the present invention will be better understood on reading the description of several exemplary embodiments of a nonwoven based on polypropylene fibers and polyester fibers and a coating flame retardant based on an acrylic polymer binder, polyphosphate ammonium as the acid salt of the intumescent composition and a reduced amount of at least one synergistic agent.
  • the textile substrate which one seeks to improve the fire resistance is formed of threads or fibers. He can therefore be a woven, knitted or non-woven article. In the examples given below, it is, preferably but not exclusively, a nonwoven, for example needled as used in floor coverings.
  • the threads or fibers are made of a synthetic material which is hot-melt that is to say that it melts from a certain temperature then degrades under the effect of heat. Preferably it is son or polypropylene or polyester fibers.
  • the textile substrate has a flame retardant coating, which is composed of a polymeric binder, which acts as a carbon source agent, and an intumescent composition containing at least one acid salt, coating which is applied to the nonwoven while it is under the form of a paste, being applied for example to the doctor blade.
  • a flame retardant coating which is composed of a polymeric binder, which acts as a carbon source agent, and an intumescent composition containing at least one acid salt, coating which is applied to the nonwoven while it is under the form of a paste, being applied for example to the doctor blade.
  • the paste intended to form this coating is prepared under the following conditions.
  • Anti-foaming agent is optionally added, then a thickening agent to obtain the flame retardant composition comprising acrylic resin and poly ammonium phosphate in the form of a paste, which is applied with a doctor blade on one side of the nonwoven, which is then dried in an oven or an oven at a temperature of the order of 120 ° C., in order to obtain the crosslinking or polymerization of the resin.
  • the amount of paste applied on the textile substrate is determined according to the proportion by weight flame retardant coating with respect to the entire textile substrate. This proportion can be between 20 and 70%. However for applications such as floor coverings or items of furniture, this proportion is preferably of the order of 40%.
  • the proportion of acid salt relative to the polymeric binder is between 10 and 20%, preferably of the order 15%.
  • the 15% percentage is an optimum compromise in term of result and cost.
  • the performance in terms of improvement of the fire retardancy properties of two nonwovens was tested, one formed from polypropylene fibers and the other from polyester fibers, both comprising a flame retardant coating without synergistic agent. .
  • it is the fireproofing coating which forms a shield intended to protect the textile material.
  • To assess the fire resistance provided by the flame retardant coating it is checked whether the presence of this coating decreases the heat flow released when the textile substrate is subjected to an incident radiant heat flux of a value of 30 kW / m 2 .
  • the samples are arranged horizontally; the textile substrate is exposed directly to the heating resistance of a calorimeter cone.
  • the calorimeter cone tests are carried out according to ASTME 1354-90 or ISO 5660.
  • the polypropylene nonwoven web releases a heat flow of 230kw / m 2 when it is uncoated and a heat flow of 165kw / m 2 when it has a flame retardant coating of the order 40%.
  • the polyester nonwoven web of the order of 450 g / m 2 , uncoated releases a heat flow rate of 285kw / m 2 and the same sheet coated with flame retardant coating releases a heat flow rate of 153kw / m 2 .
  • the presence of the flame retardant coating, composed of acrylic binder and ammonium polyphosphate, without synergistic agent, proves to be quite effective in terms of flow reduction calorific, more particularly when the textile substrate is composed of polyester yarns or fibers, for which the reduction in heat flow is close to 50%, being close to 30% for yarns or fibers polypropylene.
  • Figures 1 and 2 illustrate this development of the heat flow as a function of time for the coated nonwoven (A), for the non-coated nonwoven (B) and also for the coating alone (C), being a polyester nonwoven (1) for FIG. 1 and a nonwoven polypropylene (2) for Figure 2.
  • the flame retardant coating composed of a binder of acrylic polymer and ammonium polyphosphate, without synergistic agent, makes it possible to reduce the normal calorific flow of a nonwoven nonwoven coated with polyester (B1) and polypropylene (B2) fibers, subjected to an incident radiant heat flux of a value of 30kw / m 2 .
  • the ignition of the polyester coated nonwoven (A1) is early compared to the uncoated nonwoven (B1). This characteristic is specific to the implementation of an intumescent system. The applicants wish to emphasize that this early ignition time leads to the rapid formation of the carbon layer of the intumescent system, which has the advantage of rapidly limiting heat transfers.
  • the ignition time should not, however, be too fast. It is preferable that it remains longer than 20 seconds.
  • the above test was carried out using a flame retardant coating composed exclusively, as main components, of a polymer type A acrylic as a polymer and polyphosphate binder ammonium as the acid salt.
  • the addition to the polymeric binder of a low amount of a synergistic agent increases the performance of the textile substrate of the invention in terms of resistance to heat and fire.
  • This synergistic agent in small proportions, preferably understood between 0.2 and 3% by weight relative to the polymeric binder, is chosen from aluminum hydroxide, magnesium hydroxide, titanium oxide, sodium silicate, zeolites, low melting point glass, nanoparticles clay, borosilicate product, polyamide nanocomposites, polypropylene and polyester so as to obtain, under the action of a heat source, a carbonaceous double layer, namely a uniform thin layer on the surface and a deep alveolar layer.
  • the X-ray analysis of the elements constituting the layer carbonaceous following the degradation of the sample makes it possible to note a concentration of metal in the thin layer on the surface of the sample, when the synergist contains a metal atom.
  • the fire performances were assessed by measuring two parameters, namely on the one hand the maximum heat flow values and on the other hand the ignition time, obtained during the combustion of the coating films according to the different formulations using uses type A acrylic resin, acid salt and each of the mineral fillers. The results are obtained in Table 1 below.
  • the next part of the study consisted in analyzing the influence of mineral charges on the morphology of the intumescent structure. This has was carried out using a scanning electron microscope. The examined samples were obtained by degrading the coating films under an oxidizing atmosphere, for 15 minutes at 400 ° C, temperature of formation of the intumescent structure when using a resin type A acrylic as a polymeric binder.
  • Ammonium polyphosphate associations and respectively bauhemite, aluminum hydroxide, titanium oxide, sodium silicate allow to slow down the degradation rate of the systems. In presence of type A acrylic resin, they lead to the formation of an expanded cellular structure, associated with a ceramization of area.
  • said mineral charges have a certain capacity to form bridges between the chains of ammonium polyphosphate, thus forming complexes promoting the formation of a stable alveolar system.
  • the next part of the study consisted in assessing the influence of mineral charges on the fire behavior of the coated textile substrate.
  • This part of the study was carried out with a non-woven fabric substrate polypropylene whose flame retardant coating is composed of type A acrylic resin as polymer binder, polyphosphate ammonium as the acid salt.
  • Three formulations were selected for flame retardant coating, with 2% mineral filler respectively aluminum hydroxide, zinc borate and titanium oxide.
  • Table 2 presents the fire performance of the different samples tested in terms of ignition time and heat flow.
  • the last column of the table indicates the morphology of the intumescent structure.
  • % APP % of mineral charges % fiber Minimum ignition time Heat output Morphology of the intumescent structure 12% 60% 30 seconds 210 kw.m -2 10% 2% aluminum hydroxide 59% 35 seconds 165 kw.m -2 Cellular system, surface glass 10% 2% zinc borate 58% 29 seconds 250 kw.m- 2 Unexpanded system 10% 2% titanium oxide 61% 31 seconds 180 kw.m -2 Compact, low-expansion honeycomb system
  • Table 3 below groups together the fire performances of the samples tested as a function of the particle size of the aluminum hydroxide, in a flame-retardant coating composed of 85% of acrylic resin of type A, of 13% of ammonium polyphosphate. and 2% aluminum hydroxide. It appears from this comparison for a particle size of 45 and 12 ⁇ m respectively that it has an impact both on the minimum ignition time or ignition time and on the heat flow rate. To facilitate the representation of the results, the evolution of the energy acceleration rate as a function of the time of these samples was also measured (FIG. 4). It is found that the presence of aluminum hydroxide leads to an increase in the ignition time and a decrease in the speed of energy acceleration.
  • Table 4 groups the fire performances of the samples according to the proportion of aluminum hydroxide relative to the acid salt; respectively 1, 2 and 5% of aluminum hydroxide replacing the 15% of ammonium polyphosphate. It is found that the formulation which has the best fire performance contains from 1 to 2% of aluminum hydroxide, 13 to 14% of acid salt and 85% of acrylic resin of type A.
  • Ceramization is at the origin of the limitation of the diffusion of gases flammable to the flame and diffusion of oxygen to the material.
  • the presence of concentrated aluminum on the surface strengthens the cohesion of the alveolar system.
  • Table 5 shows that the use of 2% sodium silicate is more efficient than 2% aluminum hydroxide in terms of heat flow rate for a type B acrylic resin.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Fireproofing Substances (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Laminated Bodies (AREA)
EP02370038A 2001-10-02 2002-10-02 Textiles Substrat mit verbesserter Feuerbeständigkeit Withdrawn EP1300506A3 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0112674A FR2830268B1 (fr) 2001-10-02 2001-10-02 Substrat textile a resistance au feu amelioree
FR0112674 2001-10-02

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EP1300506A2 true EP1300506A2 (de) 2003-04-09
EP1300506A3 EP1300506A3 (de) 2003-10-01

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007048547A1 (de) * 2005-10-28 2007-05-03 Fibertex A/S Material mit oder bestehend aus fasern und nanoclay
ITMO20110259A1 (it) * 2011-10-13 2013-04-14 Chih-Hwa Kuo Materiale ritardante di fiamma

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114958123A (zh) * 2022-05-10 2022-08-30 单俊昊 一种水性生物基膨胀阻燃隔热材料

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0460516A2 (de) * 1990-05-29 1991-12-11 Albright & Wilson Limited Beschichtungszusammensetzung und -verfahren
WO1998022555A1 (fr) * 1996-11-19 1998-05-28 Chavanoz Industrie Composition ignifugeante sans halogene, fil ignifuge avec celle-ci, et structure textile ignifuge comportant de tels fils
US6150448A (en) * 1997-12-18 2000-11-21 Kyowa Kabushiki Kaisha Flame retardant for mesh sheets and flameproof mesh sheet including the same
US6248160B1 (en) * 1997-07-18 2001-06-19 Kyowa Kabushikikaisha Flame retardant for mesh sheets and flameproof mesh sheet

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0460516A2 (de) * 1990-05-29 1991-12-11 Albright & Wilson Limited Beschichtungszusammensetzung und -verfahren
WO1998022555A1 (fr) * 1996-11-19 1998-05-28 Chavanoz Industrie Composition ignifugeante sans halogene, fil ignifuge avec celle-ci, et structure textile ignifuge comportant de tels fils
US6248160B1 (en) * 1997-07-18 2001-06-19 Kyowa Kabushikikaisha Flame retardant for mesh sheets and flameproof mesh sheet
US6150448A (en) * 1997-12-18 2000-11-21 Kyowa Kabushiki Kaisha Flame retardant for mesh sheets and flameproof mesh sheet including the same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007048547A1 (de) * 2005-10-28 2007-05-03 Fibertex A/S Material mit oder bestehend aus fasern und nanoclay
ITMO20110259A1 (it) * 2011-10-13 2013-04-14 Chih-Hwa Kuo Materiale ritardante di fiamma

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Publication number Publication date
FR2830268A1 (fr) 2003-04-04
EP1300506A3 (de) 2003-10-01
FR2830268B1 (fr) 2005-02-25

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