FR2566703A1 - FLAME RETARDANT LAYER ELEMENT AND METHOD FOR DELIVERING FLAME RETARDANT FOAM GENERATING LAYERS - Google Patents

Abstract

TO IMPROVE ESPECIALLY THE STABILITY IN FOAM OR INFLATION OF COMBINATIONS OF FLAME RETARDANT LAYERS, THE FOAM GENERATING LAYER 3 IS COMBINED AT LEAST WITH A STOP LAYER 2A, 2B WHICH LIMITS THE FORMATION OF FOAM OF THE GENERATOR AND MOUSSE LAYER MECHANICAL COHESION WITHOUT NOTABLE PARTICULAR SWELLING.

Description

2S66703

  The invention relates to a layered flame retardant element with at least one foam generating layer capable of foaming at high temperatures and at least one other layer adjacent to this foam generating layer as well as a method for conducting the formation of foam by the

  flame retardant layers generating foam.

  One such layered flame retardant element is already known (DE-OS 30 42 788). Foam generating layers alternate with so-called stop layers which have the role of preventing the formation of crevices through the layered element. Although such layered flame retardants have a proven track record because they prevent progression, for example 30 to 60 minutes,

  heat, they may give rise to difficulties

  tees if strong air movements or other mechanical forces

  exert their action on the foam generating layer.

  Despite attempts to form a strategic structure

  tified composed of numerous individual layers which are separated by barrier layers containing glass fibers,

  such disadvantages have not yet been overcome.

  The object of the invention is therefore to propose a flame retardant element of this type which is characterized by a flame retardant action.

  effective even when special forces are applied-

mechanical in nature.

  The invention consists in that the additional layer is constituted as a barrier layer which prevents or limits the formation of foam by the foam-generating layer or

  by foam-generating layers.

  The invention is based on this observation that the foam-generating layers of known type can foam very irregularly so that large voids can partly form. The carbon structure that forms is often so weak that it crumbles and the heat barrier action is then partially lost. According to the invention, the uncontrolled formation of foam in the generating layer of foam is to a certain extent "braked" and this in such a way that there is no formation of such large voids but on the contrary so that structures finer foam with smaller pores are formed. By wrapping the foam-generating layer on both sides with such barrier layers, a "hard structure" with relatively small pores is formed which does not break up so easily under the action of strong gusts of wind or other tremors. . It is therefore advisable to provide the stop layer with a filler body in the form of fibers and / or flakes.

  such as mica and / or silicates to guarantee a forma-

  shell in cooperation with the formation of a

  carbon framework or with carbonization in case of fire

  die. Carbonization is promoted by the addition of melamine.

  In addition, other fillers can also be used, such as magnesium and calcium carbonates or their oxides.

and silicates.

  According to another alternative implementation of the in-

  vention, we solve the problem by loading the general layers

  foam which can foam at high temperatures by at least one barrier layer which does not foam at such high temperatures which are responsible for the formation of foam in the foam generating layer but which prevent

  contrary to the uncontrolled formation of foam at temperatures

  high tures, in particular in the event of fire and ensure a relatively long period of solidity or stability on

a desired thickness.

  Other embodiments of the invention will appear

  in the following description, including the description of the figures

of the attached drawing.

  The glass fibers should be very fine, preferably

  Rence of a diameter or a thickness of 6 to 15 microns and a length of about 2 to 6 millimeters. For particular purposes it is also possible to incorporate elements called microballoons or glass flakes. While the foam generating layer has an average thickness of 0.5 to 3 mm, each barrier layer which limits the formation in

  foam should be 1 to 2 mm thick.

  While the non-foaming barrier layer swells no more than 5-10 mm in the event of a fire, the foam-generating layer will swell in an uncontrolled state to 10-20 cm, but will only foam in half and even less under the action of control

  of the non-foaming barrier layer.

  Examples of execution will be indicated in more detail

  with reference to the appended drawing, of which FIGS. 1 and 2 represent

  feel schematic partial sections of layered elements. According to FIG. 1, on the support to be protected 1 on which a layer of adhesive agent 4 can be applied and

  polyvinyl corrosion protection for steel-

  butanol, first applying the stop layer 2a and then on it the foam-generating layer 3 which is covered by the second stop layer 2b. The layer of adhesion agent 4 is also prevented from foaming by the stop layer 2ao.

  two layers 4 and 2a must also be protective layers

  tion in the case where by an external action, such as in the case of a fire, falling objects or splashing water, the foam-generating layer 3 would be damaged. The good mechanical quality of the layer still allows part of the layer of the adhesion agent 4 to foam even more if the layers 2b and 3 become faulty.

  against fire is guaranteed for a longer duration.

  According to Figure 2, the laminate structure is further improved. Wherever a rapid formation of foam must be established at low temperatures and o the support 1 - here wood covered with a sheet 5 must receive the first protection, the foam-generating layer 3b and the stop layer 2a are applied while the other layers 2a, 3a and 2b have the same roles as those described above. The foam-generating layer 3b and the stop layer-2a are then made thinner to initiate the first formation.

  of foam. At the same time, they prevent the general layer

  main foam scavenger 3a is reached too strongly and too quickly; this contributes with the stop layers

  more regular formation of the necessary small pores.

  This arrangement has an additional advantage because the barrier layer 2b has a double function including a role of limiting or preventing the formation of foam for the adjacent foam-generating layers 3a, 3b. A

  corresponding double role is fulfilled by the stop layer 2a.

  The stop layers 2a, 2b, 2c are provided with

filling in strips 6.

  The result in the event of a fire always includes robust, vitrified, hard layers which are very stable against external actions. All the outer barrier layers 2b or 2c can also be covered with a protective layer which must in particular resist the action of water and the constraints of the environment. Polyurethanes of all kinds are suitable for this purpose, mainly polyesters of adipic acid, triol phthalic acid.

  and 80% diol in ethyl glycol acetate and with mixtures

  aromatic diisocyanates (Desmadur VPKL Bayer A.G.).

  In the following, the compositions of the elementary layers will be described, specifying that the method can be applied to all fire protection systems and that the

  type of commodities may vary from layer to layer.

  1. The stop layers 2a, 2b, 2c are composed as follows: Components A: a) VE 3100 / SE / A (epoxy resin emulsion from the company RUtgerswerke AG) parts by weight b) MF 910 (melamnin resin completely unplasticized etherified from Hoechst AG) weight parts c) Antiblaze 78 (chlorophosphoric ester from Mobil Oil AG) parts by weight d) Mica 4.5 parts by weight e) Titanium RD 2 4.5 parts by weight f) glass fibers EC 10 (from Vetrotex AG) parts by weight The fluid products are first mixed then the solid constituents are added, the glass fibers being added slowly using dissolver D. At 1 kg of this mixture, it is added again with solvent g of mica and 30 g of Aerosil R 805 as well as 100 g of ethanol

or another solvent.

  Components B: a) VE 3100 / SE / B (addition hardener from RUgerswerke AG) parts by weight b) S 3111 (hardener system from Odenwald Chemie GmbH) parts by weight c) EC 10 (from the company Vetrotex AG) parts by weight AI kg of constituents B can also be added 30 g of Aerosil R 805, 200 or 250 g of mica and 100 g of tethanolo The mixing is carried out by slow addition of EC 10 using the solvent or '' a three-roller mixer for

one hour.

  The mixing of components A with components B takes place

  in the proportion of 2 parts by weight per 1 part. -

  The action of the barrier layer controlling foaming can vary in different ways. This is done for example by variation of the basic material of the components A, a), the proportion by weight being adjusted between 70 and 30 parts by weight. With 30 parts by weight of a) the Plastorit mica or silicate forming the "solidity load" can be increased

double.

  In the event of a fire, the various constituents form a solid composite layer of carbon, glass, mica and Aerosil which melt at a fire temperature of 900 C and which limit the foaming of the generating layer of

  foam, i.e. the thickness of the layer.

  b) The same effect can be obtained by the thickness of the barrier layer. For each application case, the corresponding choice is made between the composition and the thickness of the barrier layer. 2. The layer of the adhesion agent 4: The composition of this layer is as follows Coposants A: a) VE 4001 (mixture of epoxy resin A / F with Novolack from the company RUtgerswerke AG) parts by weight b) MF 910 (melamine resin as 1 component A b) from Hoechst AG) 2 parts by weight c) VVE (stabilizer from RUtgerswerke AG) 2 parts by weight d) water 2 parts by weight e) penta-erythritis 18 parts by weight f) Phoscheck P30 18 parts by weight g) Antiblaze 78 (chlorophosphoric ester from Mobil Oil AG) 11 parts by weight

h) Titan RD2-

  2 parts by weight i) mica 2 parts by weight To 1 kg of this mixture, it is also possible to add 10 parts by weight of Aerosil R 805 and another 50 parts by weight of mica, then as a diluent a mixture of 60 parts by weight chloride

  methylene and 40 parts by weight of toluol.

  Components B: a) VE 4001 (hardener resulting from the addition of amine and polyamidoamine from RItgerswerke AG) 16 parts by weight b) water 2 parts by weight c) Dicyandiamit EH (SKW Trostberg) 3.2 parts by weight d ) Aerosil R 805 (from Degussa AG) 0.4 parts by weight Components A and B are mixed in the proportion of 4 to 1. In the event of splashing, it is sufficient to use a small quantity of the solvent mixture while for a coating

  the quantity indicated should be used.

  For good adhesion to the support 1 and for greater solidity to receive the action exerted by the upper foam-generating layers, the layer of adhesion agent 4 must be applied in two operations. Between the first operation and the second it is advisable to spare a

rest of at least 24 hours.

  3. Foam generating layers 3, 3a, 3b: Components A: a) OS 98 (epoxy-Novolack mixture with diluent S from RUtgerswerke AG) 44 parts by weight b) Maprenal 980 (Hoechst AG) 4 parts by weight c) MF 910 (melamine resin from Hoechst AG) 6 parts by weight d) Exolit 454 (activated ammonium polyphosphate from Hoechst AG) 20 parts by weight e) penta-erythrite parts by weight f) mica 4.5 parts by weight g) Titan RD2 4.5 parts by weight h) Antiblaze 78 (chlorophosphoric ester from Mobil OilAG) 12 parts by weight i) glass fibers EC 10 (from Vetrotex AG) 20 parts by weight At 1 kg of components A, we still add 35 parts

  by weight of Aerosil R 805 and 700 parts by weight of ethanol.

  The proportion of ethanol may increase depending on the temperatures.

  external erasures or decrease depending on whether the composition must

be coated or sprayed.

  Components B: a) polyamidoamide parts by weight b) addition of amine 10 parts by weight c) amine H91 (from the company RUtgerswerke AG) parts by weight A further 30 g of mica and 25 parts can be added to 100 parts of this mixture by weight of an addition of amine

additional.

  This mixture is stirred for a long time in the other constituents.

  killing with solvent, advantageously with another 10 g of Aerosil R 805 or corresponding parts by weight of Sylodex 24 or Bentone or bentonite. The material which foams by heat is mixed in the proportion of the components - A

  compared to components B from 4 to 1.

  In all the examples, resins and hardeners from RUiltgerswerke AG were used; these products can however be replaced by other products

  firms such as Bayer, Hoechst, Schering, Ciba-Geigy, Dow.

  When applying foam-generating layers, it is advisable to quickly apply the layers on top of each other. In particular, the epoxy resins with the hardeners provided have a long curing time which is desired, for example for coating. In addition, we have already achieved by means of high-pressure machines and special injection guns with separate admission of compressed air, to find a remarkable distribution of mixtures capable of foaming Precisely on objects whose current service should not

  be interrupted, fast work must be ensured.

  For epoxy resins with amines, there was no

  So far suitable accelerators. Against all expectations

  te, we managed to find such an accelerator for the present system, which acts with amines, polyamides or

amidoamines.

  It is a resin of polymercaptans which is used with hardeners. The Mercaptan figure must be at least 3.3 and the consistency must be approximately 15,000 m Pasc (at 20 C). The resin is a colorless liquid in the clarity of water. Polymercaptans react very quickly with epoxy resins. The reactions are carried out in thin layers as also in thick layers and even start at

  low temperatures. An addition of 25-35% is possible without loss-

  behavior and in special cases we can

  even go up to 75% compared to the total amount.

  The process indicated opens up a wide range of applications.

  because all the difficult problems of a foamable material are solved and for each application the appropriate foam structure and the foam height

  (layer thickness after foaming) are deter-

  mined in advance. A deviation from the setting is practically impossible and the guarantee of a fire resistance already set is

  obtained from the start. The process thus ensures that with the formu-

  the uncertainties observed so far for the

  overcoming the thermoplastic state of a missing resin

  because the way of combining the material which does not foam with heat or which hardly foam with a material which foam strongly with heat allows rapid crossing

of this state.

  Thus a sliding of the combination of the foam layers is prevented by the support or by the other layers and a high fire resistance is obtained which can reach a duration of resistance up to 120 minutes. The fields of application are for example the steel and other metal building elements as well as all wooden parts. The possibilities of a good

  fire protection both indoors and outdoors

  These are obvious, as in petroleum operations or installations at sea. It is also important that there are multiple possibilities of exchanging a few constituents such as glass which can be replaced for example by other fibers. The invention can also be applied to the military sector.

Claims (15)

R E V E N D I C A T I O N S.   1. Fire-retardant element in layers with at least one foam-generating layer capable of foaming at high temperatures and at least one other adjacent layer, characterized in that this other layer is constituted as a barrier layer (2) which prevents or limits the foaming of the foam generating layer (3) and gives the combination of the barrier layer (2) and the foam generating layer (3), after setting   foam of the latter, a relatively stable structure.   2. Layered element according to claim 1, character-   rised in that the barrier layer (2) comprises at least 50% load material.   3. Layered element according to claim 2, charac-   terized in that the barrier layer (2) contains glass fibers in a proportion of more than 30% and of a length between 0.2 and 6 mm.   4. Layered element according to claim 3, character-   laughed in that the glass fibers are at least partially replaced by carbon fibers, quartz fibers,   steel fibers, boron fibers and / or organic fibers   aromatic polyamide, aromatic diamine and   arylene-dicarbonic acids or ARAMID. -   5. Layered element according to one of claims 2   to 4, characterized in that the barrier layer (2) comprises laminated load bodies.   6. Layered element according to claim 5, character-   laughed at in that the laminated load bodies consist of   mica, PLASTARIT or magnesium-potassium silicate-   aluminum, a waxy mixture of moscovite, chlorite * and quartz, silicates, silicic acid or Aerosil and / or   carbonates and / or magnesium and / or calcium oxides.   7. Layered element according to any one of the res-   above, characterized in that the general layer   foam (3) and / or barrier layer (2) include chlorophosphoric esters with at least 12% phosphorus   and 34% chlorine, the chlorine compounds can be replaced   cés at least partially by a bromine compound.   8. Layered element according to any one of the res-   dications 1 to 7, characterized in that the barrier layer (2)   practically does not foam when heated.   9. Layered element according to any one of the res-   dications 1 to 8, characterized in that the barrier layer (2) has approximately the same layer thickness as the layer   associated foam generator (3).   10. Layered element according to any one of the res-   dications 1 to 8, characterized in that the barrier layer (2) has a layer thickness of one, two and up to three   times the thickness of the associated foam generating layer.   11. Layered element according to any one of the res-   above, characterized in that the thicknesses of the foam generating layer (3a) or of the barrier layer (2a, 2b) on the side of the support to be protected (1) are greater than the thickness of the generating layer foam (3b) or barrier layer (2b) away from the support to be protected (1) o   12. Layered element according to any one of the res-   above, characterized in that the general layer   foam (3) and / or barrier layer (2) include   as binders for epoxy resins and corresponding hardeners heavy.   13. Layered element according to claim 12, charac-   terized in that the foam-generating layer (3) and / or the stop layer (2) comprise a polymercaptan resin in a proportion between 25 and 75% (relative to the quantity - total).   Layered element according to claim 12 or claim 13, characterized in that hydrophilic epoxy resins or water-containing epoxy resin emulsions are used as starting materials   15. Layered element according to any one of the res-   above, characterized in that the general layer   foam foam (3) and / or barrier layer (2) include polyurethanes, unsaturated polyesters, vinyl esters, melamine and / or polymer acetates of vinyl or MOWILITHE.   16. Layered element according to any one of the res-   previous indications, characterized in that the support (1)   is coated with a layer (4) of an adhesive agent.   -12 17. Layered element according to any one of   previous claims, characterized in that on the   support (1) or the layer (4) of the bonding agent, a barrier layer (2a) is first applied and then a foam-generating layer (3, 3a). 18. Method for conducting the formation in foam of flame-retardant layers which generate foam which can foam at high temperatures, characterized in that the layer   foam generator (3) is covered at least partially-   ment of practically no foaming material which interferes with the free foaming of the foaming layer.