EP0484480A1 - Agent de protection incendie et son utilisation - Google Patents

Agent de protection incendie et son utilisation

Info

Publication number
EP0484480A1
EP0484480A1 EP91908524A EP91908524A EP0484480A1 EP 0484480 A1 EP0484480 A1 EP 0484480A1 EP 91908524 A EP91908524 A EP 91908524A EP 91908524 A EP91908524 A EP 91908524A EP 0484480 A1 EP0484480 A1 EP 0484480A1
Authority
EP
European Patent Office
Prior art keywords
fire protection
protection agent
agent according
parts
fire
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Withdrawn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
EP91908524A
Other languages
German (de)
English (en)
Inventor
Heinz Balle
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.)
BIOCHEMTEC HOLDING S.A.
Original Assignee
BIOCHEMTEC HOLDING SA
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 BIOCHEMTEC HOLDING SA filed Critical BIOCHEMTEC HOLDING SA
Publication of EP0484480A1 publication Critical patent/EP0484480A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

Definitions

  • Fire protection agents are used: trwenc_3.-u.rier
  • the present invention relates to a fire protection agent and its use.
  • Fire protection is of increasing importance due to the constantly increasing number of artificial, industrially manufactured raw materials and products.
  • many plastics have excellent technical properties in many disciplines and are also much more interesting in terms of price than any natural alternative materials.
  • they cannot be used in many obvious areas of application because they often fail to meet the relevant fire protection regulations.
  • Various fire protection agents are known which aim to reduce the flammability of raw materials or products or at least to eliminate their most dangerous properties, in particular their most dangerous reactants, from fires that actually occur.
  • Known possibilities for the flame-retardant finishing of polyurethanes are, for example, the use of radioactive compounds, mostly chlorinated and phosphorized polyols, which react with the isocyanate.
  • the flame retardant is a component of the synthetic resin.
  • non-reactive flame retardants namely compounds which contain liquid halogens and phosphorus.
  • PUR foams trimizing the isocyanate to the isocyanurate (PIR foams) can do a good job Fire behavior can be achieved.
  • PUR flexible foams are increasingly protected by post-impregnation with appropriately equipped dispersions.
  • the object is achieved by a fire protection agent which contains at least one dehydrating agent.
  • the fire protection agent according to the invention can also contain other components, in particular a carbohydrate or a starch as a binder.
  • other components in particular a carbohydrate or a starch as a binder.
  • it also proves to be advantageous if it still contains aluminum hydroxide.
  • the following is a compilation or a list with the generic terms of 6 possible main components and their sub-terms, which, taking into account the minimum requirement that at least one dehydrating agent must be present, can theoretically be combined completely freely into a fire protection agent according to the invention.
  • the fire protection agent according to the invention is generally applied by adding it to the substance or product itself and by subsequent treatment of a raw material, semi-finished product or finished product by impregnation.
  • the impregnation can be carried out, for example, by means of an immersion process or by spraying or brushing on the fire protection agent.
  • the specific composition of the fire protection agent can be varied.
  • a fire protection agent composed according to the invention can be added to any raw material as filler and this can then be processed as usual with the effect that the raw material treated in this way ultimately leads to a product that no longer burns can.
  • the respective exact composition depends on the raw material or product to be treated and on the type of application, for example on whether the fire protection agent is added directly to the raw material to be treated or whether a finished product is subsequently treated with impregnation with the fire protection agent .
  • the most outstanding advantages of the fire protection agent according to the invention are as follows:
  • foams according to DIN 4102, class B1 can be produced without problems.
  • the bulk density of a plastic foam is increased by admixing the fire protection agent according to the invention.
  • the fire protection agent according to the invention has better values with regard to arcing strength, hardness, weather resistance and impact resistance.
  • the admixture of the fire protection agent according to the invention improves the rheology, that is to say the flow behavior of a plastic.
  • the fire protection agent according to the invention Due to its polar character, the fire protection agent according to the invention is easily dispersible in water. 10. As a result of its physical and chemical properties, a high filler content (up to 1000 per hundred resin [phr]) of fire protection agents according to the invention is permissible, which means that a correspondingly high level of flame protection can be achieved.
  • the fire protection agent according to the invention is environmentally friendly since it is halogen-free and therefore non-toxic.
  • the fire protection agent according to the invention is also interesting in terms of price, since its cost is approximately half that for the common raw materials for foams.
  • the fire protection agent advantageously consists of a mixture of a dehydrating agent, binder, propellant, and a stabilizing agent.
  • the dehydrating agent used is urea, a known compound of carbon, nitrogen, hydrogen and oxygen, but also a phosphate salt, for example Monophosphoric acid, Monoammnoiu hydrogen phosphate, Diammnoium hydrogenphosphate or urea phosphate used.
  • a phosphate salt for example Monophosphoric acid, Monoammnoiu hydrogen phosphate, Diammnoium hydrogenphosphate or urea phosphate used.
  • boric acid aluminum hydroxides or, for example, aluminum sulfate 18 hydrate according to German Pharmacopoeia 7.
  • Carbohydrates such as monosaccharides, disaccharides or polysaccharides or starches can be used as binders.
  • Melamine and ammonium hydrogen carbonate can be used as blowing agents, while tripentaerytrite, pentaerytrite or a borate is suitable as stabilizing agent.
  • a fire protection agent composed in this way forms a foam and is advantageously added to the stock solution in a proportion of about 30 percent by weight.
  • the fire protection agent can in principle easily make up to 230 percent by weight, based on the weight of the stock solution.
  • the foaming of the stock solution with the added fire protection agent to the end product must take place below the reaction temperature of the fire protection agent, typically at temperatures between 150 ° C. and 200 ° C.
  • the pores are closed, as a result of which the oxygen supply to the foamed substance is closed interrupted and as such is flame retardant.
  • An afterglow in the event of a fire is also no longer possible, since the resulting insulation layer prevents the fire from entering the fabric and prevents the supply of oxygen.
  • the mixtures of the fire retardant advantageously consist of aluminum hydroxide parts, carbohydrates, namely saccharides or another starch, melamines, ammonium hydrogen carbonates, water, di-ammonium hydrogen phosphate with a few parts of the finished product which is to be produced as a fire-protected product.
  • the foam-forming additive consists of two binders, namely aluminum hydroxide parts with starch or saccharides, and a blowing agent, especially ammonium hydrogen phosphate, supported by melamine.
  • starch can be modified anionically and cationically.
  • the production of molded ceramic fiber parts can be cited as an example of the use of a cationic starch.
  • the cationic starch functions multifunctionally as a flocculant, retention agent and binder.
  • the temperature load in drying systems is so high in some starch-bound products that particularly thermostable special starches have to be used. Binders are possible in many variations. Therefore, starch binders can also be adapted to a wide variety of conditions. Starches are used in low-water systems with, for example, low water consumption, low water retention, low gelatinization point, but high binding capacity and high temperature and color stability. Native and modified maize and wheat starches meet these requirements.
  • system binders which are matched in their composition to the various requirement profiles of a wide variety of products and process technologies.
  • System binders achieve the best operating results because they enable maximum binding strength with a minimum amount of use due to various mechanisms of action such as gradual gelatinization, minimal water consumption and low drying energy, partial migration (sandwich effect) and, with a cationic property of high fiber affinity.
  • the above-mentioned selection criteria allow the optimum starch binder for the most varied of production processes to be selected in the fire protection agent according to the invention.
  • UF UF
  • PF resols and novolaks phenolic resins
  • MF melamine resins
  • the resin solution is mixed with an approximately 40% starch suspension for use as a binder for the production of particle board, laminated board, stone and glass fiber boards. Diluted to the usual application concentration and applied to the substrate, the starch breaks down in the subsequent oven drying, becomes film-forming and condenses with the synthetic resin to form a homogeneous film. This film shows up to an exchange rate of approx.
  • the fire protection agent itself is referred to below as filler type ANTIFIRE 601. It consists, among other things, of aluminum oxide, which was broken down from the raw material bauxite with sodium hydroxide solution and then mixed with carbohydrates and starches develops the fire-protective effect.
  • Standard polyether polyol branched polyether modified with ethylene oxide 100 parts 100 parts water 3.5 parts 3.5 parts
  • Tin II catalyst 0.19 parts 0.19 parts Dabco 33 LV foaming catalyst 0.12 parts 0.12 parts polysiloxane stabilizer 0.8 parts fire retardant (ANTIFIRE 601) 20-30 parts Cl and P-containing polyol (13, 5% P; 20% Cl) 20 parts toluenediisocyanate (TDI) 44.2 parts 44.2 parts
  • Adding ANTIFIRE 601 as a filler increases the viscosity. However, this increase in viscosity can be significantly reduced by adding special additives, for example dimethyl methylphonophonate (DMMP).
  • DMMP dimethyl methylphonophonate
  • Another method for the flame-retardant treatment of open-cell PUR calibration foams is the subsequent treatment in aqueous binders containing the fire retardant.
  • This method avoids the problems of handling higher-viscosity polyol dispersions, but only protects the material up to a penetration depth of approx. 10 to 20 mm and makes the use of special machines necessary.
  • the binder When the fire retardant is used, the binder must not be dried and crosslinked at temperatures above 200 ° C., since otherwise the hydroxide will already thermally decompose and the flame retardant effect will be reduced. Crosslinking the binder significantly increases the flame retardancy that can be achieved.
  • the mechanical properties of the foam can be changed in accordance with the binder and the thickness of the application.
  • the impregnation agents used must ensure good wetting of the foam.
  • the soaking depth can be increased by up to a few centimeters.
  • PUR foam of class B1 according to DIN 4102 can be achieved without problems if polychloroprene latexes are used for the impregnation.
  • the latex is cross-linked using the usual methods (S, ZnO, MgO).
  • S, ZnO, MgO The addition of a wetting agent for better dispersion is recommended.
  • a foam equipped in this way is particularly suitable, for example, for upholstery material.
  • a recipe that brings good mechanical properties with very good flame resistance is, for example, as follows:
  • ANTIFIRE 601 50th parts sb 2 or 3 7 parts
  • the bulk density is 50 to 60 kg / m, the tensile strength 80 to 90 kPa, the elongation about 110% with a tensile strength of approx. 200 N / m.
  • Tolylene diisocyanate-methylene diphenyl diisocyanate mixture 45 parts
  • This foam has an oxygen index of approx. 30% 0 according to MVSS 30 and the best flame protection imaginable. Since processing with normal high-pressure machines is limited to a viscosity of approximately 3 to 3.5 Pas (Pascal seconds), processing with filler machines must be carried out for higher viscosities. NEN done. With this formulation, there is little separation of the polyol after 24 hours of standing. However, there is no hard sediment. The viscosity can be further reduced by adding suitable additives.
  • the following recipe is suitable for the production of insulating foams, which can be used, for example, as impact protection walls in sports halls:
  • a monium polyphosphate 15 parts
  • This foam complies with the DIN 4102, class B1 and has
  • ANTIFIRE 601 can also be easily processed with polyurethane glue.
  • suitable formulations for the respective area of application have to be processed, since the adhesives have to meet certain standards not only in combination with other materials.
  • the adhesives have to meet certain standards not only in combination with other materials.
  • it is also a question of its thickness and the equipment of the materials to be joined.
  • Polyurethanes for fabric coatings have the advantage of better mechanical properties than the commonly used PVC. Difficulties caused by plasticizer migration cannot occur with this material. In the event of a fire, there are no corrosive gases.
  • One-component solvents containing solvents such as polyurethane, lacquers and two-component coatings can also be made flame-resistant with ANTIFIRE 601.
  • An important area of application for this is, for example, the waterproof coating and the flame protection of fine-pored PUR foams.
  • additional flame retardants such as Cl and Br-containing compounds, including the addition of PVC powder, may be required.
  • the formulations can be varied in accordance with the foam in order to achieve an optimal bond. These materials point a high weather resistance and are therefore suitable for outdoor applications such as for roof PUR casting compounds, for cable fittings, for casting components etc. In addition, they are characterized by high volume resistances and high heat resistance.
  • ANTIFIRE 601 For outdoor insulators, good weather resistance is obtained when using cycloaliphatic polyurethanes, which, unlike EP resins, are resistant to hydrolysis.
  • ANTIFIRE 601 lends these materials good arc and tracking current resistance, as well as good high-voltage arc resistance and a corresponding dielectric strength.
  • ANTIFIRE 601 is superior to all other fillers.
  • silanized products When using silanized products, the good bond results in better resistance to water storage and thus an improvement in the dielectric strength in the creep test. Since usually very high concentrations of fillers (approx. 70% of the total amount) are used, it is advisable to use a mixture of three components which gives an optimum in terms of viscosity and sedimentation behavior.
  • a mixture of 400 parts of ANITFIRE consisting of 3 components is advantageous.
  • viscosities of approx. 70 Pas are achieved in cycloaliphatics with the mixture standing for 60 hours without sedimentation.
  • the filler is predried here, with the addition of zeolite paste, stirred into the isocyanate and the polyol is added as the hardener.
  • a recipe consists of, for example
  • ANTIFIRE 601 components 300 parts achieve the following values, for example:
  • aluminum hydroxide (A1 2 0 3 ) can additionally increase the hardness, the flexural strength and the impact strength.
  • the following recipe notes can be given in tabular form for the flame-resistant finishing of rigid polyurethane foams.
  • the filler component like all other additives, is added to the polyol.
  • TMBDA Termethylene butanidiamine
  • ANTIFIRE 601 methyl methylphonate (DMMP) X, Y parts
  • DMMP Dirnethyol methylphophonate
  • ANTIFIRE 601 is a well-suited synergist to ANTIFIRE 601.
  • ANTIFIRE 601 is preferably only added to the polyol component.
  • Each addition of filler causes an increase in the viscosity of the polyol a good reduction in smoke density is achieved in the event of a fire using ANTIFIRE 601.
  • the flame-retardant equipment of ANTIFIRE 601 is based, among other things, on the fact that a protective layer of char products protects the plastic from further decomposition, it works best in the systems with polyurethanes , which is characterized by a pronounced carbonization behavior favor the formation of a closed protective layer.
  • Polyol and ANTIFIRE 601 can be mixed using a high-shear mixer or kneader.
  • the change in the reaction times when adding fillings is of great importance for the processing.
  • the start time generally remains the same, while the tack-free time and the rise time are increased by approximately 20% when 50 parts of ANTIFIRE 601 on polyurethane are added.
  • the density of the foam increases due to the higher density of the filler, namely with ANTIFIRE 601 with 37 phr by 1 to 5 times.
  • the reaction times the pore structure is also changed to a small extent.
  • the density is related to polyol depending on the ANTIFIRE 601 concentration.
  • the thermal conductivity of rigid PU foams is the most important criterion for use in the construction sector. When up to 100 parts of ANTIFIRE 601 are added, the thermal conductivity changes only slightly with respect to PUR.
  • the pressure test of rigid foams shows one with increasing ANTIFIRE 601 content
  • the modulus of elasticity [N / mm] can be increased by adding DMMP, which is called
  • Foam with modified polyols and ANTIFIRE 601 can be used, or
  • Hydrophilic foam with a very high content of ANTIFIRE 601 is used.
  • these are polyols (PHD) with polyurea dispersions, which form a solid crust during the fire and do not drip.
  • PLD polyols
  • ANTIFIRE 601 By adding about 70 to 120 parts of ANTIFIRE 601, this tendency towards crust formation is significantly increased and a foam results, in which there is no fire behavior.
  • Approx. 7% Cl and 7% P can be added as an additive.
  • a foam which is based on the reaction of a polymer.
  • ANTIFIRE 601 can achieve 55% oxygen indices.
  • the filler is added to the isocyanate.
  • the mechanical properties can be varied over a wide range by varying the additives.
  • a further application of the fire protection means according to the invention consists in the flame-retardant treatment of wood, textiles, papers and cardboards, but also carpets, foils, cellulose, cellulose and similar products.
  • the fire protection agent consists of twists and turns of at least one phosphate salt as a dehydrating agent and at least one carbohydrate as a binder, and optionally of borates and is used as an impregnating agent for the aftertreatment.
  • urea monophosphoric acid as a dehydrating agent, a polysaccharide or a wax malt starch as a binding agent, and borax as a stabilizing agent.
  • Diammonium hydrogen phosphate and boric acid as a dehydrating agent and a polysaccharide or another carbohydrate as a binder.
  • Such a fire protection agent according to the invention is hereinafter referred to as ANTIFIRE 501.
  • ANTIFIRE 501 By decomposing the ANTIFIRE 501 fire retardant at temperatures above its reaction temperature creates inert gases that prevent the entry of oxygen. Furthermore, the flame-retardant property of the treated substance is achieved in that its flammable materials undergo dehydration at the high fire temperatures.
  • the materials treated with the fire protection agent ANTIFIRE 501 according to the invention therefore do not burn or ' immediately extinguish themselves after the ignition flame has been removed. Even afterglow is not possible since no oxygen can get to the material.
  • the fabrics are treated with the fire protection agent ANTIFIRE 501 by spraying them on the fabric or by immersing the fabric in the fire protection agent ANTIFIRE 501 and soaking it.
  • the flame-retardant active substance content is determined quantitatively after the treated material has dried by determining its weight gain. Because the material experiences almost no handle influence during the treatment, the fire protection agent ANTIFIRE 501 according to the invention can also be used in the cellulose and cellulose industry. The binder added to the fire protection agent achieves a high level of compatibility with many substances.
  • the fire protection agent according to the invention is distinguished by precisely defined quality properties such as high purity, constant distribution, low water content, low electrolyte content and a defined specific surface.
  • Especially surface-treating ANTIFIRE 501 types allow easy dosing and incorporation.
  • ANTIFIRE improve the processing, especially the rheology (flow behavior) and have a positive effect on the mechanical properties of the end products.
  • special aluminum hydroxides can be used as coating pigments and fillers in the cardboard and paper industry.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Fireproofing Substances (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

Un agent de protection contre des incendies contient au moins un déshydratant. De préférence, il contient en outre au moins un glucide ou un amidon en tant que liant. On utilise par exemple comme déshydratant des sels de phosphate, de l'urée, de l'acide borique et des hydroxydes d'aluminium, alors qu'on utilise comme liants des glucides ou des amidons.
EP91908524A 1990-04-26 1991-04-26 Agent de protection incendie et son utilisation Withdrawn EP0484480A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH1434/90 1990-04-26
CH143490 1990-04-26

Publications (1)

Publication Number Publication Date
EP0484480A1 true EP0484480A1 (fr) 1992-05-13

Family

ID=4210374

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91908524A Withdrawn EP0484480A1 (fr) 1990-04-26 1991-04-26 Agent de protection incendie et son utilisation

Country Status (6)

Country Link
EP (1) EP0484480A1 (fr)
KR (1) KR920702715A (fr)
AU (1) AU7657291A (fr)
CA (1) CA2062756A1 (fr)
DE (1) DE4190848D2 (fr)
WO (1) WO1991016403A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08165468A (ja) * 1994-12-12 1996-06-25 Erika Balle 防火物質及び防火物質の製造方法及び防火物質を付着する方法
AT405409B (de) * 1996-02-23 1999-08-25 Baumgartner Johannes Feuerbeständiges stoffgemenge
DE19748210B4 (de) * 1997-10-31 2005-09-01 Südzucker AG Mannheim/Ochsenfurt Polyurethane mit Kohlenhydratbausteinen
DE102012204238B4 (de) 2012-03-16 2017-06-08 Technische Universität Dresden Verwendung wasserlöslicher stickstoff- und phosphorhaltiger Polysaccharidderivate als Flammschutzmittel, Holzverbundwerkstoff mit verbesserten Flammschutzeigenschaften sowie Verfahren zu dessen Herstellung

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2078805A (en) * 1980-06-27 1982-01-13 Tba Industrial Products Ltd Fire and Weld Splash Resistant for Glass Fabric
DE3024738A1 (de) * 1980-06-30 1982-10-21 Raspik Ltd., Ir Ganim, Kiryat-Ata Hitze- und feuerschutzmaterial sowie ein verfahren zu dessen herstellung
DE3545001A1 (de) * 1985-01-16 1986-07-17 Avenir-Wärmedämmplatten Dipl.-Ing. Peter Steyer, 3436 Hessisch Lichtenau Aus naturprodukten hergestellte waermedaemmplatte
DE3729867C1 (de) * 1987-09-05 1989-03-23 Flachglas Ag Verfahren zur Herstellung einer Brandschutzmasse und nach dem Verfahren hergestellte randschutzmasse
DE3730204A1 (de) * 1987-09-09 1989-03-30 Bayer Ag Brandschutzmittel
US4764539A (en) * 1987-11-24 1988-08-16 Norton Company Flame resistant polymers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9116403A1 *

Also Published As

Publication number Publication date
KR920702715A (ko) 1992-10-06
WO1991016403A1 (fr) 1991-10-31
CA2062756A1 (fr) 1991-10-27
AU7657291A (en) 1991-11-11
DE4190848D2 (de) 1994-04-28

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