FR2486088A1 - FLAME RETARDANT FOAM GENERATOR COATING BASED ON EPOXIDE RESIN AND LAMINATED FIRE PROTECTIVE ELEMENT AND PROCESS FOR PRODUCING FIRE RETARDANT PROTECTIVE ELEMENTS - Google Patents

Abstract

THE INVENTION PROVIDES A FLAME RETARDANT ACTION BY A COATING BASED ON EPOXY RESIN WITH FOAM-GENERATING ADDITIONS AND POSSIBLY WITH FILLERS. THIS COATING IS CHARACTERIZED BY A WATER-EMULSIBLE EPOXIDE RESIN WHICH WITH A HARDENER IS USED AS A BINDER OF ADDITIONS AND FILLERS AND IT IS USED AS A LAMINATED ELEMENT WITH FIBROUS LAYERS 4 SEPARATING FROM THE GENERATOR LAYERS OF FOAM 5, THE ELEMENT BEING APPLIED ON A STRUCTURE TO BE PROTECTED 1 WITH COATING 2 AND BEING COVERED WITH A PROTECTIVE LAYER 6.

Description

The invention relates to a flame retardant coating product which generates

  foam based on epoxy resin with endothermic reaction additives, foam generators, giving off gases and / or breaking the chalnes of chemical composition and / or with fillers and it also relates to a laminated element protecting against fire, manufactured with use of such a product

coating.

  Products based on epoxy resin which, in addition to the epoxy resin, contain phosphoric acid compounds or nitrogen compounds or both and also optionally blowing agents such as

  starch or penta-erythritis are known per se.

  The function of flame retardant additives is to produce by heating a foam structure which acts as a thermal insulator, particularly if the foam structure is charred. If the additives contain more than 20 mole percent nitrogen and / or phosphorus, they decompose at temperatures of 100 to 400 G; and are in a proportion of 30 to 70% by weight, relative to the weight of the epoxy resin and the hardener, nitrogen gas and flame retardant phosphorus compounds are released under the action of the

  heat, so that protective coatings can be produced

  particularly favorable flame retardants. Such materials are known from the French patent application

  77.02876 published - under number 2 340 346.

  Other attempts to render.lg fug es ls

  materials & base of epoxy resins including additives

  tions of antimony compounds, phosphorus compounds, boron compounds, chlorine or bromine-releasing compounds, organic tin salts and calcium, cadmium, lead, magnesium and ammonium. It has appeared, however, that by the use of these bodies, alone or in combination, it is not possible to obtain sufficiently long protection against fire, in particular in buildings or other constructions exposed to fire. In particular, according to the German standard DIN 4102 with heat input, it is difficult to obtain protection of class F 50. These materials based on epoxy resins tear quickly superficially under the action of the

  heat from small fires and quickly forma-

  tion of deep cracks through which heat quickly reaches the body or the substrate which must be protected.

  A similar effect is already obtained by the addition of heat.

  It has been found that some epoxy resin emulsion-

  nables in water used as binders in suitable mixtures are able to retain water in combination

  relatively long and only give it up gradually-

  ment and that, when using such coatings on substrates, these coatings under the action of heat are at most divided into laminated layers which themselves have a fire-retardant action so that ultimately a very good long-term protection against the action of fire. This action is further improved if such coatings are used alternately with fibrous or fleece coatings and possibly with one or more layers of non-hydrophilic epoxy resins with the usual hardeners, hardening accelerators, gas-generating bodies and / or the

  fire resistant charges in suitable succession and 6ven-

  with an impermeable protective covering layer, for example made of polyurethane resin,

  polyacrylate resin or other coating resins

compatible with epoxy.

  The flame-retardant foam-generating coating product according to the invention based on epoxy of the type mentioned above is characterized according to the invention by Milk as a hydrophilic epoxy resin emulsifiable in water with a polyamine hardener and / or of polyamido-amine and / or a polycarbonate carbonic hardener and / or with dicyanamide serves as a binder for additives or bodies

dump.

  "5 Such hydrophilic epoxy resins are known from German patent application 27 26 269 but are only described therein as means protecting against corrosion and not as having fire protection properties as these emulsifiable binders in water, in particular in combination with also known bodies protecting against fire or delaying its action,

  give substrates, buildings, building materials

  tion or parts of other constructions exposed to fire. According to a preferred embodiment, one uses

  as a binder of an aqueous emulsion of hydro- epoxy resin

  phile and 1 to 40% by weight, of water (relative to the total weight). It is further preferred that the aqueous emulsion further contains organic emulsion stabilizers which are compatible with water and with the epoxy resin. The hydrophilic epoxy resin preferably contains -bisphenol A and / or bisphenol P. It is also preferred that the hydrophilic epoxy resin contains an epichlorohydrin with an epoxide equivalent between 175 and 210 and a di- or triglucidyl ether of diols or triols with 2 to

  carbon atoms and possibly 1 to 8 oxy-

  ether gene in a proportion of 75 to 95% by weight

  of binder for 25 to 5% of glucidyl ether. As hardened

  its amine is preferably used a derivative of a polyamine or of a polyamido-amine with at least two amino groups

and an epoxy bond.

  According to another preferred embodiment, the binder comprises a cycloaliphatic or aromatic carbon dioxide which, at temperatures between 100 and 250 C but

  even also up to 300 0C, reacts with epoxy resin.

  Such bodies are known as hardeners and include, for example, hexahydrophthalic anhydride, trimellitic anhydride and pyromellitic anhydride. In particular, the last two bodies react at temperatures between 160 and 290 OC with the usual epoxy resins and produce materials which are particularly resistant to heat.

  We still prefer to use as general additions

  foam or gas-forming additives which contain nitrogen, phosphorus, sulfur and / or bromine and which decompose at temperatures from 10 to 600 e0. Such bodies are for example melamine phosphate, melanin borate, guanidine phosphate, guanylurea, guanylurea phosphate, N-phenyl-N-cyclohexyl-pphenylenediamine, guanidine carbonate, benzosulfohydrazide and other compounds. We

  Particularly as the coating product contains

  contains 30 to 70% by weight of such substances, while the proportion of nitrogen and / or phosphorus amounts to more

  by 20 mole percent and that decomposition temperatures

  tion in the presence of at least two of these substances will spread

try at least 50 o0.

  In addition, according to a preferred embodiment, it is possible to add as a water-soluble foaming agent a condensing product of dicyandiamide phosphate and / or a silicate of dicyandiamido and / or guanidine in

  an epoxy resin coating product.

  If the coating medium still contains in addition to the binder a novolak resin in an amount of 10 to 40 parts% by weight (relative to the weight of the rine

  epoxy), partial fire stability values are obtained

  highly favorable, this effect being able to be further improved

  by the addition of blowing agents, such as silicones

  cates and / or water-soluble alkali metasilicates, aluminum phosphate, aluminum oxide tribhydrate and / or antimony trioxide. It is then possible with heat input to obtain values according to the German standard 4102 ranging up to F 90, which represents a value which cannot be obtained for the usual flame-retardant synthetic resins. This result is particularly confirmed if the binder contains resins modified by phenolic resins

or phenolic resins.

  Additionally, it is possible to add to the coating product according to the invention, as stabilizers and / or as other means giving off gases, pentaerythlite, melanin, tylose or dioxane as well as, for constructive parts which are particularly exposed. , glass fibers, gypsum, asbestos, graphite, boron, tungsten, steel or another material resistant to temperature increase. By such additions, the carbon framework resulting from the action of

fire is mechanically stabilized.

  According to another preferred embodiment, the coating product contains 1 to 30% by weight (relative to the total weight) of diphngyl-cresyl phosphate

  as a plasticizer and flame retardant.

  During the application of the coating, the coating product based on epoxy resin according to the invention is applied either as an emulsion on the body to be protected,

  either in the form of an independent carrier material applied

  later on the substrate or on the object to be protected against fire. In the combination of several layers we can obtain fire stabilities according to German standard 4102 up to 150 minutes (without heating) * As the coating product is chemically neutral and even resistant to the action of water , heat and cold, it can be used both inside and outside. The epoxy resin coating product according to the invention applies in particular to the protection of steel structures, aircraft hangars, tall buildings, bridges, refineries in the oil fields or on tube platforms and other structures or constructions exposed to fire. In addition, the product is also particularly suitable for the protection of wooden constructions and synthetic materials such as

ferries or ships.

  During implementation, the object to be protected is preferably first provided with a coating, depending on the object or the substrate receiving the protection, for example for the steel of an epoxy-based coating. . Then, the epoxy resin protection product according to the invention is applied in several layers by coating, with a roller or by spraying and in general, 2 to 3 layers of 900 g / m2 each already provide remarkable protection. The application thickness is only 1 to 2 mm, but by heating, the coating swells up to 20 cm. By the fact that between two layers is disposed each time a layer of mechanical separation in fibers or fleeces which are either in the form of fabric, or pulverized and are applied in the dry state or with the coating product in epoxy resin according to the Invention in a wet working operation, the carbon structure resulting from a fire can be stabilized. As fibers, we can

  use all fibers resistant to high temperatures

  tures which have been listed previously. We can however

  also use the swelling silicates mentioned above.

  demment and other metallic salts which can hydrate

  aluminum, lead, tin, boron, phosphorus.

  The use of aluminum phosphate or aluminum oxide trihbdrate or other products which strongly bind to water and yield it only at high temperature, such as zeolite and / or klieselguhr, is particularly favorable. It is the same for the use of organic pyrolytic materials yielding water which at the same time reinforce carbonization and / or activated carbon. The separating layers of hydratable substances give, under the action of fire, swollen layers which are stable due to the evaporation of the water contained in the epoxy resin material. In addition, they have a strong action

  endothermic, so that they cause cooling

of the interlayer.

  Optionally, on the two or three or more layers of the epoxy resin coating, a covering layer compatible with the epoxy can be applied, in particular a weather-resistant layer of polyurethane or an acrylate dispersion or a

other synthetic material.

  During the application, it is possible, in addition to the epoxy resin coating product according to the invention, to still use a usual epoxy resin material which does not hydrate, this material being used as second or third layer in combination with the coating means according to the invention. It is then also possible to use intermediate layers as mentioned above. In many cases it is not then necessary 7? apply a covering layer because the epoxy resin on the outside does not contain water and is

thus weather resistant.

  The invention also relates to a laminated fire protection element by using the coating product described while between two generating layers

  foam formed by the coating product is incorporated

  porée a layer of separation forming intermediate layer.

  A laminated fire protection element is already known from the German patent application 28 28 839; a layer of glass and polyester fibers is coated on both sides with a gel coating which, in addition to the polyester resin, contains still other fillers or additions, such as melanin, penta- erythbrite, potato starch and ammonium phosphate. It is also known to manufacture a laminated element using an epoxy resin which contains a polyamine as hardener. The use of reinforcing layers of glass is also known; such laminated fire protection elements are used especially for the protection of buildings or parts of buildings. For reinforcement, they contain glass or metal fibers. Their fire protection properties are however often insufficient to meet the

severe requirements.

  In addition, an epoxy resin emulsion composed of bisphenol A and / or bisphenol F liquid epoxy, of a reactive diluent based on d, is known for the protection against corrosion of parts of large-area steel buildings. '' a di- or triglucidyl ether and a hardener based on an amino adduct derived from a polyamine which contains at least two primary amino groups or a primary amino group and a secondary amino group and a bond epoxy (German patent application 27 26 269). The advantage of this means of protection against corrosion is that it can be applied directly to wet surfaces and has, in addition to good adhesion, a

  good corrosion protection action.

  A laminated fire protection element according to the invention must be improved so as to have remarkable fire protection properties despite a simple application and a simple shelter. We have to

  thus above all obtain protection against lou su-

  long enough for the parts of the construction exposed to -eu, bet which are the buildingsa in particular when salt n lae nore nore German protbection cont ie> u 4102 it is necessary to count with a contribution of heat. The drawbacks of such known protoetion ratiLies hitherto known which by the heat even in small homes tear on the surface, allowing a rapid passage of heat from the outside to the building part The invention further consists in the fact that these foam-generating layers at high temperatures which start to foam at high temperatures are separated by a separation layer forming an intermediate layer and are covered at least on one side by another separation layer. which in turn is covered with a covering layer. Separating layers include in particular glass fibers and an epoxy resin as binder. The foam generating layers should then include as a binder an epoxy resin which is cured by a

  hardener based on amine, by a hardener based on anhy-

  polycarbonic and / or dicyandiamide dride and comprise endothermic reaction additions forming foam, giving off gases and / or breaking chains of chemical compounds and / or fillers and the covering layer

  in epoxy and / or polyurethane.

  It has been found that this succession according to the invention of different partial layers of the laminated element

  Advantageously solves the problem stated above.

  Thus, by the fact that the foam generating layers proper are separated by intermediate layers or are covered at least on one side, the F 30 values of the fire stability according to the German standard 4102 are easily reached with heat input. . The formation of deep cracks sinking through the laminate element is pocketed and this not only by providing heating but also in the event of a fire. In addition to good mechanical properties, extraordinarily high fire stability values according to German standard 4102 can be achieved by increasing up to 160 minutes without heat input. Another advantage is that the laminated fire protection element can be used not only in indoor rooms, but also outside and that despite the action of water, heat and cold the good fire protection properties are not lost. So for a job outside, we would reach for the degree of stability at

  fire values Up to F 90 with heat input.

  The laminated element for fire protection according to the invention can be used especially for the protection of steel structures, aircraft hangars, high-rise houses, bridges, petroleum refineries or drilling rigs. The protection of parts of wooden and wooden constructions

  synthetic materials, including that of ships and trans-

  curlers is ensured despite a simple application.

  According to another embodiment of the invention, it is advantageous that the laminated element is joined to the

  part of the structure to be protected as a set of constructions

  tion; it is therefore advisable that the construction element

  tion be coated with a protective layer before its meeting

to the laminate element.

  The laminated element according to the invention provides good protection, that is to say that it opposes to the flames a good retarding action against radiant heat as well as convection heat; it establishes a stable closed envelope up to temperatures of about 1000 ° C; if this temperature is exceeded there is a collapse of the layer by a surprisingly slow peeling of the thin layers or elementary envelopes, that is to say that good protection of long duration is still ensured during the release of heat d '' a fire hearth, By using emulsions of phenolic epoxy-rezine, such as the resin Beckopox V: I 2t55 of Hoechst, for the protection against the corrosion and the reinforcement of the carbonization, one can obtain with contribution of heat values according to German standard 4102 up to r 90, which represents a value that cannot be achieved with flame retardant resins

usual.

  It is also possible to use mixtures based on general epoxy resins and if sle ve s

  mixtures based on non-emulsifiable flame retardant resins.

  In particular, good results are obtained with a laminated element of the type described lai, in which the separation layers and / or the foam-generating ouhs comprise materials, more particularly thermoplastic materials such as a product based on

nitrile acrylic and butadiene.

  We will now describe in more detail two particularly preferred embodiments of the laminated element according to the invention with reference to the appended drawing in which: FIG. 1 is a laminated fire protection element which is associated with a building element in wood; and FIG. 2 shows a variant which is associated with a part made of metal sheet forming the

support of the laminated element.

  According to Figure 1, the building element 1 forming a wooden beam is coated with a protective layer 2. On the protective layer 2 is worn an additional layer. 3 on which there is a separation layer 4 surmounted by a layer 5 of foam generator, then successively a separation layer 4, a second layer of foam generator 5, another separation layer 4 and finally a layer of

recovery 6.

  The composition of successive partial layers

  will be described later in the presentation.

  According to Figure 2 the building element 1 is

  consisting of a metal sheet which is covered externally

  laughingly and on its two front faces with a protective layer 2. This part is joined with the laminated fire protection element in a set and can be transported thus to constitute an overall cover of the objects to be protected. In this case, the layer

  protection 2 is close to one of the generat-

  these of foam 5 and the additional layer 5 is located near a separation layer 4 which is inserted between this additional layer 3 and the other foam-generating layer 5. The external separation layer 4 is also covered with a cover couch 6 This structure set is placed on supports 8, for example walls or posts and can be anchored to it in an appropriate way The manufacture of the laminated element can be done in different ways, in particular by constitution

  successive elementary layers, the construction element

  tion I being first coated with the protective layer, in particular an adhesive base, a corrosion protection layer or a similar primer layer. In the case where the building element 1 is made of steel, it is advisable to establish the protective layer 2 using an epoxy resin. By heating, the laminate element expands with the foam-generating layers

  in a ratio of 10 to 100, for example up to 20 cm.

  Because against each foam generating layer 5 is inserted a mechanical separation layer 4 of fibers, fleeces, fabrics and the like, the charred framework which is formed under the action of fire is stabilized. The fibers can be projected; they can also be injected in the dry state or even sprayed at

  wet condition with epoxy resin coating.

  Separation layers do not stabilize alone-

  mechanically but they constitute, during development

  fire and under the action of heat, stable layers swollen as a result of the vaporization of the water contained in the epoxy resin. They also have a strongly endothermic action, so that there is at the same time cooling. The cover layer 6 must be compatible

  with epoxy and resist the influences of bad weather.

  It is recommended to use a polyurethane or a

acrylate dispersion.

  The following composition is particular

preferred for diapers.

  As a protective layer 2 on a steel structure serving as a building element 1, a Uità end based on thick resin is used which is applied to the building element 1 in a very thin layer according to

Figure 2.

  In the generating layers of mouse 5, we use the following onstituanto A as liat Ot B as hardener. parts by weight A) Hydratable epoxy resin composed of bisphenol A and epichlorohydrin, epoxide index 24-25, epoxy equivalent 172-178, Gardner color index 1-3, density 1.3 (20 0 ), viscosity 1200-1500 oP (RUtapox VE 2913) 22 Novolac resin, 80% acrylate dispersion (4186 RUtgerswerke) or an acrylate modified epoxy resin, such as VEM 37/1 (Hoechst) 5.0 Stabilizer (VVE, RUtgerswerke Duisburg) (possibly tylosis - MHB 10000, Hoechat AG-) 1.2 Penta-erythritis 9.0 Melamine resin (Maprenal VMP 3910) 5.0 Flame retardant with phosphate ff (Phoscheck I 30) 13.0 Titanium dioxide 9.9 Tris (dichloroethyl) phosphate with emulsifiers (Rhosgard 022R) 6.5 Ground glass fibers (ground fiber EC-10S) 2.4 Distilled water 20.0 parts by weight B) Polyamine hardener , amine equivalent 125-150 viscosity 7000- 8000 cP, density 1.0 (20 00) Gardner coloring power 8-10, 75% of solid body (ABS4 RUtgerswerke or H 553) 53.6 Friendly hardener do-amide (105 / B, RUtgerswerke) 26.8 Anhydride hardener (Y. RUtgerswerke) 79 Guanylurea 10,0o Trisdimethylaminophenol (DMI 30) 10,7 An aqueous emulsion is established composed of five parts of the constituents A and one part of the constituents

  B and the first foam-generating layer 5 is applied.

  The storage time is 2 hours. therefore, for an application of several coats, 1 to 2 days pass

  Until the next layer can be applied. -

  On the first foam-generating layer 5, in this case the lowest or the most interior, is applied to

  wet or dry the first layer of separation

  tion 4 with the use of glass fibers and so that a layer 5 with a thickness of 100 to 300 μm is applied first and that on this layer, by means of glass cutting members with air flow or by means of a resin sprayer, the cut glass fibers are projected from a

  length of 4-20 mm, especially 6 mm.

  A particularly favorable process consists

  according to the invention in that the emulsion epoxy resin

  wheat which is already filled with additions and / or fillers by forming a slightly pasty mass and the hardener also provided with additions and / or fillers by forming a pasty mass are first heated to reduce the viscosity or the improved fluidity. The constituents, reduced to a viscosity of less than approximately 10%, are

  then mixed under high spray pressure of approx.

  ron 200 to 300 bar in a static mixer in which the current of each component is divided by producing a dynamic mixture without dynamic treatment. At the same time, the proportions of the mixture can be adjusted. It is recommended, however, to use a proportion of 4: I between the emulsifiable epoxy resin containing additions, for example according to components A, and the hardener composed according to components B. p5 a After mixing, the mixture is new separated into two flows to coat glass fibers

  finely hung in the field of a projection pistol

  tion and to be projected in layers of coating on the object to be protected, for example on a chest wall of

or a shielding plate.

  The total layer thickness is 0.6 to 1.5 m Then the foam-generating layer is applied

  next 5 analogously; as shown above.

  After applying the next layer of separa-

  tion 4, the application of one or more additional layers is carried out 7 which contains 4 parts by weight of the components 3 and 1 pea part of the components F according to the following formulation: parts by weight E) epoxy resin bisphenol A and epichlorohydrin (not hydrated) (Beekopox EW 117, Hoechst AG) 29.0 Novolac resin (VS 4186, 80% RUtgerswerke) 11.5 Penta erythritis 12.0 Phosoheck P 30 18.0 Melamine resin (Maprenal MF 980) 3.5 Titanium dioxide 8.4 Tris (dichloroethyl) phosphate 9.3 Melanin resin (Maprenal MF 590) 6.5 Glass fiber (ground fiber EC-10S) 1.8 parts by weight Y) amine hardener (Euredur 43, Hoechst AG) 40.8 - amine hardener (LO, 'RUtgerswerke) 25.4 anhydride hardener (Y, RUtgerswerke) 7.7 tris dimethylaminophenol (DMP 30) 7.7 asbestos fibers ( Sylodex 2X) 1.1 guanylurea 15.4 glass fibers (ground fiber EO 10S) 1.9 The shelf life of this mixture of constituents

  is 40 minutes: proportion of the mixture E: F = 4: 1.

  After applying another layer of separator

  tion 4, finally applying the covering layer 6 which consists of 4 parts of the constituents C and a part of the constituents D, according to the following formulation s parts by weight 0) polyester of adipic acid, phthalic acid, 80% triol and diol in ethylglycolacetate

(VPEL 5 2332 BAYER AG) 39.14

  titanium dioxide 27.48 montmorillonite thickener - alkylammonium salt (Bentone 34) 10% in benzen 544 zinc accelerator (Nuvofex, 8% Zn) 0O11 silicone oil (OL, 10%) 0 53 tris phosphate (dichloroethyl) 77 aluminum oxide trihydrate 7.7 ethyl glycol acetate 4.37 butyl glycol acetate 7.6 D) mixture of aromatic diisocyanates (Desmodur VPEL Bayer AG) proportion of mixture C: D- m 4 I The material obtained gave a stability value

  with flames of 150 min. according to German standard 4102.

  To avoid contraction of the layers during hardening, plasticizers and possibly dicresyl-methyl phosphate are added to all the layers.

  amounts of 2 to 10% / of each composition.

  It is possible to mix the constituents A of the emulsifiable resin with the constituents E of the non-emulsifiable resin for maximum action and this in the

  proportion A: E = 10 to 60: 90 to 40.

  In many cases, building elements for layer combinations must be shaped before they are used. We then use thin t8les

  which are more or less strongly bent or bent.

  As these sheets in the bent state allow themselves to differ

  Sky coating, it is advantageous to coat the sheets in the flat state by hand or by machine. In the machine, the successive layers can be brought one after the other by a conveyor belt and between the layers a zone of curing by hot air or infrared radiation can be interposed. It is thus possible to

  set a conveyor belt speed from 20 to 90 m / min.

  The compositions are however to be modified for bending because the layers must be analogous to rubber. This result is obtained by mienx by adding 10 to 40% of dicresyl-phenyl phosphate and / or thermoplastics. Particularly suitable are butadiene homopolymers and copolymers of butadiene and acrylic nitrile which contain reactive groups in the dax positi0n Aerzmes These groups can be carboxyl, hydroxyl, vinyl groups and even

terminal amino groups.

  In the present example, the hardeners B where the hardeners F can be used with a product containing terminal amine groups, for example HYGAR AIBN 1300 x 6 (BF Goodrich) Viscosity, Brookfield cP 225,000 Total amine equivalent 800 - 1000 content of acrylic nitrile 16.5 specific gravity at 25 0 0.956 To hardener B, for example, 60 parts are added

  by weight of HYOAR ATBN. The proportion of the mixture of the ex-

  ple is modified as follows: A: B = 2.5: 1.

  60 parts of HYCAR ATBN are also added to hardener X and the proportion of the mixture is changed as

follows: E Y = 22: 1.

  After hardening, elastic layers are obtained.

  those which do not have cracks on bending

edges.

  Instead of the hardener, the epoxy resin itself can be homopolymers of acrylic nitrile or

butadiene.

  For this purpose, the copolymers of acrylic nitrile and of butadiene containing carboxyl groups are

  mixed with epoxy resins and used 8 hot.

  Example: Epoxy resin from example E 100 g HYCAR 1300 XB RLP 20 g Processing takes place at around 130 eG

for about 16 hours.

  As long as the composition is liquid, add in

  the composition E 40 parts by weight.

  It is also possible to apply additionally

  hardener F transformed by HYCAR.

  Outside the application for curved t8les

  or folded, you get the advantage of additional protection

  keep silent about fire because compounds with a high nitrogen content have an additional action of stability

fire during charring.

  As a result of the homopolymer content, it is even possible to prevent contraction even better, so that in the event of fire there is no formation of microcracks and the action of plasticizers such as phosphate

  diphenyl-cresyl is reinforced.

  The protective elements delaying the action of fire are generally applied as a protective layer against fire on a body to be protected, for example a wall of a safety deposit box, an armor plate or a building construction. It is however also possible

  to establish the element of protection as an independent part

  dante and in particular flexible to bring it only afterwards instead of incorporation in the desired position. So

  the invention is applicable in a variety of ways.

RE V EN D C A TI ON S.

  1. Fire-retardant coating product generating foam based on epoxy resin with foam-generating additives, endothermic reaction, which give off gases and / or break combination chains and / or with fillers, characterized in that a hydrophilic epoxy resin emulsifiable in water with a polyamine and / or polyamidoamine hardener and / or a polycarbonic acid hardener and / or with dicyandiamide serves as

  binder for additions or charges.

  2. Coating product according to claim 1, characterized in that one uses as lan ume aqueous solution composed of hydrophilic epoxy resin and from 1 to 40% by weight of water (counted relative to the weight

total).

  3. Garment product according to Reveudication 2, characterized in that loSmuli'on aqueous pee in addition to emulsion stabilizers which are compatible

with water and epoxy resin.

  4. Coating product according to claim 2 or claim 3, characterized in that the hydrophilic epoxy resin contains bisphenol A or

  bisphenol Y as well as epichlorohydrin.

  5. Coating product according to claim 4, characterized in that the hydrophilic epoxy resin comprises epichlorohydrin with an epoxide equivalent between 175 and 210 and a di- or triglucidylether of diols or triols with 2 to 20 atoms of carbon and possibly

  1 to 8 oxygen atoms of ether in a weighted proportion

  75 to 95% binder for 25 to 5% carbohydrate ether. 6. Coating product according to claim 5, characterized in that, as amine hardener, a derivative of a polyamine or of a polyamidoamine is used

with at least two amino groups.

  7. Coating product according to any one

  of the preceding claims, characterized in that

  the binder contains a cycloaliphatic or aromatic carbon dioxide which reacts with the epoxy resin to

temperatures between 100 and 300 O C.

  8. Coating product according to any one

  of the preceding claims, characterized in that

  that the additions contain nitrogen and / or phosphorus and decompose at temperatures between 100

and 600 C.

  9. Coating product according to claim 8, characterized in that between 30 and 70% by weight of additions (counted on the total weight of the coating means) which contain nitrogen and / or phosphorus are used. more than 20 moles% 10. Product of rsvteent according to evendioation 9% characterized by the Milk that at least two of these additions are used whose decomposition temperatures deviate

at least 50 C.

  11. Coating product according to. Claim 9, characterized in that at least two of the following additions are used: melamine phosphate, guanylurea phosphate, N-phenyl-N-cyclohexyl-p-phenyldiamine, guanidine carbonate, benzosulfohydrazide, other sulfur-containing organic compounds and bromine compounds with

more than 10% bromine.

  12. Coating product according to any one

  of the preceding claims, characterized in that, -

  as a water-soluble addition generating foam, a condensation product of dicyandiamide phosphate, a dicyandiamide and / or a guanidine silicate is used. 13. Coating product according to any one

  of the preceding claims, characterized in that,

  as foam-generating and / or flame-retardant additions, products belonging to the group comprising alkali silicates, alkali metasilicates, aluminum phosphate, aluminum oxide trihydrate, - zeolite, kieselguhr, l starch, pentaerythritis, bodies which at the same time reinforce carbonization and

pure activated carbon.

  14. Coating product according to any one

  of the preceding claims, characterized in that

  as an additional stabilizer and / or as a means giving off gas, a body from the group comprising melamine is used,

tylose and dioxaime.

  o Coating product according to any one

  of the preceding claims, characterized in that

  that the binder based on epoxy resin is a novolak resin with a part of 10 &. 40% by weight (relative

with epoxy resin).

  16o coating product according to any one

  of the preceding claims, characterized in that

  the binder contains resins modified by -resin

* p, .iqu, s or des -se p6énoliquep.

  1 Coating product, se! On! Where it is erected for as long as fillers, glass fibers, asbestos mse, gwaphite, boron, tungsten, steel

  or other materials resistant to high temperatures.

  18o coating product according to any one

  of the preceding claims, characterized in that

  that it comprises from 1 to 40% by weight. (relative to the total amount) of diphenylaresyl phosphate as

plasticizer and fire retardant.

  19. Laminated fire protection element using a coating means according to any one

  of the preceding claims, characterized in that

  that between two layers of foam generators (5) of the covering is interposed a separation layer (4)

forming an intermediate layer.

    Laminate element according to claim 19, characterized in that one of the layers generating

  foam (5) is covered with an additional separation layer

  (4) and that it is covered with a layer

cover (6).

  21. Laminated element according to claim 20, characterized in that the covering layer (6)

  contains epoxy and / or polyurethane.

  22. Laminated element according to any one of

  Claims 19 & 21, characterized in that a

  additional layer (3) is linked to the generating layer

  foam (5) through a layer of separat

  tion (4) and that the additional layer 3 contains a

  epoxy resin which is not hydrophilic or cannot hydrate.

  23. Laminated element according to any one of

  Claims 19 to 22, characterized in that the

  separating layers (4) contain fibers and / or inorganic substances released by heat, such as

  as glass-like constituents.

  24. Laminated element according to any one of

  Claims 19 to 23, characterized in that the

  separating layers (4) and / or the generating layers (5)

  of foam contain organic substances, pyrolyti-

  ques yielding water and / or starch which reinforce carbonization. 25. Laminated element according to any one of

  Claims 19 to 24, characterized in that the

  separation layers (4) and / or the foam-generating layers (5) contain thermoplastic materials such as

1 acrylonitrile-butadiene.

  26. Laminated element for protection against

  the fire according to one of claims 19 to 25, character-

  laughed at by the fact that the laminated element is associated with a building element coated with a protective layer

  (2) by forming a construction unit (7).

  27. A process for the manufacture of flame retardants, wherein a component which contains an epoxy resin

  emulsifiable in water is mixed with another constituent

  killer which contains a hardener based on polyamines, polyamidoamines, polycarbonic anhydride and / or dicyandiamide with the addition of foam-generating bodies giving off gases and / or breaking chains of chemical composition and / or fillers, and is applied to a structure

  support on which it is fixed.

  28. Method according to claim 27, characterized in that each of the constituents is provided, before mixing, with the corresponding additives and / or fillers.

  29. The method of claim 27 or the res

  dication 28, characterized in that the two constituents after mixing are still mixed with other non-foaming fillers, in particular fibers

  of glass and applied to the support structure.