DE19718876A1 - Flame and heat resistant barrier consisting of flame resistant cellulosic - Google Patents
Flame and heat resistant barrier consisting of flame resistant cellulosicInfo
- Publication number
- DE19718876A1 DE19718876A1 DE19718876A DE19718876A DE19718876A1 DE 19718876 A1 DE19718876 A1 DE 19718876A1 DE 19718876 A DE19718876 A DE 19718876A DE 19718876 A DE19718876 A DE 19718876A DE 19718876 A1 DE19718876 A1 DE 19718876A1
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- Prior art keywords
- flame
- fibers
- thermal barriers
- fire
- textile
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04B—GENERAL BUILDING CONSTRUCTIONS; WALLS, e.g. PARTITIONS; ROOFS; FLOORS; CEILINGS; INSULATION OR OTHER PROTECTION OF BUILDINGS
- E04B1/00—Constructions in general; Structures which are not restricted either to walls, e.g. partitions, or floors or ceilings or roofs
- E04B1/62—Insulation or other protection; Elements or use of specified material therefor
- E04B1/92—Protection against other undesired influences or dangers
- E04B1/94—Protection against other undesired influences or dangers against fire
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/24—Coatings containing organic materials
- C03C25/26—Macromolecular compounds or prepolymers
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
- C03C25/10—Coating
- C03C25/42—Coatings containing inorganic materials
- C03C25/44—Carbon, e.g. graphite
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/06—Organic materials
- C09K21/12—Organic materials containing phosphorus
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- 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
- D06M11/73—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 carbon or compounds thereof
- D06M11/74—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 carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
- D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
- D06M13/288—Phosphonic or phosphonous acids or derivatives thereof
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- 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
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
- D06M13/44—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen containing nitrogen and phosphorus
- D06M13/453—Phosphates or phosphites containing nitrogen atoms
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- 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
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- 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
- D06M15/327—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof
- D06M15/333—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated alcohols or esters thereof of vinyl acetate; Polyvinylalcohol
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- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/39—Aldehyde resins; Ketone resins; Polyacetals
- D06M15/423—Amino-aldehyde resins
- D06M15/43—Amino-aldehyde resins modified by phosphorus compounds
- D06M15/432—Amino-aldehyde resins modified by phosphorus compounds by phosphonic acids or derivatives 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
- 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
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
-
- 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
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
- D06M23/04—Processes in which the treating agent is applied in the form of a foam
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/0056—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the compounding ingredients of the macro-molecular coating
- D06N3/0063—Inorganic compounding ingredients, e.g. metals, carbon fibres, Na2CO3, metal layers; Post-treatment with inorganic compounds
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Architecture (AREA)
- General Life Sciences & Earth Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Electromagnetism (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Physics & Mathematics (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Laminated Bodies (AREA)
- Fireproofing Substances (AREA)
Abstract
Description
Thermisch expandierbare Brandschutzmassen bzw. Brandschutzlaminate, die Blähgraphit und polymere Substanzen neben anderen Bestandteilen enthalten, sind bereits vorbeschrieben.Thermally expandable fire protection compounds or fire protection laminates, the expanded graphite and contain polymeric substances in addition to other components have already been described.
Die meisten dieser Anmeldungen, wie z. B. EP-B 9109, EP-A 338347, die DE 41 35 678 und EP 338347, setzen Blähgraphit mit Polymeren ein, die selbst flammhemmend sind und unter Verwendung von Additiven, wie z. B. parakristalline Kohlenstoffgerüst bildende Substanzen, eine thermisch expandierbare Brandschutzmasse ergeben.Most of these applications, such as B. EP-B 9109, EP-A 338347, DE 41 35 678 and EP 338347, use expandable graphite with polymers that are themselves flame retardant and under Use of additives, such as. B. paracrystalline carbon-forming substances, a result in thermally expandable fire protection compound.
EP 338347 bringt die erfindungsgemäße Brandschutzmasse durch Rakeln auf Trägerbahnen, wie Folien oder Vliese, die mit Deckschichten z. B. aus PVC, Papier oder Aluminiumblechen ein- oder beidseitig abgedeckt werden können.EP 338347 brings the fire protection composition according to the invention by knife coating onto carrier webs, such as Films or nonwovens that are covered with cover layers such. B. from PVC, paper or aluminum sheets can be covered on both sides.
Das Prinzip der beschriebenen Brandschutzmassen liegt in der Expandierfähigkeit, speziell des Blähgraphits, die als Intumeszenz bezeichnet wird.The principle of the fire protection materials described is the expandability, especially the Expandable graphite, which is called intumescence.
Die meisten Anmeldungen, so z. B. DT-OS 40 07 075, beschränken die Intumeszenz auf Formteile, die im wesentlichen Blähgraphit enthalten.Most registrations, e.g. B. DT-OS 40 07 075, restrict intumescence to molded parts, which essentially contain expanded graphite.
Nicht beschrieben werden Feuer- und Thermosperren, bei denen Textilien als Trägermaterialien für Blähgraphit wirken.Fire and thermal barriers in which textiles are used as carrier materials are not described act for expandable graphite.
Zwar weist die erwähnte DT-OS 40 07 075 auf Trägermaterialien aus Blech, Holz, Keramik oder textile Gebilde hin, bei denen durch einseitiges, doppelseitiges oder partielles Aufbringen eine Sandwichplatte entstehen kann, jedoch werden als textile Gebilde, Glasvliese, Glasgewebe oder Polyaramid-Gewebe eingesetzt.The mentioned DT-OS 40 07 075 refers to carrier materials made of sheet metal, wood, ceramic or textile structures, where one-sided, double-sided or partial application one Sandwich panel can arise, however, as a textile structure, glass fleece, or glass fabric Polyaramid fabric used.
Die vorliegende Erfindung beansprucht dagegen textile Feuer- und Thermosperren, beinhaltend Blähgraphit und Bindersysteme, bei denen als Trägermaterialien vorab flammfest ausgerüstete native Fasern auf cellulosischer Basis zur Anwendung kommen.The present invention, however, claims including textile fire and thermal barriers Expandable graphite and binder systems in which flame-retardant materials were previously used as carrier materials native cellulosic fibers are used.
Die vorbeschriebenen Trägermaterialien z. B. auf Polyaramidbasis sind zwar selbst teilflammhemmend, bei Beflammungszeiten von über 30 Minuten, die im Brandfall sehr häufig sind, schmilzt jedoch das Trägermaterial auf Synthesefaserbasis weg, tropft ab, so daß der Intumeszenzträger durch das gebildete Brandloch weg bricht.The carrier materials described above z. B. based on polyaramide are themselves partially flame retardant, with flame exposure times of over 30 minutes, which is very common in the event of fire are, however, the carrier material based on synthetic fibers melts, drips off, so that the Intumescent carrier breaks through the fire hole formed.
Überraschenderweise wurde gefunden, daß native Trägermaterialien auf Basis Cellulose (Baumwolle, Viskose usw.), nach Flammfestausrüstung mit üblichen salzartigen oder permanenten Flammfestmitteln in Verbindung mit Blähgraphit und flammfesten Bindemitteln (Polymeren, Latices), hervorragende Feuer- und Thermosperren ergeben, die Langzeitbeflammungen von über 30 Minuten bis zu Stunden standhalten.Surprisingly, it was found that native carrier materials based on cellulose (Cotton, viscose etc.), after flame retardant treatment with common salt-like or permanent flame retardants in connection with expandable graphite and flame retardant binders (Polymers, latices), excellent fire and thermal barriers that result Withstand long-term flames of over 30 minutes to hours.
Als Grundlage für die erfindungsgemäßen Thermo- und Feuersperren dienen textile Flächengebilde, aus Geweben, Maschenwaren, non-woven (Vliesen oder Filzen), die flammfest ausgerüstet sind, wobei als salzartige Flammfestmittel die üblichen Ammonphosphate oder -sulfate, Borate oder ähnliche Produkte eingesetzt werden.Textiles serve as the basis for the thermal and fire barriers according to the invention Flat structures, made of fabrics, knitwear, non-woven (nonwovens or felt) that are flame-retardant are equipped, the usual ammonium phosphates or as salt-like flame retardants -sulfates, borates or similar products are used.
Als permanente Flammfestmittel zur Vorbehandlung cellulosischer Fasern können Produkte wie APO, Trisaziridinylphosphat oder N-Methylolphosphonate des Typs ®Pyrovatex CP oder andere eingesetzt werden. Products like. Can be used as permanent flame retardants for the pretreatment of cellulosic fibers APO, trisaziridinyl phosphate or N-methylolphosphonate of the type ®Pyrovatex CP or others be used.
Erfindungsgemäß werden die vorab flammfest ausgerüsteten Trägermaterialien mit einer Mischung aus Blähgraphit, polymeren Bindern und Flammfestadditiven beschichtet und bei Temperaturen von über 100°C ausgehärtet.According to the invention, the previously flame-retardant carrier materials are provided with a Mixture of expanded graphite, polymeric binders and flame retardant additives coated and Cured at temperatures above 100 ° C.
Die eingesetzten Blähgraphitmaterialien enthalten expandierbare Moleküle in den Zwischengitterebenen und expandieren (blähen) beim Erhitzen auf Temperaturen von über 150°C. Es werden Graphite verwendet, in die beispielsweise Salpetersäure, Schwefelsäure und/oder andere starke Säuren eingelagert sind. Die Herstellung derartiger Blähgraphite wird beschrieben in der GB-PS 1497118.The expanded graphite materials used contain expandable molecules in the Intermediate grid levels and expand (expand) when heated to temperatures above 150 ° C. Graphites are used, in which, for example, nitric acid, sulfuric acid and / or other strong acids are stored. The production of such expandable graphites is described in GB-PS 1497118.
Als polymere Binder werden halogenfreie Polymere auf Basis Acrylsäureester, PVAc, PUR, Latex u. a. eingesetzt.Halogen-free polymers based on acrylic acid esters, PVAc, PUR, latex are used as polymeric binders u. a. used.
Die in der DT-OS 41 35 678 bevorzugten Chloroprenkautschuke sind zwar flammhemmend, spalten jedoch im Brandfall hochtoxische AOX-Verbindungen ab.The chloroprene rubbers preferred in DT-OS 41 35 678 are flame retardant, split however, in the event of fire, highly toxic AOX compounds.
Die dort ebenfalls angeführten halogenfreien Binder auf Basis PVAc, Polyethylen oder Polyacrylat sind selbst brennbar und mindern, ohne den beanspruchten Zusatz von Flammfestmitteln, nicht das Brennverhalten bei Beanspruchungen von über 30 Minuten im Brandfall.The halogen-free binders based on PVAc, polyethylene or polyacrylate also listed there are flammable themselves and do not diminish without the claimed addition of flame retardants the burning behavior in case of fire for more than 30 minutes.
Erfindungsgemäß kommen somit, neben den flammfest ausgerüsteten Trägermaterialien auf nativer Basis und den Blähgraphiten, noch flammfest gemachte halogenfreie Bindersysteme zur Anwendung.According to the invention, in addition to the flame-retardant carrier materials native base and the expandable graphites, still flame-retardant halogen-free binder systems for Application.
Die Flammhemmung der Binder erfolgt vorzugsweise beim Herstellen der Kaschierung durch Zumischen organischer Phosphorverbindungen z. B. organischer tricyklischer Phosphonate zum Binder-Blähgraphitgemisch.The binder is preferably flame retarded when the lamination is manufactured Mixing organic phosphorus compounds such. B. organic tricyclic phosphonates Binder expandable graphite mixture.
Überraschenderweise ergibt das Aufbringen der Mischung Binder/Flammfestmittel/Blähgraphit und eventueller Zuschläge wie Verdicker, Schutzkolloide, Stabilisatoren, Netzmittel u. a. auf die flammfest präparierten textilen Trägermaterialien, die aus nativen Fasern bestehen, Thermo- und Feuersperren, die Beflammungen von über 1000°C über Zeiträume von 0,5-2 Stunden aushalten.Surprisingly, the application of the mixture results in binder / flame retardant / expandable graphite and possible supplements such as thickeners, protective colloids, stabilizers, wetting agents and the like. a. on the flame-retardant prepared textile carrier materials, which consist of native fibers, thermal and Fire barriers, the flames of over 1000 ° C for periods of 0.5-2 hours withstand.
Meßbar sind diese Thermosperr-Effekte durch Temperaturfühler, die auf der Seite, die der Flamme abgewendet ist, Temperaturen von unter 200°C anzeigen.These thermal blocking effects are measurable by temperature sensors on the side that the Flame is turned away, show temperatures below 200 ° C.
Überraschenderweise zeigen die erfindungsgemäß hergestellten Thermo- und Flammsperren keinerlei Kantenbrennbarkeit, sollten die Flammen nicht auf den Mittelpunkt der Trägermaterialien, sondern auf deren Kanten gerichtet werden.Surprisingly, the thermal and flame barriers produced according to the invention show no edge flammability, should the flames not be on the center of the substrate, but are aimed at their edges.
Die erfindungsgemäßen Systeme enthalten, bezogen auf das Trägermaterial, 10-150 Gew.-% vorzugsweise 20-60 Gew.-% Blähgraphit, bezogen auf Blähgraphit die in etwa gleichen Mengen an Binder (bezogen auf Feststoff), so daß das Verhältnis Blähgraphit/Binder 0,6 : 1 bzw. 1 : 0,6 vorzugsweise 0,8 : 1 bis 1 : 0,8 beträgt. The systems according to the invention contain, based on the carrier material, 10-150% by weight preferably 20-60 wt .-% expandable graphite, based on expandable graphite in about the same amounts on binder (based on solids), so that the ratio of expandable graphite / binder 0.6: 1 or 1: 0.6 is preferably 0.8: 1 to 1: 0.8.
Die vorab flammfest ausgerüsteten Trägermaterialien enthalten 10-30% an Flammfestprodukten Salzen etc, wie vorbeschrieben), der Binder wird im Unterschuß mit der organischen Phosphor verbindung (Phosphat- oder Phosphonat) mit 0,2-0,6: 1 Gewichtsteilen Phosphorderivat/Binder flammfest gemacht.The carrier materials, which have been previously flame-retardant, contain 10-30% of flame-retardant products Salts etc, as previously described), the binder is in deficit with the organic phosphorus compound (phosphate or phosphonate) with 0.2-0.6: 1 parts by weight of phosphorus derivative / binder made flame retardant.
In der Applikation empfiehlt es sich, den meist durch den Herstellprozeß sauer eingestellten Blähgraphit durch Zugabe von Alkali (NaOH, KOH, Ammoniak) auf Werte von über 9 zu stellen, um Verträglichkeitsprobleme mit den eingesetzten Bindersystemen zu vermeiden.In the application, it is advisable to set the acidic one, which is usually acidic due to the manufacturing process Expandable graphite by adding alkali (NaOH, KOH, ammonia) to values above 9, to avoid compatibility problems with the binder systems used.
Das gleiche Procedere gilt für die Flammfest-Inhibierung des Bindersystems mit den meist sauer eingestellten organischen Phosphorverbindungen, die ebenfalls auf einen pH-Wert von über 9 gebracht werden müssen.The same procedure applies to the flame retardant inhibition of the binder system with the mostly acidic one adjusted organic phosphorus compounds, which also have a pH of over 9 have to be brought.
Die Applikation in der Praxis enthält Beschichtungen auf einer Seite und beidseitige Laminate (Sandwich-Bildungen) durch Auftragen mit Rakeln, aber auch durch Schaumapplikation.The application in practice contains coatings on one side and laminates on both sides (Sandwich formation) by application with doctor blades, but also by foam application.
Letztere erfolgt durch übliche Schaumbildner, wie Aminoxiden, Alkansulfonaten u. a., die mit üblichen Schaumauftragsgeräten in Verbindung mit den erfindungsgemäß beanspruchten Mischungen appliziert werden.The latter is done by conventional foaming agents such as amine oxides, alkanesulfonates and the like. a. that with usual foam applicators in connection with the claimed according to the invention Mixtures can be applied.
Die erfindungsgemäß beanspruchten Textillaminate können besonders im Baubereich, z. B. als Innenschicht für Brandschutztüren oder für Deckenkonstruktionen Anwendung finden.The textile laminates claimed according to the invention can be used particularly in the construction sector, e.g. B. as Inner layer for fire doors or for ceiling constructions.
Vorteilhaft sind ihre geringen Gewichte und ihre Flexibilität. Die Flexibilität der textilen Träger erlaubt eine hohe Elastizität im Brandfalle. Sie neigen im eingespannten Zustand beim Beflammen weniger zum "Platzen", das durch den Blähdruck beim Expandieren des Blähgraphits verursacht wird.Their low weights and flexibility are advantageous. The flexibility of the textile carrier allows high elasticity in the event of fire. They tend to flame when clamped less about the "burst" caused by the expansion pressure when expanding the expansion graphite becomes.
Zur Applikation in der Praxis empfiehlt es sich, den Blähgraphit, der als feste, schuppenförmige Masse vorliegt, zu einer handhabbaren, gießbaren Masse vorzudispergieren.For application in practice it is recommended to use expandable graphite, which is a solid, scale-like Mass is present to pre-disperse into a manageable, pourable mass.
Rührt man Blähgraphit, der auf Grund seines Herstellprozesses mit pH-Werten von 1-5 (10%ig) anfällt, unter Zusatz von Alkali in Wasser, so setzt diese Dispersion schnell ab. Durch Zugabe von Schutzkolloiden, auf Basis gefällter Kieselsäuren, PVAI etc. gelingt es, stabile Dispersionen in Wasser zu erhalten, deren pH-Werte mit den vorher erwähnten Alkalimengen auf Werte von über 9 gebracht werden.If you stir expanded graphite, which due to its manufacturing process has pH values of 1-5 (10%) accumulates, with the addition of alkali in water, this dispersion settles quickly. By adding Protective colloids based on precipitated silicas, PVAI etc. succeed in stable dispersions in To get water whose pH values with the previously mentioned amounts of alkali to values of over 9 are brought.
Diese Vorabdispersion, enthaltend 40-60% Gewichtsprozent Blähgraphit, Schutzkolloid und Alkali, wird dann zur Herstellung der Laminierungsdispersion, die auf die flammfest ausgerüsteten, cellulosischen Gewebe, Gewirke, Gestricke, Filze oder Vliese, resp. Glasfasergewebe, -gewirke -gestricke oder -vliese aufgebracht wird, weiterverarbeitet.This preliminary dispersion, containing 40-60% by weight expanded graphite, protective colloid and Alkali, is then used to make the lamination dispersion, which is flame-retarded, cellulosic fabrics, knitted fabrics, knitted fabrics, felts or nonwovens, respectively. Glass fiber fabrics, knitted fabrics - knitted or nonwoven is applied, processed.
Dieser sogenannte Beschichtungscompound besteht aus der Blähgraphit-Vordispersion, dem Flammfestmittel für den Binder, dem Binder selbst und einem pH-Regulator, der das Gesamtsystem auf pH-Werte von über 9 bringt. This so-called coating compound consists of the expandable graphite predispersion, the Flame retardant for the binder, the binder itself and a pH regulator that does it Entire system brings to pH values of over 9.
Selbstverständlich kann der Beschichtungscompound auch direkt, durch Zusammenrühren von Blähgraphit, Binder, Flammfestmittel für den Binder und Alkali zum Einstellen des pH-Wertes von über 9, hergestellt werden. Durch Zugabe von Schutzkolloiden und/oder Verdickern wird die zum Rakeln, Kaschieren nötige Konsistenz des Beschichtungscompounds eingestellt.Of course, the coating compound can also be mixed directly by stirring Expandable graphite, binder, flame retardant for the binder and alkali for adjusting the pH of over 9. By adding protective colloids and / or thickeners, the Squeegees, lamination, necessary consistency of the coating compound set.
Zur Herstellung eines Beschichtungscompounds als Schaum kann entweder über eine Blähgraphit-Vorabdispersion oder durch direktes Zusammengeben der Einzelkomponenten unter Zugabe eines "Schaumgenerators" der Schaumauftrag erzielt werden.To produce a coating compound as a foam, either a Expandable graphite pre-dispersion or by directly combining the individual components below Adding a "foam generator" the foam application can be achieved.
Das Trocknen, Kaschieren, Beschichten der flammfesten cellulosischen Faser erfolgt in der Praxis meist in kontinuierlichen Prozessen, bei denen a) das aufgebrachte Wasser entfernt wird, und b) die Vorbindung zwischen Substrat und Binder, sowie Aushärtung der Bindersysteme erfolgt.Drying, laminating, coating the flame-retardant cellulosic fiber takes place in practice mostly in continuous processes, in which a) the applied water is removed, and b) the prebinding between substrate and binder, as well as curing of the binder systems takes place.
Im sogenannten Schock-Kondensations-Verfahren erfolgt dieser Prozeß in einer Stufe bei 140- 190°C, vorzugsweise 150-160°C bei 30-360 Sekunden, vorzugsweise 2-5 Minuten, wobei die kürzeren Zeiten höhere Temperaturen erfordern und umgekehrt.In the so-called shock condensation process, this process takes place in one step at 140- 190 ° C, preferably 150-160 ° C at 30-360 seconds, preferably 2-5 minutes, the shorter times require higher temperatures and vice versa.
Die Untergewebe (Maschenwaren usw.) aus cellulosischen Fasern haben qm-Gewichte von 100- 500 g.The sub-fabrics (knitted fabrics, etc.) made of cellulosic fibers have sqm weights of 100- 500 g.
Die Flammfestprüfungen gehen über die Normalbedinungen der DIN 4102 B2 Kantenbeflammung bzw. Flächenbeflammung nach der Baustoffklasse B2 weit hinaus.The flame retardant tests go beyond the normal conditions of DIN 4102 B2 edge flame treatment or surface flame treatment according to building material class B2.
Beide Prüfungen erfolgen für die Kantenbeflammung und Flächenbeflammung nach DIN 4102 B2 15 Sekunden.Both tests are carried out for edge and surface flame treatment in accordance with DIN 4102 B2 15 seconds.
Die erfindungsgemäß hergestellten Prüflinge werden im Falle der Flächenbeflammung nach B2 mindestens 15 Minuten, meist 1-2 Stunden beflammt, für die Kantenbeflammung werden in etwa 15 Minuten an Beflammung durchgeführt.The test specimens produced according to the invention are in the case of surface flame treatment according to B2 Flamed for at least 15 minutes, usually 1-2 hours, for the edge flaming are approximately 15 minutes of flame exposure.
Neben den eingesetzten Mengenverhältnissen an Blähgraphit, Binder, Flammfestverbindungen für den Binder spielen für die Intumeszenzwirkung der Gesamtsysteme die Totalauflagen auf den cellulosischen Fasern resp. Glasfasern eine entscheidende Rolle.In addition to the proportions of expanded graphite, binder, flame retardant used for for the intumescent effect of the total systems, the total play on the binder cellulosic fibers resp. Glass fibers play a crucial role.
Erfindungsgemäß werden optimale Flammschutz- und Thermosperr-Effekte erzielt, wenn auf das Untergewebe (Maschenware usw.) 100-500 g vorzugsweise 150-400 g an Gesamtbindersystem (Blähgraphit, Binder, Verdicker, Flammfestkomponente für Binder etc.) pro qm Gewebe (Maschenware, Vlies etc.) aufgebracht werden.According to the invention, optimum flame retardant and thermal barrier effects are achieved when the Lower fabric (knitwear, etc.) 100-500 g, preferably 150-400 g of total binder system (Expandable graphite, binder, thickener, flame-resistant component for binder etc.) per square meter of fabric (Knitwear, fleece, etc.) can be applied.
Im Falle des "Sandwich" wird auf das beschichtete Untergewebe das gleiche Gewebe aufkaschiert. Die angegebenen Werte beziehen sich dabei auf das Gesamtbindersystem als 100% Trockengewicht gerechnet. In the case of the "sandwich", the same fabric is applied to the coated lower fabric laminated. The values given relate to the overall binder system as 100% dry weight calculated.
1) Herstellung eines Blähgraphit-Compounds
49,52 Gew.-% Wasser
2,50 Gew.-% NaOH 38°Be
0,29 Gew.-% Fluortensid
4,34 Gew.-% Gefällte Kieselsäure (Schutzkolloid)
43,35 Gew.-% Blähgraphit.1) Production of an expandable graphite compound
49.52 wt% water
2.50 wt% NaOH 38 ° Be
0.29 wt% fluorosurfactant
4.34% by weight of precipitated silica (protective colloid)
43.35% by weight expanded graphite.
Nach Vorlage von Wasser, Natronlauge, Fluortensid und Kieselsäure wird der Blähgraphit 30 Minuten eingerührt. Erhalten wird eine gießfähige, schwarze Dispersion mit einem pH-Wert von ca. 9,5 und einem Feststoffgehalt von ca. 50%.After presentation of water, sodium hydroxide solution, fluorosurfactant and silica, the expanded graphite 30 Minutes stirred. A pourable, black dispersion with a pH of approx. 9.5 and a solids content of approx. 50%.
2) Herstellung eines Beschichtungscompounds als Paste
44% Blähgraphit-Compound nach 1) (ca. 50 Gew.-%)
45% Acrylatbinder - selbstvernetzend (ca. 60 Gew.-%)
10% Flammfestmittel (90 Gew.-% auf Basis cykl. Triphosphonat)
10% NH3 (25%ig)
x % Acrylatverdicker zum Einstellen der Viskosität.2) Herstellung eines Beschichtungscompounds als Paste
44% Blähgraphit-Compound nach 1) (ca. 50 Gew.-%)
45% Acrylatbinder - selbstvernetzend (ca. 60 Gew.-%)
10% Flammfestmittel (90 Gew.-% auf Basis cykl. Triphosphonat)
10% NH3 (25%ig)
x % Acrylatverdicker zum Einstellen der Viskosität.2) Preparation of a coating compound as a paste
44% expanded graphite compound after 1) (approx. 50% by weight)
45% acrylic binder - self-crosslinking (approx. 60% by weight)
10% flame retardant (90% by weight based on cyclic triphosphonate)
10% NH 3 (25%)
x% acrylic thickener to adjust the viscosity. 2) Production of a coating compound as a paste
44% expanded graphite compound after 1) (approx. 50% by weight)
45% acrylic binder - self-crosslinking (approx. 60% by weight)
10% flame retardant (90% by weight based on cyclic triphosphonate)
10% NH 3 (25%)
x% acrylic thickener for adjusting the viscosity.
3) Beschichtungscompound als Schaum
44 Gew.-% Blähgraphitcompound nach 1)
40 Gew.-% Binder wie bei 2)
10 Gew.-% Flammfestmittel wie bei 2)
1 Gew.-% NH3 (25%ig)
5 Gew.-% Schaumbildner auf Acrylatbasis.3) Coating compound as foam
44% by weight expandable graphite compound after 1)
40% by weight of binder as in 2)
10% by weight flame retardant as in 2)
1% by weight of NH 3 (25%)
5% by weight foaming agent based on acrylate.
4) Ein Bw-Gewebe mit 150 g/qm Gewicht wird auf einem Foulard mit 90% Abquetscheffekt mit einer Flotte von 300 g/l (60%igem) Ammonsulfamat behandelt und bei 100°C getrocknet. Auf dieses Gewebe wird die Paste nach Beispiel 2) aufgerakelt, so daß eine Gewichtsauflage (trocken) von 250 g/qm Gewebe erzielt wird.4) A Bw fabric with a weight of 150 g / qm is placed on a foulard with a 90% squeeze effect treated with a liquor of 300 g / l (60%) ammonium sulfamate and dried at 100 ° C. The paste according to Example 2) is knife-coated onto this fabric, so that a weight support is applied (dry) of 250 g / qm fabric is achieved.
Das behandelte Gewebe wird einmal als solches bzw. mit dem nach Beispiel 4) flammfesten Gewebe kaschiert ("Sandwich") und beide Systeme nach dem SKT-Verfahren bei 150°C 5 Minuten ausgehärtet.The treated fabric becomes flame-retardant as such or with that according to example 4) Fabric laminated ("sandwich") and both systems using the SKT process at 150 ° C Cured for 5 minutes.
Beide Systeme werden folgenden Prüfungen unterzogen:
Both systems are subjected to the following tests:
- a) Kantenbeflammung 15 Minuten nach DIN 4102 B2a) Edge flame treatment 15 minutes according to DIN 4102 B2
- b) Flächenbeflammung 1 Stunde nach DIN 4102 B2b) Surface flame treatment for 1 hour according to DIN 4102 B2
Ergebnis: Gewebe bleiben stabil, kein Entzünden, Intumeszenz.Result: tissues remain stable, no ignition, intumescence.
5) Spannt man einen nach 4) hergestellten Textilsandwich zwischen 2 je 4 mm dicke Holzrahmen, deckt eine Seite mit einer 2 mm starken Sperrholzplatte ab und beflammt diese Holz-Textil- Konstruktion in horizontaler Lage von der anderen Seite mit einem Bunsenbrenner (Flammtemperatur ca. 1100°C), so ist nach 1 Stunde die Sperrholzplatte noch nicht durchgebrannt. Die Temperatur steigt auf der nicht beflammten Sperrholzoberfläche nicht über 150°C (gemessen mit Thermofühler). 5) If a textile sandwich made according to 4) is stretched between 2 4 mm thick wooden frames, covers one side with a 2 mm thick plywood panel and flames this wood textile Construction in a horizontal position from the other side with a Bunsen burner (Flame temperature approx. 1100 ° C), the plywood board is not yet after 1 hour blown. The temperature does not rise on the non-flamed plywood surface 150 ° C (measured with a thermal sensor).
Ohne erfindungsgemäßen Textilverbundstoff ist die Sperrholzplatte bereits nach ca. 2 Min. durchgebrannt.Without the textile composite according to the invention, the plywood panel is already after about 2 minutes. blown.
6) Vergleichend wurde nach DT-OS 41 35 678 ein System nach Beispiel 3) hergestellt.6) For comparison, a system according to Example 3) was produced in accordance with DT-OS 41 35 678.
Die erhaltene Masse war nicht streichfähig, wenig elastisch und konnte nicht auf Gewebe aufgebracht werden.The mass obtained was not spreadable, not very elastic and could not be applied to tissue be applied.
Ein nach EP 338347 Beispiel 1) hergestelltes System, enthaltend Chloroprenlatex, entwickelte beim Beflammen erhebliche Mengen an AOX.A system produced according to EP 338347 Example 1) containing chloroprene latex was developed considerable amounts of AOX when flaming.
7) Eine Bw-Maschenware wird mit 300 g/l Ammoniumphosphat-Mischung (40%ig) am Foulard mit 100% Aufnahme behandelt und bei 110°C getrocknet.7) A BW knitted fabric is mixed with 300 g / l ammonium phosphate mixture (40%) on the padder Treated 100% and dried at 110 ° C.
Einseitig wird ein nach Beispiel 3) hergestellter flammfester Schaum, jedoch mit 5% Cokosdimethylaminoxid (30%ig) als Schaumgenerator, aufgebracht, 5 Minuten bei 140°C das System ausgehärtet und mit der Bw verschweißt.A flame-retardant foam produced according to Example 3) is used on one side, but with 5% Coconut dimethylamine oxide (30%) as a foam generator, applied for 5 minutes at 140 ° C System hardened and welded to the Bw.
Die Prüfung der Flammfest-Effekte nach Beispiel 4) ergab absolute Flammfestigkeit sowie einen hohen Thermosperreffekt.The examination of the flame retardant effects according to Example 4) showed absolute flame resistance as well a high thermal barrier effect.
8) Ähnliche Effekte werden erzielt, wenn der Blähgraphitcompound nach Beispiel 1) mit dem Schutzkolloid PVAI anstelle von gefällter Kieselsäure hergestellt wird.8) Similar effects are achieved if the expandable graphite compound according to Example 1) with the Protective colloid PVAI is produced instead of precipitated silica.
Keine Beeinträchtigung der Effekte ergeben sich, wenn im Beispiel 2) der Beschichtungscompound mit einem Latex oder PVAc-Dispersion oder PUR-Dispersion anstelle des selbstvernetzenden Acrylatbinder hergestellt wird.The effects are not impaired if in example 2) the Coating compound with a latex or PVAc dispersion or PUR dispersion instead of the self-crosslinking acrylic binder.
In ähnlicher Weise bewirkt ein Austausch der Flammfestkomponente cyklisches Triphosphonat im Beispiel 2) gegen Tris-(3-Chlorpropyl)-phosphat resp. Tris-(2-Chlorethyl)-phosphat keine Verschlechterung der Flamm- und Thermosperren.In a similar manner, an exchange of the flame-resistant component cyclic triphosphonate in Example 2) against tris (3-chloropropyl) phosphate or. Tris ( 2- chloroethyl) phosphate does not deteriorate the flame and thermal barriers.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19718876A DE19718876A1 (en) | 1997-05-03 | 1997-05-03 | Flame and heat resistant barrier consisting of flame resistant cellulosic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19718876A DE19718876A1 (en) | 1997-05-03 | 1997-05-03 | Flame and heat resistant barrier consisting of flame resistant cellulosic |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE19718876A1 true DE19718876A1 (en) | 1998-11-05 |
Family
ID=7828628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19718876A Withdrawn DE19718876A1 (en) | 1997-05-03 | 1997-05-03 | Flame and heat resistant barrier consisting of flame resistant cellulosic |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE19718876A1 (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1108375A2 (en) * | 1999-12-15 | 2001-06-20 | Texplorer GmbH | Garment, particularly undergarment for army and civil protection workers |
| EP1589157A1 (en) * | 2004-04-20 | 2005-10-26 | Felix Schuh & Co. GmbH | Joint between two construction parts |
| DE102004043193A1 (en) * | 2004-09-03 | 2006-03-30 | Hübner GmbH | Single- or multi-layer textile with a fireproof elastic coating on both sides and an interwoven lattice of heat- and-or flame-proof material, used for production of bellows structures, e.g. to connect articulated vehicles |
| WO2009055047A1 (en) * | 2007-10-24 | 2009-04-30 | Gore Enterprise Holdings, Inc. | Burn protective materials comprising expandable graphite |
| EP2107289A1 (en) * | 2008-04-02 | 2009-10-07 | Felix Schuh & Co. GmbH | Partition for a component feed-through |
| US8722145B2 (en) | 2007-10-24 | 2014-05-13 | W. L. Gore & Associates, Inc. | Thermally protective materials |
| WO2014116791A1 (en) * | 2013-01-23 | 2014-07-31 | Firestone Building Products Co., LLC | Coated fabrics including expandable graphite |
| WO2016077527A1 (en) | 2014-11-13 | 2016-05-19 | Hanwha Azdel, Inc. | Prepregs, cores and composite articles including expandable graphite materials |
| US9523203B2 (en) | 2013-01-23 | 2016-12-20 | Firestone Building Products Co., LLC | Fire-resistant roof system and membrane composite |
| DE202017003447U1 (en) | 2017-06-29 | 2017-08-02 | Rainer Casaretto | Textile multilayer structure of non-combustible, textile fiber structures in combination with mixtures of intumescent substances to create a heat and flame protection barrier |
| US10364527B2 (en) | 2007-10-24 | 2019-07-30 | W. L. Gore & Associates, Inc. | Burn protective materials |
| AT524924A1 (en) * | 2021-04-14 | 2022-10-15 | Guenter Url | Procedure for fire protection insulation or fire protection arrangement |
| EP4194522A1 (en) * | 2021-12-09 | 2023-06-14 | Rex Industrie-Produkte Graf von Rex GmbH | Insulating layer former, arrangement with an insulating layer former and wood element and use of an insulating layer former in wooden construction |
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| EP0009109B1 (en) * | 1978-09-26 | 1981-09-30 | Chemie Linz Aktiengesellschaft | Thermoexpandable sealing material for cracks, interstices or the like and process for sealing walls or doors in case of fire |
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|---|---|---|---|---|
| EP1108375A2 (en) * | 1999-12-15 | 2001-06-20 | Texplorer GmbH | Garment, particularly undergarment for army and civil protection workers |
| EP1108375A3 (en) * | 1999-12-15 | 2002-05-15 | Texplorer GmbH | Garment, particularly undergarment for army and civil protection workers |
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| DE102004043193B4 (en) * | 2004-09-03 | 2006-09-07 | Hübner GmbH | Single or multi-ply, preferably two-ply textile |
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| EP2679109A1 (en) * | 2007-10-24 | 2014-01-01 | Gore Enterprise Holdings, Inc. | Burn protective materials comprising expandable graphite |
| US10364527B2 (en) | 2007-10-24 | 2019-07-30 | W. L. Gore & Associates, Inc. | Burn protective materials |
| US8734905B2 (en) | 2007-10-24 | 2014-05-27 | W. L. Gore & Associates, Inc. | Thermally protective materials |
| US8753461B2 (en) | 2007-10-24 | 2014-06-17 | W. L. Gore & Associates, Inc. | Burn protective materials |
| WO2009055047A1 (en) * | 2007-10-24 | 2009-04-30 | Gore Enterprise Holdings, Inc. | Burn protective materials comprising expandable graphite |
| EP2107289A1 (en) * | 2008-04-02 | 2009-10-07 | Felix Schuh & Co. GmbH | Partition for a component feed-through |
| US11168479B2 (en) | 2013-01-23 | 2021-11-09 | Firestone Building Products Company, Llc | Fire-resistant roof system and membrane composite |
| WO2014116791A1 (en) * | 2013-01-23 | 2014-07-31 | Firestone Building Products Co., LLC | Coated fabrics including expandable graphite |
| US9523203B2 (en) | 2013-01-23 | 2016-12-20 | Firestone Building Products Co., LLC | Fire-resistant roof system and membrane composite |
| US12247399B2 (en) | 2013-01-23 | 2025-03-11 | Holcim Technology Ltd | Fire-resistant roof system and membrane composite |
| US12006691B2 (en) | 2013-01-23 | 2024-06-11 | Holcim Technology Ltd | Coated fabrics including expandable graphite |
| US10273693B2 (en) | 2013-01-23 | 2019-04-30 | Firestone Building Products Co., LLC | Coated fabrics including expandable graphite |
| JP2016511332A (en) * | 2013-01-23 | 2016-04-14 | ファイアストン ビルディング プロダクツ カンパニー エルエルシー | Coated cloth containing inflatable graphite |
| US10941573B2 (en) | 2013-01-23 | 2021-03-09 | Firestone Building Products Co., LLC | Coated fabrics including expandable graphite |
| EP3218119A4 (en) * | 2014-11-13 | 2018-06-20 | Hanwha Azdel, Inc. | Prepregs, cores and composite articles including expandable graphite materials |
| WO2016077527A1 (en) | 2014-11-13 | 2016-05-19 | Hanwha Azdel, Inc. | Prepregs, cores and composite articles including expandable graphite materials |
| DE202017003447U1 (en) | 2017-06-29 | 2017-08-02 | Rainer Casaretto | Textile multilayer structure of non-combustible, textile fiber structures in combination with mixtures of intumescent substances to create a heat and flame protection barrier |
| AT524924A1 (en) * | 2021-04-14 | 2022-10-15 | Guenter Url | Procedure for fire protection insulation or fire protection arrangement |
| AT17972U1 (en) * | 2021-04-14 | 2023-09-15 | Guenter Url | Procedure for fire protection insulation or fire protection arrangement |
| EP4194522A1 (en) * | 2021-12-09 | 2023-06-14 | Rex Industrie-Produkte Graf von Rex GmbH | Insulating layer former, arrangement with an insulating layer former and wood element and use of an insulating layer former in wooden construction |
| DE102021132538A1 (en) | 2021-12-09 | 2023-06-15 | Rex Industrie-Produkte Graf Von Rex Gmbh | Intumescent coating, arrangement with intumescent coating and wooden element and use of an intumescent coating in timber construction |
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