Molding material and its use as construction and repair material

A molding material based on polyisocyanato-isocyanurates, polyols and flameproofing and fireproofing agents, as well as optionally polyisocyanates, fillers and promoters is described which is preferably in the form of a 2-component material and comprises 5 to 40% by weight of branched polyols, 20 to 40% by weight of the isocyanurate of 1,6-hexamethylene diisocyanate, 0 to 20% by weight of crude MDI and/or prepolymer of polyol and crude MDI and/or isophorone diisocyanate optionally in combination with further isocyanate groups containing compounds, 5 to 20% by weight of a fireproofing mixture mainly consisting of secondary ammonium phosphate, 0 to 50% by weight filler and 0 to 5% by weight promoter. This mass, which permits quick processing at room temperature or slighty increased temperatures, is useful as construction and repair material for many applications, especially in connection with the construction and repair of land, air and water vehicles. The products obtained after curing meet the highest requirements with regard to fire protection and possess excellent mechanical properties.

BACKGROUND OF INVENTION 
The invention relates to a novel molding material based on 
polyisocyanato-isocyanurates, polyols and flameproofing and fireproofing 
agents, as well as optionally polyisocyanates, fillers and promoters, 
which is particularly suitable for use as construction and repair material 
and especially from the quick processing and the fire protection 
standpoint leads to excellent products. 
Duroplastic compounds and foams of polyurethane with isocyanate and 
isocyanurate components, epoxy resins (EPO resins), phenolic resins and 
novolacs are known, which contain flame-inhibiting additives and which 
constitute difficultly or nonflammable materials. In order to improve the 
fire resistance and achieve a low smoke density and toxicity, a large 
number of different formulations has been proposed. As flame-inhibiting 
additives are inter alia proposed Al.sub.2 O.sub.3 .times.H.sub.2 O, 
organic and inorganic phosphates or phosphonates, borates, silicates, 
chlorinated paraffins, halogen compounds, heavy metal salts, elementary 
phosphorus, polyphosphates and antimony trioxide. Reference is made in 
exemplified manner in this connection to U.S. Pat. Nos. 4,126,473 and 
4,147,690, European Pat. No. 69 975 and DE-OS No. 31 05 047. A survey of 
the prior art appears in Becker-Braun, Kunststoffhandbuch, vol. 7, 
Polyurethanes, second edition, 1983, Hanser-Verlag; J. Troitzsch, 
Brandverhalten von Kunststoffen, Grundlagen etc., Carl Hanser-Verlag, 
1982; and Polymerwerkstoffe, vol. 2, Technologie 1, H. Batzer et al., 
Georg Thieme Verlag, Stuttgart, 1984. 
With individual additions or combinations of such flame-inhibiting 
additives in part very satisfactory results are obtained. In view of the 
great increase in the use of plastics, nowadays extreme demands regarding 
fire protection are made in the field of the conveyance of passengers 
through a number of standards and specifications, particularly with 
respect to the aircraft and car industry, as well as in ships, trains and 
in the building industry. This is documented in various national and 
international test standards, such as DIN 75200, DIN 4102, DV 899/35 
(Germany), FAR 25.853, MVSS 25.853 (USA), AFNOR P 92-507 (France), etc. As 
it is to be expected that these standards will be made even stricter in 
future and apart from non-flammability, special importance will be 
attached to the density and toxicity of the smoke gas in the case of 
charring and/or fires, in 1979 the Airbus consortium drafted its own 
stricter standards, ATS 1000.001 and made it available to the relevant 
branches of industry. In the case of an estimated aircraft life of at 
least 15 years, this standard already takes account of future technical 
developments and demands (ct. TU 21, 1980, No. 2, February, pp 79-82 and 
"Die chemische Produktion", 1983, pp 50-53). 
The one- and two-component molding materials presently used in the aircraft 
industry do not yet meet the requirements of ATS 1000.001. 
In the aircraft industry such molding materials are e.g. used for producing 
reinforcements and mountings (inserts), internal coverings (e.g. side 
walls and partitions, as well as roof coverings), floors, insulating and 
covering plates, as well as molded parts. Particular preference is given 
to the use of so-called prepreg components (sandwich honeycomb 
constructions), which are constituted by phenolic resin honeycombs coated 
with multilayer resin mats (trade name Nomex). The resin mats (prepegs) 
comprise E-glass fabrics, which are impregnated with resins based on 
phenol/formaldehyde, unsaturated polyesters, EPO and polyimides. With a 
view to increasing stability and saving edging profiles, an edge filling 
mass is often pressed into the honeycombs on the edges of the sandwich 
components. 
A molding material able to satisfy demands in the foreseeable future must 
cure without shrinkage and lead to a construction material with a low 
density of approximately 0.2 to 0.8 g/cm.sup.3, which ensures high bending 
and compression strengths both at ambient temperature and under continuous 
thermal influences up to 80.degree. or 130.degree. C. To this must be 
added the demands in connection with fire and/or charring, namely 
non-flammability, no dripping, insignificant smoke gas emission and 
substantially non-toxic pyrolysis gas evolution. For special uses (e.g. 
fire protection walls in the transportation area of aircraft) higher 
thermal stability would also be necessary, i.e. the material must be able 
to withstand e.g. a temperature of 1000.degree. to 1200.degree. C. for 10 
minutes. With regards to the conventional composite system in which such 
molding materials are used, there must be an optimum connection or 
adhesion with the materials forming the basis of such composite systems, 
such as polymers, polycondensates or polyaddition compounds (e.g. 
unsaturated polyesters, EPO resins, phenolic resins, polyimide or 
polyurethane). It is necessary or at least desirable to also have an 
optimum connection or adhesion to metals and materials such as glass and 
carbon fibres. 
The formulations and systems known from the prior art, which are described 
in numerous patent specifications and applications, only partly fulfil 
certain of the above requirements or combinations of partial ranges 
thereof. 
Thus, European Patent application No. 157 1433 describes fire-inhibiting 
sealing compounds, which comprise melamines and a number of fillers which, 
apart from other inadequacies, have densities of 0.7 to 1.0 g/cm.sup.3. 
DE-OS No. 35 19 581 describes ablation coatings of amine-cured EPO and 
polysulphide resin mixtures with pre-ox-carbon fibres as a reinforcement 
which, although resistant to high temperatures, have densities well above 
1.0 g/cm.sup.3. 
DE-OS No. 27 14 006, DE-OS No. 27 13 984 and DE-OS No. 27 40 504 describe 
molding materials comprising polyisocyanate and hollow spheres. These are 
cured through access of atmospheric humidity and optionally after addition 
of water. Preferably, shortly prior to processing phosphoric acid and/or 
phosphates or their aqueous solutions or alkali silicate solutions are 
added. The molding materials described in these patent applications only 
have a relatively low compression strength in the cured state and are only 
storage-stable in the form of premixes constituted by polyisocyanate and 
hollow spheres. However, they are not stable as moisture-curing 
one-component materials and therefore do not have the processing 
advantages linked with the latter. Tests have revealed that e.g. mixtures 
of hollow spheres with 2% polyisocyanates do not give stable materials. 
Materials produced according to the process of claim 2 of DE-OS No. 27 14 
006 (plates with a thickness of 5 to 10 mm) were unable to withstand a 
temperature of 1080.degree. C. for one minute. 
Therefore the problem existed to avoid the above described disadvantages of 
known molding materials and to obtain improvements to the characteristics, 
particularly in the fire protection field. Especially there existed the 
problem of providing molding materials which, apart from the 
aforementioned characteristics, in the cured state have high compression 
strength characteristics not only at ambient temperature but also at 
elevated temperatures up to 80.degree. C. (decrease of compression 
strength at 80.degree. C. in comparison to room temperature of less than 
40%), meet very high demands regarding flammability, smoke gas density and 
the evolution of toxic pyrolysis gases in the case of charring and/or 
fire, do not afterflame, do not drip, are resistant to water, hydraulic 
fluid and kerosene, provide excellent binding to any standard prepreg 
materials, metals and fibrous materials and cure in shrinkage-free manner. 
For the solution of these problems a one-component molding material based 
on polyisocyanato-isocyanurates and flameproofing and fireproofing agents 
as well as optionally polyisocyanates, fillers and promoters has been 
proposed in prior application Ser. No. 24026 filed on Mar. 10, 1987 
comprising: 
A. 40 to 80% by weight of the isocyanurate of 1,6-hexamethylene 
diisocyanate with a NCO content of 18 to 24% by weight, 
B. 0 to 20% by weight of crude MDI and/or prepolymer of polyol and crude 
MDI and/or isophorone diisocyanate optionally in combination with 
dimerized triazine of TDI, copolymerized triazine of TDI and HDI and/or 
naphthalene diisocyanate, 
C. 5 to 20% by weight of a mixture of: 
a. 50 to 100% by weight of secondary ammonium phosphate with the proviso 
that the amount of secondary ammonium phosphate is 80 to 100% by weight if 
component C is only present in an amount of 5 to 10% by weight, 
b. 0 to 20% by weight of primary ammonium phosphate, 
c. 0 to 20% by weight of zeolite and/or crystalline alkali silicate, 
d. 0 to 20% by weight of finely divided silica, 
e. 0 to 20% by weight of Ca.sub.3 (PO.sub.4).sub.2, 
f. 0 to 20% by weight azodicarbonamide, 
g. 0 to 20% by weight calcined calcium oxide, 
D. 0 to 50% by weight of filler and 
E. 0 to 5% by weight promoter. 
After cold shaping, the curing of this molding material takes place by 
ramming, rolling, pressing, extruding, shaking in, blowing in, etc. at 
ambient or elevated temperature through the action of atmospheric humidity 
or water vapour. At ambient temperature curing takes place within about 7 
dauys or within a single day when adding about 1 to 3% by weight of the 
above mentioned promoters. However, preferably curing takes place at 
110.degree. to 200.degree. C. (e.g. 130.degree. C.) without promoter in 
about 0.5 to 3 hours. Generally there is a not inconsiderable aftercuring, 
so that the initially obtained compression strength, e.g. after 4 weeks, 
can increase by about 20 to 30% and even up to 50%. When curing this 
molding material, the expert will obviously take account of the molding 
geometry and thermal conductivity and will choose the necessary curing 
time accordingly (cf. e.g. DE-OS No. 27 14 006, p 23). Otherwise curing 
takes place at usual pressures, e.g. atmospheric pressure (pressures of 
about 0.5 to 50 bar normally being used). 
If the relative atmospheric humidity during curing is below about 40%, it 
is advantageous to add water in concentrations of 1 to 10% by weight, 
there being no need to define the water quantity. Water can be replaced by 
aqueous basis, such as e.g. caustic soda and caustic potash solution, or 
alkaline-reacting compounds, such as sodium or potassium silicates in the 
form of their aqueous solutions. Ammonium phosphate solutions are also 
very suitable. Generally 0.5 to 5N solutions are used. 
Though the molding material according to this prior patent application 
completely fulfills the above outlined requirements, it has turned out 
that in practice it is often desirable to have a molding material which 
can be used at ambient temperature and permits a quick or quicker 
processing without using presses or autoclaves. On the one hand curing 
times of about 7 days or one day when adding promoters (see above) are 
often not acceptable and on the other hand it is often not possible or at 
least not desirable to apply temperatures in the above mentioned range of 
about 110.degree. to 200.degree. C. This is especially true for repairs 
and particularly for repairs to be carried out in situ which because of 
the minor influence of the repair material on the overall properties of 
the repaired part (e.g. volumetric weight) do not to the same extent 
require the fulfillment and achievement of all of the above mentioned 
optimum characteristics of the molding material. 
OBJECT OF THE INVENTION 
Therefore it is an object of this invention to provide a molding material 
which substantially possesses the advantageous characteristics of the 
molding material disclosed in prior application Ser. No. 24026 but permits 
much quicker processing at ambient temperature or slightly increased 
temperatures of e.g. 60.degree. to 80.degree. C., preferably the use of 
presses and autoclaves being unnecessary. 
This and further objects will become apparent as the description of the 
invention proceeds. 
DETAILED DESCRIPTION OF INVENTION 
The invention is directed to a molding material and its use as construction 
and repair material, especially fire protection construction and repair 
material as described herein and in the dependent claims. 
The molding material according to the invention is a molding material based 
on polyisocyanato-isocyanurates, polyols and flameproofing and 
fireproofing agents as well as optionally polyisocyanates, fillers and 
promoters comprising: 
A. 5 to 40% by weight of branched polyols having an OH content of 2 to 22% 
by weight, 
B. 20 to 40% by weight of the isocyanurate of 1,6-hexamethylene 
diisocyanate, 
C. 0 to 20% by weight of crude MDI and/or prepolymer of polyol and crude 
MDI and/or isophorone diisocyanate (IPDI) optionally in combination with 
dimerized triazine of TDI and/or copolymerized triazine of TDI and HDI 
and/or naphthalene diisocyanate, 
D. 5 to 20% by weight of a mixture of: 
a. 50 to 100% by weight of secondary ammonium phosphate, 
b. 0 to 50% by weight of primary ammonium phosphate, 
c. 0 to 30% by weight azodicarbonamide, 
d. 0 to 20% by weight zeolite and/or ground alkali silicate, 
e. 0 to 10% by weight finely divided silica, 
f. 0 to 10% by weight calcium orthophosphate and 
g. 0 to 20% by weight calcined calcium oxide, 
E. 0 to 50% by weight filler and 
F. 0 to 5% by weight promoter. 
Polyols with an OH content of 2 to 22% by weight serve as component A, i.e. 
bifunctional or polyfunctional polyols with functional or non-functional 
side groups or chains. Polyols with elastifying properties, e.g. linear 
polyetherols and polyesterols, are not suited for the purpose of the 
present invention since the compression strength of the resulting molding 
materials significantly decreases at higher temperatures. Branched polyols 
suitable according to the invention are well-known from the prior art and 
commercially available in unnumerous variations (cf. e.g. DE-OS No. 34 18 
877, p 7, line 25 to p 9, line 26; DE-OS No. 27 40 504, p 11, line 16 to p 
16, line 27; as well as the pertinent literature relating to 
polyurethanes, the branched polyols suitable according to the present 
invention often being described in connection with the so-called 
prepolymer technique; with regard to commercial products compare e.g. the 
information brochures of Bayer AG relating to the product line 
"Desmophen"). Due to the fact that the molding material according to the 
present invention is preferably completely or almost completely 
solvent-free only those commercial products can be used which are 
solvent-free or which can readily be freed from such constituents. 
It has been found that propoxylated trimethylol propane with an OH content 
of about 11.5% by weight is particularly useful. Further, oligomeric 
multifunctional glycolethers with an OH content of about 22% by weight, 
oligomeric bifunctional polyesterols with an OH content of about 2 to 9% 
by weight, branched blockcopolymers of these oligomeric bifunctional 
polyesterols with the aforementioned propoxylated trimethylol propane or 
the oligomeric multifunctional glycolethers and finally 
fatty-acid-modified branched oligomeric polyesterols with an OH content of 
about 5% by weight are preferred. These preferred polyols are all 
commercially available and can be used as single components or in the form 
of any kind of mixtures (cf. also Becker-Braun, Kunststoffhandbuch, loc. 
cit.). Particularly preferred is, however, the sole use of propoxylated 
trimethylol propane. 
Component B is the isocyanurate of 1,6-hexamethylene diisocyanate. In the 
preferred case of the ideally trimerized 1,6-hexamethylene isocyanurate it 
is a polyisocyanate-isocyanurate with the following formula 
##STR1## 
Obviously the crosslinking products resulting from this compound are also 
suitable. The isocyanurate of 1,6-hexamethylene diisocyanate is 
commercially available and normally contains less than 0.5% by weight of 
monomeric 1,6-hexamethylene diisocyanate. The NCO content is 18 to 24% by 
weight and preferably 20 to 22% by weight. Conventionally the density is 
about 1.2 g/cm.sup.3 and the viscosity about 1000 to 3000 mPas, 
maintaining a suitable viscosity obviously being important from the 
processing standpoint. The content of the preferred ideally trimerized 
1,6-hexamethylene diisocyanate differs in the various commercial products 
and can be e.g. 98% and higher. 
The "crude MDI" consists of polyisocyanates based on diphenyl methane 
diisocyanate, as produced by aniline-formaldehyde condensation and 
subsequent phosgenation. Volatile constituents and part of the diphenyl 
methane diisocyanate formed are distilled off. Thus, crude MDI is a 
polyisocyanate from the bottom of the technical production or distillation 
of diphenyl methane diisocyanate (cf. e.g. DE-OS No. 27 14 006, pp 9, 18 
and especially 28; Kunststoffhandbuch, vol. 7, Polyurethane, second 
edition 1983, p 63). It is advantageous according to the invention if the 
crude MDI has a high functionality, i.e. the NCO content of the crude MDI 
is advantageously 28 to 33% by weight, although it is also possible to use 
materials with a lower NCO content, such as e.g. 20% by weight. The 
density (20.degree. C.) of crude MDI is normally 1.2.+-.0.1 g/cm.sup.3, 
whilst the viscosity is normally about 130 mPas. 
In place of crude MDI, component C can also be constituted by a prepolymer 
obtained by reacting crude MDI with polyol in known manner. Polyols 
suitable for the production of prepolymers are known to the expert and 
therefore require no further illustration (cf. e.g. DE-OS No. 27 14 006, p 
10 ff). 
Instead of crude MDI or prepolymer of polyol and crude MDI or in 
combination with crude MDI or prepolymer of polyol and crude MDI, in 
component C also isophorone diisocyanate (IPDI) can be used. Also this 
product is commercially available. 
In a further preferred embodiment of the invention in component C the crude 
MDI and/or isophorone diisocyanate can be combined with dimerized triazine 
of TDI, copolymerized triazine of TDI and HDI and/or naphthalene 
diisocyanate (NDI), these additional ingredients being charged as solids. 
Dimerized triazine of TDI is commercially available, e.g. dissolved in 
ethyl or butyl acetate, and has the following idealized structure: 
##STR2## 
Copolymerized triazine of TDI and HDI is also commercially available 
dissolved in ethyl or butyl acetate and has the following idealized 
structure: 
##STR3## 
Preferably component C is present in the molding material according to the 
invention in an amount of 1 to 10% by weight and particularly 2 to 6% by 
weight, because this leads to optimum compression strength of the cured 
molding material. 
Component D is decisively responsible for the extremely advantageous 
characteristics of the cured inventive molding materials with respect to 
non-flammability. Secondary ammonium phosphate (diammonium hydrogen 
phosphate, (NH.sub.4).sub.2 HPO.sub.4), azodicarbonamide, zeolite, 
particularly sodium or potassium aluminosilicate, ground alkali silicates 
like sodium and potassium silicate, finely divided silica, particularly 
pyrogenic silica, calcium orthophosphate (Ca.sub.3 (PO.sub.4).sub.2) 
and/or calcined calcium oxide. The mixture consists of at least 50% 
secondary ammonium phosphate and up to 50% of the remaining components. 
Experience up to now has shown that in particular a mixture of secondary 
ammonium phosphate, crystalline alkali silicate, pyrogenic silica and 
calcium orthophosphate is suitable. 
It is decisive for the storage stability of the inventive molding material 
or its component II that the water content of the individual components 
thereof amounts to no more than about 0.2% by weight, based on the molding 
material weight, and component D consists of particles with a size in the 
range of 0.5 to 150 .mu.m. Particular preference is given to a particle 
size distribution such that 70 to 90% by weight have a size of 5 to 100 
.mu.m, no more than 5% by weight a size of more than 100 .mu.m and no less 
than 5% by weight are smaller than 5 .mu.m. This particle size 
distribution applies to component D overall, but preferably also to each 
of its mixing components (a) to (g). To the extent that the materials used 
in component D are not already commercially available in the desired 
particle size, the particle size setting can take place in the usual way, 
e.g. by grinding. 
The finely divided silica or calcium orthophosphate in component C mainly 
has a stabilizing action, so that component C can be used in the form of a 
free-flowing premix in the production of the inventive molding material. 
Suitable quantities of these components under this aspect are about 1 to 
3% by weight, it being pointed out that the percentages by weight 
concerning the mixing constituents of component C only relate to the 
latter, both in the claims and in the description, i.e. the total 
component C corresponds to 100% by weight. 
Fillers suitable for component E are practically all known fillers for such 
molding materials, as a function of the intended use of the inventive 
molding material. Examples for such fillers are talcum, stone powder, 
chalk, non-flammable plastic granules, inorganic solids such as CaO, 
Mg(OH).sub.2, Al(OH).sub.3, metal flakes, chips and powders, zeolites, 
pigments etc. 
In view of the good results obtained therewith particular preference is 
given to fly ash and hollow microspheres made from glass or phenolic 
resins having a particle size of 5 to 200 .mu.m and a true density of 0.15 
to 0.7 g/cm.sup.3. Suitable are the conventional commercial products which 
are known to the expert and therefore require no further explanation (with 
regards to hollow glass microspheres reference can e.g. be made to 
Kunststoffe 75, 1985, 7, pp 421 to 424). From the fire protection 
standpoint it is particularly preferred to use in the inventive molding 
material those hollow spheres which are filled with non-flammable or 
fire-extinguishing gases. These generally involve nitrogen and carbon 
dioxide, but there are also hollow spheres filled with inert gases such as 
argon, although they can scarcely be considered from economic standpoints. 
Carbon, glass and metal fibres are also very suitable fillers. The use of 
carbon fibres is particularly advantageous if a high compression strength 
is required in the case of a low density of the cured molding material. 
Particularly suitable are carbon fibres and so-called pre-ox fibres formed 
from polyacrylonitrile (cf. e.g. DE-OS 35 19 581, pp. 6 and 7) having a 
thickness of 0.001 to 0.1 mm and a length of 0.005 to 50 mm and 
particularly 0.1 to 5 mm. Suitable metal fibres are mainly fibres of 
copper and stainless steel, the latter having preferably a diameter of 4 
to 12 .mu.m and a length of 1 to 12 mm. 
Other suitable fillers are silica or B.sub.4 C (tetraboroncarbide) with 
particle sizes of 1 to 70 .mu.m. 
Very suitable as filler are also aluminum flakes. Further so-called 
"cobweb-whiskers" have proven as extremely valuable fillers. These are 
fibre materials on the basis of SiO.sub.2, Si, SiC and C, which consist of 
single fibres interlaced in the submicron and micron range. Alternatively 
the "cobweb-whiskers" can consist of silicon carbide fibres in admixture 
with silicon carbide particles (cf. e.g. the brochure of Norwegian Talc 
Deutschlland GmbH relating to fibre additives "XEVEX" and "XPW 2"). 
In addition melamine resin powders, which are commercially available, have 
proven to be well suited fillers. The same is true for foamed clays, e.g. 
commercially available under the trade name "NORPRIL" (cf. the data sheet 
of Norwegian Talc Deutschland GmbH of September 1986). 
Inventive molding materials containing no component D, i.e. no filler, are 
suitable as non-flammable laminate resin for prepreg components. Low 
filler contents are advantageous if the inventive molding materials are to 
be processed to foams. In this context especially the use of hollow glass 
microspheres in a quantity of about 5 to 20% by weight has proven 
advantageous. In this connection, these spheres are also used for the pore 
regulation of the foam to be produced. The density of the hollow glass 
microspheres in the inventive molding material is preferably less than 0.4 
g/cm.sup.3. 
As has been stated hereinbefore, the choice of the particular filler is 
dependent on the intended use of the inventive molding material. The 
expert is well aware of the way and to the extent he can influence the 
characteristics of the molding material by the choice of the fillers (cf. 
also the examples given hereinafter). However, it has been found that when 
using the molding material according to the invention the expected effects 
frequently occur in a surprisingly marked form and to an above-average 
extent. 
Useful materials for component F are well known in the art. Thus it is 
possible to use as promoter or catalyst all known materials such as amines 
dibutyl tin dilaurate, tin mercaptate, etc. (cf. e.g. DE-OS No. 27 14 006, 
pp 20 and 21 and DE-PS No. 23 10 559, column 7), preference being given to 
tertiary amines. 
The production of the molding material according to the invention causes no 
particular problems and is brought about by bringing together and mixing 
components A, B and D as well as components C, E and F, if the latter are 
present. It is important that moisture is substantially excluded. The 
inventive molding material is therefore preferably produced in an 
atmosphere of a dried inert gas, such as nitrogen. When using hollow 
microspheres, it is generally necessary to dry these beforehand, e.g. for 
4 hours at 200.degree. C. As already stated above, it is important for 
achieving an adequate storage stability that the water content of the 
individual constituents of the inventive molding material is in all no 
more than about 0.2% by weight. 
The order in which the components of the inventive molding material are 
brought together is normally unimportant. In case of producing a 
one-component molding material (see below with regard to stability) it is 
however preferred to add the branched polyol at last. Further, when using 
hollow glass microspheres as filler, it has proven particularly 
advantageous if they are first introduced, followed by component B and/or 
C in random order and then the remaining constituents. As already 
mentioned above for component D, it is also preferred to prefabricate 
premix components C and D, if these components consist of mixtures of 
several constituents. 
The mixing of the constituents forming the inventive molding material can 
take place in conventional means, e.g. forced kneaders, double Z forced 
kneaders, planetary mixers, suitable extruders, drum mixers, Nauta 
mixtures etc. Kneading is continued until a homogeneous mass is obtained, 
which can be established by inspection on a glass disk under a microscope. 
Generally kneading times of 3 minutes are adequate. In case of a 200 liter 
batch, the maximum kneading time is generally no more than 15 minutes, but 
generally much shorter kneading times are adequate as a function of the 
materials used. 
The so produced homogeneous molding material has in the absence of 
component F a processing time (pot life) of 8 to 12 hours. Since this in 
practice is often too short, the molding material according to the 
invention is advantageously strongly cooled directly after its production 
and thereby frozen. This takes place by shock freezing to low 
temperatures. Temperatures around -18.degree. or -30.degree. C. have 
proven suitable, which lead to a stability of the molding material 
according to the present invention of about one month. After thawing to 
ambient temperatures the processing time is about one hour. 
Storage life and processing time of the molding material according to the 
invention can be substantially extended by producing a two-component 
molding material, component I comprising component A and component II 
comprising component B, and if present, component C. 
In particular components I and II have the following composition: 
Component I: 
1. 40 to 80% by weight component A, 
2. 10 to 20% by weight component D, 
3. 0 to 50% by weight component E and 
4. 0 to 5% by weight component F 
and 
Component II: 
1. 40 to 80% by weight component B, 
2. 0 to 20% by weight component C, 
3. 5 to 20% by weight component D, 
4. 0 to 50% by weight component E and 
5. 0 to 5% by weight component F, 
the weight percentages being based on the total amount of each of 
components I and II. 
The thus produced homogenous components I and II are filled with the aid of 
conventional devices (e.g. presses) in the usual way, e.g. into cartridges 
or containers (e.g. hobbocks). Filling can also take place into containers 
of aluminum composite film as well as of polyethylene or polypropylene, 
preference being given to polypropylene over polyethylene due to the lower 
water vapour permeability. 
Unless it is coloured for practical or esthetic reasons, the inventive 
molding material or its components I and II are colourless to white, low 
viscosity, putty-like to liquid materials. In case the inventive molding 
material is in the form of a two-component molding material, component I 
and component II are mixed with each other as homogeously as possible 
before processing, which mixing again takes place by using conventional 
devices. It is desirable that the mixtue of components I and II is a low 
viscosity putty-like material, i.e. it shall not flow but stand. However, 
it remains cold-workable and its viscosity is always sufficient to enable 
it to be pressed into the smallest honeycombs, e.g. with a key width of 
2.8 mm. The mixing ratio of components I and II is usually in the range of 
3:1 to 1:10. 
The advantage of the inventive molding material, especially in form of a 
two-component material, over the one-component molding material of prior 
application Ser. No. 24 026 is the quicker curing at room temperature or 
temperatures up to 80.degree. C. Thus at temperatures of 60.degree. to 
80.degree. C. curing usually is achieved within 15 minutes or less. At 
these temperatures the curing times of the one-component molding material 
according to prior application Ser. No. 24 026 are six hours and more. 
Due to the quick curing, which even takes place without the use of presses 
or autoclaves, the inventive molding material is not only useful as a 
construction material and especially a fire protecting construction 
material, which is advantageously used for the production and coating of 
molded parts and plate elements for the construction of land, air and 
water vehicles, but also particularly as repair material and especially a 
fire protection repair material with which the aforementioned molded parts 
and plate elements can be repaired. Thus it is now possible for the first 
time to repair damaged construction units or components in such a manner 
that they meet the requirements of international test standards like FAR 
25.853 and ATS 1000.001. 
Repair methods with mastics and honeycomb or prepreg substitutes are known. 
However, in case of phenol or epoxyresin prepregs the construction 
component has to be removed from the airplane and to be costly repaired in 
the aircraft works in the press at high pressure and temperatures of 
120.degree. to 170.degree. C. According to another method the repair is 
carried out with stiff or precured prepreg pads coated with a hot melt, 
which pads are ironed at 70.degree. to 80.degree. C. However, this 
procedure does not lead to such a great stability as it is obtained when 
using the inventive molding material. Further this method is only 
applicable to a limited extent with bent or otherwise formed construction 
components. Finally working at room temperature or temperatures up to 
60.degree. C. is also not possible. Furthermore exceeding the ironing 
temperature leads to adhesion problems. 
In contrast stable and optically unobjectionable repairs can be achieved 
with the inventive molding material alone (without prepreg pads) or 
covered with polyvinyl fluoride film pads (Tedlar films) and the like with 
or without heating (room temperature to 60.degree. C.). 
In addition construction components can be produced with the inventive 
molding material according to the OMC process (open mold compound) in 
which an open mold is lacquered and the lacquer is cured. In this mold the 
molding material is cured (room temperature to 80.degree. C.) and a 
construction component ready for the proposed end-use is obtained, i.e. no 
further finishing treatment is required. By this procedure a 
non-flammability for lacquer coatings of up to 200 .mu.m thickness is 
achieved which meets the test standards FAR 25.853 and ATS 1000.001. 
Another important advantage of the inventive molding material is that it is 
solvent-free. This facilitates to a considerable extent the processing 
thereof, because in view of the ever stricter regulations protecting the 
environment solvent-containing molding compounds lead to considerable 
additional costs. 
When curing the inventive molding material, the expert will obviously take 
account of the molding geometry and thermal conductivity and will choose 
the necessary curing time accordingly. Curing takes place at usual 
pressures, e.g. atmospheric pressure (pressures of about 0.5 to 50 bar 
normally being used). 
As indicated hereinbefore, the molding material according to the invention 
can be used in many ways, i.e. as a construction material and especially a 
fire protection construction material for the most varied purposes (a 
large number of possible applications for the inventive molding material 
are e.g. given in the paragraph bridging pp 25 and 26 of DE-OS No. 27 14 
006). Thus, the molding material according to the invention can be used 
for producing foams (rigid foams with bulk densities between 150 and 300 
kg/m.sup.3). A particularly important use is in the production of 
composite systems or sandwich structures constituted by surfaces made from 
glass fabric or carbon fibre prepregs and cores of molding compounds or 
foams with bulk densities of 150 to 1000 kg/m.sup.3. Particular reference 
is made in this connection to the processing of the inventive molding 
material in conjunction with the honeycomb materials especially used in 
aircrft building. The inventive molding material can be pressed into these 
honeycomb materials and then cured therein, which leads to moldings with a 
great hardness, compression strength and excellent fire protection 
characteristics. 
For many applications it is recommendable to combine the inventive molding 
material with glas or carbon fibre fabrics. Satin, linen, atlas, roving, 
unidirectional material and staple fibre fabrics are particularly suitable 
for this. Also fleeces and tubular braids can be used. Another suitable 
fabric material is constituted by aramide glass fibres or 
poly-(p-phenylene terephthalic amide)-carbon fibre fabric (re aramide and 
PPDT cf. e.g. Neue polymere Werkstoffe, 1969-1974, Carl Hanser Verlag, 
1975, chapters 9.1 and 9.2). As a function of the intended use such 
fabrics, fleeces or braids can be filled with the inventive molding 
material and then cured or can be applied externally to the molding 
material, followed by the curing of the latter. The latter can e.g. take 
place in such a way that a mold is lined with one of said fabrics, fleeces 
or braids and then the inventive molding compound is introduced and cured. 
This leads to an extremely stable union between the cured molding material 
and the fabric, fleece or braid. The introduced fabrics and fleeces have 
preferably weights of 50 to 600 g/m.sup.2 and mainly of 100 to 200 
g/m.sup.2. 
The products produced from the molding material according to the invention 
have excellent non-flammability characteristics, e.g. 10 mm thick plates 
without reinforcement withstand a fire test in the form of a five minute 
flame exposure (1080.degree. C.) to the extent that no dripping, 
afterflaming or burning through is observed. 
The inventive molding material is suitable as a filling mass and putty, as 
well as a coating material. However, the main use is in composite 
structures of fabrics and masses. Without going into detail, the most 
important uses are indicated: reinforcing sandwich panels and composite 
components in the aircraft industry, ships, railways and other vehicles 
(e.g. racing cars and tankers), where fire protection is required; for the 
car industry: engine enclosures, lining of engine cowlings for preventing 
carburettor fires and the like; building industry: fire inhibiting seals 
for wall opeings, closures for manholes, airconditioning shafts, cover 
plates, fire protection-walls, fillings for fire protection doors, or in 
an embodiment with a greater thickness of 30 to 50 mm as doors; linings or 
coverings of data protection cabinets and safes. 
The products obtained with the inventive molding material following the 
curing thereof can be sawn, milled, drilled, nailed, screwed, bonded and 
mechanically worked in any other way (cf. DE-OS No. 27 14 006, last 
paragraph on p 26, where processing examples are given which also apply to 
the inventive molding material). 
The inventive molding material can obviously also be processed in 
conjunction with the conventional aids used in the present technical field 
and these aids can be incorporated into the molding material or e.g. added 
during processing and curing. These aids are known to the expert, so that 
there is no need to illustrate them (cf. e.g. DE-OS No. 27 14 006, pp 20 
to 22). 
It is pointed out in this connection that it is particularly advantageous 
to cure the inventive molding material in union with polycondensation 
products, such as phenolic resins, where splitting off water occurs. It is 
also of interest that a curing action is obtained with excess monomers 
(e.g. styrene) of the laminates (prepreg components). The interaction with 
e.g. styrene leads to an extremely strong connection with the laminate. 
The aforementioned characteristics of the inventive molding material 
provide a considerably difference compared with the known molding 
compounds (e.g. DE-OS No. 27 14 006) and the commercially available edge 
and core filler materials based on epoxy resin, as well as formulations 
with phenolic resin components (see above), which either do not fulfil the 
requirements of ATS 1000.001 or the necessary bonding of prepregs to 
polycondensation products, such as phenolic resin masses, and furthermore 
cannot be cured at ambient temperature. 
It is finally pointed out that the inventive molding material, after 
curing, has a very good attachment, adhesive strength and compatibility 
with all commercially available plastics and even provides usable adhesion 
to polyolefins, Teflon (PTFE) and the like. Satisfactory adhesive 
strengths are also obtained on metal, so that the filling mass according 
to the invention can also be used for the construction of sandwich 
components with metal outer surfaces and a filling mass core or as 
coatings on metallic materials as structural fire protection layer. 
Suitable metallic materials are e.g. steel, aluminum etc. 
The following examples describing preferred embodiments are given for 
illustrative purposes only and are not meant to be a limitation on the 
subject invention. In all cases, unless otherwise noted, all parts and 
percentages are by weight.

EXAMPLE 1 
A one-component molding material of components A, B, C, D and E was 
prepared. 50 g of commercially available isocyanurate of 1,6-hexamethylene 
diisocyanate with a NCO content of 21.5% (hereinafer referred to only as 
isocyanurate), 5 g crude MDI with a NCO content of 31%, 12 g secondary 
ammonium phosphate, 1 g zeolite, 1 g pyrogenic silica and 28 g hollow 
glass microspheres with a density of 0.35 g/cm.sup.3 were mixed. Into the 
obtained mixture 50 g of a propoxylated trimethylolpropane with an OH 
content of 11.5% were homogeneously pugged. The resulting mixture had a 
processing time of about 8 hours. It was cured in a closed mold for 30 
minutes at 80.degree. C. The cured product had a bulk density of 650 
kg/m.sup.3 and a compression strength at ambient temperature of about 22 
N/mm.sup.2. 
EXAMPLE 2 
A two-component molding material was prepared by using the same components 
as in Example 1. Component I was prepared from 500 g propoxylated 
trimethylolpropane, 30 g hollow glass microspheres, 19 g secondary 
ammonium phosphate and 1 g zeolite. Component II was prepared from 500 g 
isocyanurate, 50 g crude MDI, 101 g secondary ammonium phosphate, 9 g 
zeolite, 10 g pyrogenic silica and 250 g hollow glass microspheres. 
Components I and II were prepared separately by homogeneously mixing the 
aforementioned components. In this maner two stable components were 
obtained, component II having a stability of 10 days at room temperature 
and 90 days at -18.degree. C. After mixing the two so produced components 
the resulting mixture had a processing time of about 8 hours. Curing took 
place as in Example 1 and the cured product had practically the same bulk 
density and compression strength as stated in Example 1. 
EXAMPLE 3 
Example 2 was repeated except that in component I the propoxylated 
trimethylol propane was replaced by 500 g of an oligomeric multifunctional 
glycolether with an OH content of 22%. After mixing components I and II 
the available processing time at ambient temperature was six hours. After 
curing in a closed mold for 30 minutes at 80.degree. C. a molded article 
having a bulk density of about 630 kg/m.sup.3 and a compression strength 
of about 19.5 N/mm.sup.2 was obtained. The curing of the mixture at 
ambient temperature required about 12 hours. 
EXAMPLE 4 
The procedure of Examples 2 and 3 was repeated but 500 g of an oligomeric 
difunctional polyesterol with an OH content of 2.0% were used as polyol. 
The processing time of the mixture of components I and II was about 12 
hours. Curing took place for 60 minutes at 80.degree. C. while the curing 
time at room temperature was about 36 hours. The cured product had a bulk 
density of about 655 kg/m.sup.3 and a compression strength at ambient 
temperature of about 14.2 N/mm.sup.2. 
EXAMPLE 5 
The procedure of Example 3 and 4 was repeated but 500 g of a branched 
polyalcohol with ether and ester groups with an OH content of 5% were used 
as polyol, said polyalcohol being a blockcopolymer according to definition 
(d) of component A (see above and compare claim 5). The mixture of 
components I and II provided a processing time of about 8 hours. Again 
curing could take place within 60 minutes at 80.degree. C. or within 24 
hours at ambient temperature. The cured product had a bulk density of 600 
kg/m.sup.3 and a compression strength at ambient temperature of about 14.8 
N/mm.sup.2. 
EXAMPLE 6 
The procedure of Examples 2 to 5 was repeated but 500 g saturated low 
molecular fatty-acid-modified, oligomeric polyesterol with an OH-content 
of about 5% were used as polyol. The processing time of the mixture of 
components I and II was about 12 hours. Again curing could take place 
within 60 minutes at 80.degree. C. or within 24 hours at ambient 
temperature. The cured product had a bulk density of 580 kg/m.sup.3 and a 
compression strength at ambient temperature of about 17 N/mm.sup.2. 
EXAMPLE 7 
A two-component mass was prepared from: 
Component I: 
60 g propoxylated trimethylolpropane (OH content=11.5%) 
10 g of a mixture of 
50% secondary ammonium phosphate, 
5% primary ammonium phosphate, 
20% azodicarbonamide, 
5% potassium silicate, 
10% calcium orthophosphate and 
10% CaO 
10 g carbon fibres with cutting length of 400 .mu.m 
10 g hollow glass microspheres with a density of 0.35 g/cm.sup.3 
2 g finely divided silica 
0.5 g dibutyl tin laurate and 
Component II: 
150 g isocyanurate 
20 g of a mixture of 80% crude MDI, 20% IPDI and 10% dimerized triazine of 
TDI, 
50 g of a mixture of 80% secondary ammonium phosphate, 15% zeolite and 5% 
finely divided silica, 
100 g hollow glass microspheres with a density of 0.40 g/cm.sup.3 
10 g carbon fibres with a cutting length of 100 .mu.m. 
The mixture of crude MDI, IPDI and dimerized triazine of TDI were produced 
in such a manner that IPDI and dimerized triazine of TDI were partially 
dissolved and partially finely suspended in the crude MDI 
Components I and II were homogeneously mixed and cured within two hours at 
40.degree. C. in a closed mold. The cured product had a bulk density of 
750 kg/m.sup.3. The compression strength at ambient temperature was 38 
N/mm.sup.2 after seven days and 52 N/mm.sup.2 after 30 days. At 80.degree. 
C. the compression strength after seven days was 12 N/mm.sup.2 and after 
30 days 19 N/mm.sup.2. 
EXAMPLE 8 
A two-component mass was prepared from: 
Component I: 
10 g fatty-acid-modified, oligomeric polyesterol with an OH content of 5%, 
3 g primary ammonium phosphate, 
1 g azodicarbonamide 
4 g foamed clay (NORPRIL 250) with a bulk density of 250 kg/m.sup.3, 
1 g hollow glass microspheres with a density of 0.35 g/m.sup.3 and 
Component II: 
60 g isocyanurate, 
5 g of a mixture of 80% crude MDI, 10% NDI and 10% of a copolymer triazine 
of TDI and HDI, 
1 g finely divided silica, 
14 g secondary ammonium phosphate 
0.1 g triethylamine, 
0.1 g dibutyl tin dilaurate, 
10 g cobweb-whiskers (XEVEX) 
10 g hollow glass microspheres with a density of 0.38 g/cm.sup.3 
The mixture of crude MDI, NDI and copolymeric triazine of TDI and HDI was 
produced like in Example 7 by partially suspending and dissolving NDI and 
copolymeric triazine of TDI and HDI in the crude MDI. 
The components were separately conveyed through a tandem unit with bucket 
piston pumps at about 80 to 120 bar (pipe diameter 30 mm) and 
homogeneously mixed in a mixing ratio of component I to component II of 
3:1 through a static mixer. Then curing took place for one hour at 
60.degree. C. in a closed mold. The cured product had a bulk density of 
680 kg/m.sup.3 and a compression strength at ambient temperature of 32.0 
N/mm.sup.2 after 14 days. 
EXAMPLE 9 
A two-component mass was produced from: 
Component I: 
80 g oligomeric multifunctional glycolether with an OH content of 22% 
20 g secondary ammonium phosphate and 
Component II: 
32 g isocuanurate 
8 g secondary ammonium phosphate. 
Components I and II were homogeneously mixed in a ratio of 2:5 and cured 
for 120 minutes at 80.degree. C. in a closed form. The cured product had a 
bulk density of 1300 kg/m.sup.3 and a compression strength at ambient 
temperature of 40 N/mm.sup.2 or at 80.degree. C. of 6.5 N/mm.sup.2. 
EXAMPLE 10 
Two-component molding masses were produced as in Example 2 except for the 
addition of different amounts of promoters: 
a. Example 2+0.2 g DBTDL 
b. Example 2+0.2 g DBTDL+0.1 g TEA 
c. Example 2+0.8 g DBTDL 
DBTDL=dibutyl tin dilaurate 
TEA=triethylamine 
The properties of the mixtures of components I and II and the obtained 
cured products are summarized in the following table: 
______________________________________ 
(a) (b) (c) 
______________________________________ 
Bulk density (kg/m.sup.3) 
680 640 610 
Processing time at 
2 h 20 min 5 min 
ambient temperature 
Compression strength 
18.0 19.2 34.5 
at ambient temperature 
after two days: (N/mm.sup.2) 
at ambient temperature 
22.8 25.4 36.8 
after 30 days (N/mm.sup.2) 
______________________________________