Textured polyurethane molded articles having multiple sheet layers

The present invention deals with textured, molded articles having multiple sheet layers, comprising: PA1 a) an outer coating layer; PA1 b) a middle layer of a urethane and/or urea group containing film prepared from a heat curable composition storage stable at room temperature; and PA1 c) a backing layer of non-cellular or cellular polyurethane which optionally can contain an insert and/or reinforcing material. Moreover, the invention deals with a process for the preparation of said polyurethane molded articles and their use.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention deals with textured polyurethane molded articles 
having multiple sheet layers, which comprise: 
a) an outer coating layer; 
b) a middle layer of a sheet containing urethane groups and/or urea groups 
prepared from a heat curable composition which is storage stable at room 
temperature; and 
c) a backing layer made from noncellular or cellula polyurethane which 
optionally contains an insert and/or reinforcing material. 
2. Description of Related Art 
The preparation of molded foam from polyisocyanate addition polymerization 
products, for example, from hot or cold molded, or integral skin foams is 
the subject of numerous patents and publications. Specific examples are: 
Advances in Urethane Science and Technology, Vol. 1 through 8, K. C. 
Frisch et al, Technomic Publishing Company, Inc., 1971 through 1981; the 
Monograph of J. H. Saunders and K. C. Frisch High Polymers, Vol. XVI, 
Polyurethanes parts 1 and 2, Verlag Interscience Publishers, 1962 and 
1964; or Integral Skin Foams by H. Piechota and H. Roehr, Carl 
Hanser-Verlag, Munich and Vienna, 1975. 
If the molded articles made from integral skin foams are not used as, for 
example, construction elements in the interior of motor vehicles, then the 
molded foams must be provided with a decorative surface, for example, 
woven material from plastic or natural fibers or thermoplastic films. The 
decorative layer can be bonded, for example, with a core layer. Following 
another process technology, preformed covering materials can be foamed in 
place. There are basically two methods available for achieving this. Gas 
impervious covering materials or films are deep drawn in closed molds; or 
single component or dual component coatings are injected into the mold 
according to the in mold coating process. After either processing 
variation, the covering material or the coating layer is subsequently 
foamed in place (Plastics Handbook, Vol. 7 "Polyurethanes", second edition 
1983 edited by G. Oertel, Carl Hanser-Verlag, Munich and Vienna). 
Typical predominantly used covering materials are polyvinyl chloride (PVC) 
films or PVC/acrylonitrile-butadiene-styrene (ABS) copolymer films. 
However, such plastic films have many disadvantages. For achieving the 
required product applications, material properties such as for example, 
tear propagation strength, tear elongation, or the correct feel, the PVC 
or PVC/ABS films generally must be modified by adding plasticizers such as 
for example, phthalic acid esters. For assuring the necessary thermal 
stability of approximately 130.degree. C., the aforesaid films must be 
equipped with heavy metal stabilizers. The plasticizers used either 
contain, or after curing form volatile constituents which lead to the 
undesired formation of a coating, particularly on windows, for example the 
so-called fogging. 
As the plasticizer bleeds out over the course of time, the films become 
rigid, brittle and cracked. Another serious disadvantage is based on the 
mutual negative influence of PVC and/or PVC/ABS films with poured in place 
polyurethanes; particularly if the polyurethane foams are prepared in the 
presence of conventional amine catalysts which results in the rapid 
embrittlement of the decorative layer. In addition, a problem is the 
recycling of PVC waste and the formation of HCl in fires. 
Numerous experiments were aimed at replacing PVC or PVC/ABS films by other 
suitable materials such as, for example, films of thermoplastic 
polyurethanes (TPU). Since TPU films after deep drawing exhibit the 
so-called memory effect, i.e. in deep drawing the desired, needled upper 
surface structure is lost, their use did not lead to the desired success. 
Textured polyurethane films such as for instrument panels, indeed can be 
manufactured from TPU powder employing a powder sintering process. 
However, since this method necessitates a significant energy requirement, 
it is unprofitable and normally only leads to certain light fast 
polyurethane films. 
Textured polyurethane films prepared according to the dual component 
thermosetting process overcome this disadvantage as seen in 
Kunststoffberater 32, pages 27 through 28, October, 1987, Booklet 10. With 
the help of this process, molded articles can be obtained having a natural 
surface structure such as for example, leather grain, seams, etc. The 
exact proportioning of the polyol and polyisocyanate components pose 
difficulties in this production process since even small fluctuations in 
the mix ratio of the starting components lead to a sharp decline in the 
mechanical properties, particularly in the thermal stability of the films 
prepared. Moreover, preruns and postruns lead to a significant loss of 
material. 
SUMMARY OF THE INVENTION 
The object of the present invention was to develop suitable textured films 
which had none or only a minor degree of the aforesaid disadvantages and 
which could be foamed in place or filled with mixtures to form cellular or 
noncellular polyurethanes. 
This object was surprisingly met with the help of a textured, urethane 
group and/or urea group-containing film which is prepared from a heat 
curable mixture which is storage stable at room temperature and which can 
be used as the middle layer (b) for forming the polyurethane molded 
article. 
Accordingly the subject of the present invention is a textured, multiple 
sheet, layered polyurethane molded article, comprising: 
a) an outer coating layer; 
b) a middle layer of a sheet containing urethane and/or urea groups; and 
c) a backing layer made from noncellular or cellular polyurethane which 
optionally contains an insert and/or reinforcing material; 
wherein the middle layer (b) comprising a sheet containing urethane and/or 
urea groups is prepared by curing at 60.degree. C. to 150.degree. C. a 
heat curable mixture, storage stable at room temperature, which comprises: 
i) an organic polyisocyanate; 
ii) at least one compound having two hydrogen atoms reactive to isocyanate 
groups and having an average molecular weight of 250 to 8500; 
whereby a room temperature solid organic polyisocyanate (i), in the form of 
distinct particles having a particle diameter of 0.1 to 150 microns, is 
deactivated on the particle surface by a chemical reaction with a 
deactivating agent so that from 0.1 to 20 equivalent percent of the total 
available isocyanate groups from (i) are reacted with the deactivating 
agent and the resulting surface modified polyisocyanate is dispersed into 
at least one compound having two hydrogen atoms reactive to isocyanate 
groups; 
iii) chain extending agents and/or crosslinking agents having an average 
molecular weight of 62 to 500 and having an average functionality of 2 to 
4 and; 
iv) catalysts. 
The subject of the present invention is also a process for the preparation 
of textured multiple sheet layered molded articles, comprising: 
a) an outer coating layer; 
b) a middle layer of a sheet containing urethane and/or urea groups; and 
c) a backing layer made of noncellular or cellular polyurethane which 
optionally contains an insert and/or reinforcing material wherein the 
coating layer is applied to the textured inside of a mold heated to from 
60.degree. to 150.degree. C. 
After the coating layer achieves a sufficient viscosity, it is coated with 
a heat curable composition, comprising: 
i) an organic polyisocyanate; 
ii) at least one compound having two hydrogen atoms reactive to isocyanate 
groups and having an average molecular weight of 250 to 8500; 
whereby a room temperature solid organic polyisocyanate (i), in the form of 
distinct particles having a particle diameter or 0.I to 150 microns, is 
deactivated on the particle surface by a chemical reaction with a 
deactivating agent so that from 0.1 to 20 equivalent percent of the total 
available isocyanate groups from (i) are reacted with the deactivating 
agent and the resulting surface modified polyisocyanate is dispersed into 
at least one compound having two hydrogen atoms reactive to isocyanate 
groups; 
iii) chain extending agents and/or crosslinking agents having an average 
molecular weight of 62 to 500 and having an average functionality of 2 to 
4 and; 
iv) catalysts. 
The composition is allowed to cure and then the multiple layered film 
formed is treated with a reactive, blowing agent-containing or blowing 
agent-free mixture to form the polyurethane, or the film formed is taken 
out of the mold and then directly or following interim storage, is treated 
in a separate processing step with a reactive, blowing agent-containing or 
blowing agent-free mixture to form the polyurethane and finally the 
textured multiple sheet layered polyurethane articles of claim 1 are used 
as construction elements in the automobile industry, preferably as 
instrument panels or as coverings for doors or as compartment shelves in 
automobiles.

DESCRIPTION OF THE PREFERRED EMBODIMENT 
The polyurethane molded articles of the present invention demonstrate 
clearly improved light stability and excellent thermal stability. Even at 
a temperature of 130.degree. C. and over 500 hours no significant 
discoloration of the molded article occurs. The urethane and/or urea group 
containing films retain their original extensibility. A particular 
advantage is that poured in place molded articles, unlike molded articles 
poured in place with PVC or PVC/ABS films, demonstrate no negative 
interaction between the polyurethane foam of the poured in place foaming 
and the film, i.e. the molded articles do not become brittle and they 
possess excellent film-polyurethane foam-adhesion. Moreover, the films of 
the middle layer (b) can, for example, be pigmented and in this manner 
they can be adjusted to the color tone of coating layer (a). 
The following pertains to the starting components for the preparation of 
said molded articles as well as for the preparation of the urethane and/or 
urea group containing sheet used as middle layer (b): 
1) For achieving an essentially light stable surface, said polyurethane 
molded articles are provided with a covering layer made of a coating. 
Suitable, preferably quick curing coating systems, are applied to the 
surface of the mold, efficaciously heated, and treated with a release 
agent. Typical examples are polyester coatings which are partially solvent 
free and therefore dry quickly; epoxide coatings which have a high hiding 
power, as do polyester coatings; and preferably polyurethane coatings 
which demonstrate excellent adhesion due to their chemical relationship to 
urethane and/or urea groups; whereby the bonding to the films occurs 
partially via reactant groups in the film. The polyurethane coatings are 
normally solvent free, demonstrate a good mechanical property level and 
most preferably, have a high elasticity. For shortening the drying times, 
the polyurethane coatings are efficaciously dried at 60.degree. C. to 
150.degree. C., more preferably, 80.degree. C. to 110.degree. C. 
Release coatings are also suitable for forming coating layer (a) which on 
one hand demonstrate good adhesion to the urethane and/or urethane group 
containing films however, on the other hand, they do not adhere to the 
mold material. These release coatings are applied to the surface of the 
mold in a conventional fashion for example, preferably by spraying and 
thus one can dispense with an additional release agent. 
The outer covering layer (a) efficaciously has a thickness of 0.01 to 200 
microns, more preferably 0.4 to 100 microns, whereby the coating system is 
applied in a quantity of 0.15 to 60 g/m.sup.2, more preferably 6 to 30 
g/m.sup.2, calculated as a solvent free dried composition. 
2) Middle layer (b) of the molded article in this invention comprises a 
film containing urethane and/or urea groups which is prepared by curing at 
60.degree. C. to 150.degree. C., more preferably 80.degree. C. to 
130.degree. C., a heat curable composition storage stable at room 
temperature which comprises: 
i) an organic polyisocyanate; 
ii) at least one compound having two hydrogen atoms reactive to isocyanate 
groups and having an average molecular weight of 250 to 8500; 
whereby a room temperature solid organic polyisocyanate (i), in the form of 
distinct particles having a particle diameter of 0.1 to 150 microns, is 
deactivated on the particle surface by a chemical reaction with a 
deactivating agent so that from 0.1 to 20 equivalent percent of the total 
available isocyanate groups from (i) are reacted with the deactivating 
agent and the resulting surface modified polyisocyanate is dispersed into 
at least one compound having two hydrogen atoms reactive to isocyanate 
groups; 
iii) chain extending agents and/or crosslinking agents having an average 
molecular weight of 62 to 500 and having an average functionality of 2 to 
4 and; 
iv) catalysts. 
Suitable room temperature storage stable, heat curable compositions of the 
aforesaid type are known and are disclosed, for example, in EP-A-0 062 780 
(U.S. Pat. No. 4,400,497), EP-A-0 100 507 (U.S. Pat. No. 4,507,456) and 
EP-A-0 100 508 (U.S. Pat. No. 4,525,570). 
The following starting materials are efficaciously used in preparing said 
compositions: 
Typical organic polyisocyanates (i) are conventional, commercially readily 
available, aliphatic, cycloaliphatic, aromatic, cycloaliphatic-aliphatic, 
and aromaticaliphatic multivalent isocyanates which as long as their 
melting point is not over 30.degree. C., are efficaciously modified by 
suitable methods. 
Individual examples are: alkylene diisocyanates having 2 to 12, more 
preferably 4 to 6, carbon atoms in the alkylene radical such as 1,2-ethane 
diisocyanate; 1,4-butane diisocyanate; 2-ethyl-1,4-butane diisocyanate; 
2-methyl-1,5-pentane diisocyanate; 1,6-hexane diisocyanate; 
2-ethyl-1,6-hexane diisocyanate; 1,8-octane diisocyanate; 1,10-decane 
diisocyanate; and 1,12-dodecane diisocyanate; cycloaliphatic diisocyanates 
such as for example, 1,3- and 1,4-cyclohexane diisocyanate as well as 
optional mixtures of their isomers 4,4'-, 2,2'- and 
2,4'-dicyclohexylmethane diisocyanate; as well as optional mixtures of at 
least two of these isomers; arylaliphatic diisocyanates such as for 
example, 1,2-, 1,3- and 1,4-xylylene diisocyanate and 
2,3,5,6-tetramethyl-1,4-xylylene diisocyanate, and aromatic 
polyisocyanates such as for example, 4,4'-, 2,4'- and 
2,2'-diisocyanatodiphenylmethane and the corresponding mixtures of at 
least two of these isomers, 2,4- or 2,6-diisocyanatotoluene and the 
corresponding isomeric mixtures, 1,5-diisocyanatonaphthalene, polyphenyl 
polymethylene polyisocyanates and mixtures of the isomeric 
diisocyanatodiphenylmethanes and polyphenyl polymethylene polyisocyanates. 
The aforesaid diand polyisocyanates can be used individually or in the form 
of mixtures. 
The so-called modified multivalent isocyanates are also suitable, i.e. 
products which are obtained by the chemical reaction of the 
above-mentioned di- and/or polyisocyanates. Individual examples are, room 
temperature solid di- and/or polyisocyanates containing ester, urea 
biuret, allophonate, carbodiimide, and preferably urethane, uretdione, 
and/or isocyanurate groups. 
Room temperature solid di- and/or polyisocyanates which are primarily 
insoluble in the compounds having at least two reactive hydrogen atoms 
(ii) or which are only soluble in small quantities, which have been used 
successfully and are therefore preferred are 
4,4'-diisocyanatodiphenylmethane and 1,5-naphthalene diisocyanate and 
diand/or polyisocyanates modified with urea, urethane uretdione ester 
and/or isocyanurate groups, based on 1,6-hexane diisocyanate, 
1-isocyanato-3,3,5-trimethyl-5-(isocyanato-methyl)cyclohexane, 
2,3,5,6-tetramethyl-1,4-xylylene-diisocyanate, 2,4'- and 
4,4'-diisocyanatodiphenylmethane and most preferably 2,4- and/or 
2,6-diisocyanatotoluene. 
Modified polyisocyanates of the preferred type are most preferably addition 
products of diisocyanatotoluenes and trimethylolpropane, trimerized 
isocyanurate group-containing diisocyanatotoluenes and 
diisocyanatodiphenylmethanes and dimerized uretdione group-containing 
diisocyanatotoluenes, 4,4'- and/or 2,4'-diisocyanatodiphenyl methanes as 
well as diisocyanato aryl ureas having the following general structural 
formula: 
##STR1## 
in which R is a lower molecular weight, linear or branched alkyl radical 
having I to 4 carbon atoms, for example, methyl; alkoxy having 1 to 4 
carbon atoms, for example, ethoxy; or a halogen atom, for example, 
chlorine; and diisocyanato benzoic acid phenyl esters having the following 
general structural formula: 
##STR2## 
Most preferred are modified diisocyanates containing uretdione groups in 
bonded form based on 2,4- and/or 2,6 diisocyanatotoluene, 2,4'- and/or 
4,4'-diisocyanatodiphenylmethane, 1,6-hexanediisocyanate and 
1-isocyanato3,3,5-trimethyl-5-(isocyanato-methyl)cyclohexane, whereby in 
the preparation of light-fast films, most preferably compositions based on 
aliphatic or cycloaliphatic modified diisocyanates as well as 
2,3,5,6-tetramethyl-1,4-xylylene diisocyanate are used. The organic and/or 
modified organic polyisocyanates (i) can be used individually or in the 
form of mixtures. 
Compounds having at least two reactive hydrogen atoms are preferably those 
having a functionality of 2 to 8, more preferably, 2 to 4 and most 
preferably 2 and/or 3, and have a molecular weight from 250 to 8500, more 
preferably 600 to 5600, and most preferably 1800 to 4000 whereby as a 
function of, for example, the structure, molecular weight, and the 
functionality of the compounds, the final products containing urethane 
and/or urea groups made from the foam compositions can be varied in a 
conventional fashion from flexible to brittle hard. Particularly suitable 
are, for example, polyether polyamines, hydroxyl group containing 
polyether polyamines and/or more preferably polyols selected from the 
group consisting of polyether polyols, polymer modified polyether polyols, 
polyester polyols, polythioether polyols, hydroxyl group containing or 
hydroxyl group free polyester amides, hydroxyl group containing 
polyacetals and hydroxyl group-containing aliphatic polycarbonates or 
mixtures of the polyether polyamines and polyols or mixtures of at least 
two of the aforesaid polyols. Preferably used are polyester polyols and/or 
most preferably polyether polyols. 
Suitable polyester polyols may be prepared, for example, from organic 
dicarboxylic acids having from 2 to 12 carbon atoms, preferably aliphatic 
dicarboxylic acids having from 4 to 6 carbon atoms, and polyfunctional 
alcohols, for example, diols having from 2 to 12 carbon atoms, preferably 
from 2 to 6 carbon atoms. Typical dicarboxylic acids are: succinic acid, 
glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 
decanedicarboxylic acid, maleic acid, and fumaric acid. The dicarboxylic 
acids may be used individually or as mixtures Instead of the free 
dicarboxylic acids, corresponding dicarboxylic acid derivatives may also 
be used, for example, the dicarboxylic acid esters of alcohols having from 
1 to 4 carbon atoms or dicarboxylic anhydrides. Preferred are dicarboxylic 
acid mixtures of succinic, glutaric, and adipic acid in proportions of, 
for example, 20-35:35-50:20-32 parts by weight, respectively, and most 
preferably adipic acid. Examples of difunctional and polyfunctional 
alcohols, in particular diols, are: ethanediol, diethylene glycol, 1,2- 
and/or 1,3-propanediol, dipropylene glycol, 1,4-butanediol, 
1,5-pentanediol, and 1,6-hexanediol, or mixtures of at least two of the 
cited diols, more preferably mixtures of 1,4-butanediol, 1,5-pentanediol, 
and 1,6-hexanediol. In addition, polyester polyols of lactones, for 
example, .epsilon.-caprolactone, or hydrocarboxylic acids, for example, 
.omega.-hydroxycaproic acid may be used. 
The polyester polyols preferably have a functionality of from 2 to 3 and a 
molecular weight of from 1000 to 3000, preferably from 1800 to 2500. 
Preferred for use as polyols are polyether polyols prepared by anionic 
polymerization of cyclic ethers with alkali hydroxides as catalysts, for 
example, sodium hydroxide or potassium hydroxide, or alkali alcoholates, 
for example, sodium methylate, sodium or potassium ethylate, or potassium 
isopropylate, or by the cationic polymerization with Lewis acids such as 
antimony pentachloride, boron trifluoride etherates, etc., or bleaching 
earth as catalysts. Preferably used as alkylene oxides are those having 
from 2 to 4 carbon atoms in the alkylene radical. The preferred initiator 
molecule contains from 2 to 8, preferably from 2 to 4, reactive hydrogen 
atoms bonded to it. 
Suitable cyclic ethers are, for example, tetrahydrofuran, styrene oxide, 
and epichlorohydrin, and alkylene oxides such as 1,2- and 2,3-butylene 
oxide, and preferably ethylene oxide and 1,2-propylene oxide. The cyclic 
ethers may be used individually, alternating one after another, or as 
mixtures. Typical initiator molecules which may be used are: water, 
organic dicarboxylic acids such as succinic acid, adipic acid, phthalic 
acid, and terephthalic acid. Aliphatic and aromatic, optionally N-mono-, 
N,N- and N,N'-dialkyl substituted diamines having from 1 to 4 carbon atoms 
in the alkyl radical, such as optionally mono- and dialkyl-substituted 
ethylene diamine, 1,4-butylenediamine, 1,2-, 1,3-, 1,4-, 1,5- and 
1,6-hexamethylenediamine, phenylene diamine, 2,4- and 2,6-toluylene 
diamine and 4,4'-, 2,4'- and 2,2'-diaminodiphenylmethane can be utilized. 
Typical initiators which may be used are alkanol amines such as 
ethanolamine, diethanolamine, N-methyl- and N-ethylethanolamine, N-methyl- 
and N-ethyl-diethanolamine, and triethanolamine, ammonia. Preferably used 
are polyfunctional, more preferably di- and/or trifunctional alcohols such 
as ethanediol, 1,2-propanediol and 1,3-propanediol, diethylene glycol, 
dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, 
trimethylolpropane, pentaerythritol, sorbitol, sucrose, and saccharose. 
The polyether polyols, preferably polyoxypropylene-, 
polyoxypropylene-polyoxyethylene- and polyoxytetramethylene-glycols have a 
functionality of from 2 to 4 and molecular weights from 250 to 8500, more 
preferably from 600 to 5600, most preferably from 1800 to 4000. As with 
the polyester polyols, they may be used individually or in the form of 
mixtures. They may also be mixed with the polyester polyols as well as the 
hydroxyl group-containing polyesteramides, polyacetals, polycarbonates, 
and/or polyetherpolyamines. 
Polymer modified polyether polyols or mixtures of polyether polyols and 
polymer modified polyether polyols may also be used in place of the 
aforesaid polyether polyols. Suitable polymer modified polyether polyols 
contain efficaciously 2 to 50 weight percent, or preferably 3 to 25 weight 
percent, based on the total weight, of inorganic fillers such as, for 
example, kaolin or aluminum oxide; organic fillers such as, for example, 
carbon, rosin or melamine or polymer particles whereby the polymer 
particles preferably are selected from the group consisting of polyureas, 
polyhydrazides, polyurethanes containing tertiary amino groups in bonded 
form, and graft polymers which preferably are prepared by the in situ 
polymerization of olefinic unsaturated monomers, most preferably styrene 
and/or acrylonitrile in the above-mentioned polyether polyols. Examples of 
such polymer modified polyether polyols and processes for their preparation 
are disclosed in EP-B 00 11 752 (U.S. Pat. No. 4,304,708), U.S. Pat. No. 
4,374,209 and DE-A-32 31 497. 
Typical hydroxyl group-containing polyacetals which may be used are 
compounds which may be produced from glycols such as diethylene glycol, 
triethylene glycol, 4,4'-dihydroxyethoxy-diphenyldimethylmethane, 
hexanediol, and formaldehyde. Suitable polyacetals may also be prepared 
through the polymerization of cyclic acetals. 
Typical hydroxyl group-containing polycarbonates which may be used are 
those of the essentially known type which may be prepared through the 
reaction of diols such as 1,3-propanediol, 1,4-butanediol, and/or 
1,6-hexanediol, diethylene glycol, triethyleneglycol, or tetraethylene 
glycol with diaryl carbonates such as diphenyl carbonate, or phosgene. 
Among the polyester amides which may be used are, for example, those 
obtained from polyfunctional saturated and/or unsaturated carboxylic acids 
or their anhydrides and polyfunctional saturated and/or unsaturated amine 
alcohols or mixtures of polyfunctional alcohols and amine alcohols and/or 
polyamines, preferably linear condensates. 
Suitable polyether-polyamines may be prepared from the polyether polyols 
cited above. Examples of preparation methods are the cyano-alkylation of 
polyoxyalkylene polyols and the subsequent hydrogenation of the nitrile 
which is formed (U.S. Pat. No. 3,267,050) or the amination of 
polyoxyalkylene polyols with amines or ammonia in the presence of hydrogen 
and catalyst (Federal Republic of Germany Patent No. 12 15 373) whereby the 
hydroxyl groups are either partially or completely aminated. 
The storage stable, heat curable compositions of the present invention 
comprising an organic polyisocyanate (i), at least one compound having 
reactive hydrogen atoms (ii), chain extending agents and/or crosslinking 
agents (iii) and catalysts (iv) contain the polyisocyanates (i) in the 
form of discrete particles having particle diameters of 0.1 to 150 
microns, more preferably, 1 to 50 microns, dispersed in (ii), or in (ii) 
and (iii). 
In order to prevent an addition polymerization reaction at room temperature 
between the organic polyisocyanates and starting components (ii) and (iii) 
the dispersed polyisocyanate particles are deactivated on their surface. 
The deactivating agent is efficaciously chosen so that chemical or 
physical forces are associated with the surface of the polyisocyanate 
particles and in this manner phase separation is achieved between 
deactivated polyisocyanate particles and the remaining starting components 
(ii) through (iv). 
For the chemical deactivation, 0.01 to 20, more preferably 0.1 to 10 and 
most preferably 0.3 to 5 equivalent percent of the total available 
isocyanate groups are reacted with the deactivating agent. 
In addition, the deactivating agent can be added to the formulations in the 
claimed equivalent ratios. Also suitable is a process in which the 
deactivating agent is added in an excess over the claimed equivalent 
ratio. 
After coating the surface of the dispersed phase with the deactivating 
agent the deactivating reaction is terminated. 
Typical deactivating agents are: water, primary or secondary aliphatic 
mono- or polyamines, mono- and polyalcohols. Most preferred are longer 
chain aliphatic monoamines, for example, stearyl amine which react into a 
type of grafted emulsifier. Higher molecular weight aliphatic polyamines 
such as, for example, polyamide amines and hydroxyl terminated polymers 
such as, for example, hydroxyl terminated polybutadienols react to form 
grafted protective colloids. Most preferred for deactivating the 
isocyanate groups on the surface of the polyisocyanate particles, i.e. for 
stabilizing dispersions of components (i) through (iii), are also reactions 
which convert the isocyanates into urea and/or polyurea structures because 
these are insoluble in most polyols and organic solvents. Reagents forming 
ureas and/or polyureas are water and primary or secondary aliphatic amines 
whereby short chain aliphatic diamines such as ethylene diamine or 
propylene diamine are preferred. The polyureas formed from these short 
chain aliphatic diamines are more organophobic than those formed from long 
chain amines and therefore possess a better stabilizing effect in many 
instances. 
Other deactivating agents are: compounds containing carboxyl groups such 
as, for example, homo- and co-polymers of acrylic acid, methacrylic acid, 
maleic acid, and other polymerizable acids, acidic polycondensation 
products such as for example, polyesters prepared with an excess amount of 
acid, acidic polymers obtained by the reaction of adducts of maleic acid 
anhydride with unsaturated polymers, for example, linseed oil or 
hydroxyl-terminated polybutadiene polymers; amide group containing 
compounds such as, for example, soluble polyamides and polymers of 
acrylamide and methacrylamide or copolymers of acrylamide and/or 
methacrylamide with acrylic acid and/or methacrylic acid esters. 
Reaction products are preferably used as deactivating agents which are 
prepared by reacting one mole of a primary organic amine having 2 to 32, 
more preferably 6 to 18 carbon atoms selected from the group consisting of 
aromatic, aliphatic, cycloaliphatic, cycloaliphaticaliphatic and 
aromatic-aliphatic diamines or mixtures thereof with 1.5 to 2.5 moles, 
more preferably 1.8 to 2.2 moles and most preferably about 2 moles of an 
organic monocarboxylic acid having at least 6 carbon atoms, more 
preferably 12 to 36 carbon atoms and most preferably 12 to 18 carbon atoms 
at a temperature in a range of approximately 10.degree. C. to 100.degree. 
C., more preferably 20.degree. C. to 80.degree. C. 
Examples of suitable primary organic amines are: linear or branched 
aliphatic diamines having 2 to 12, more preferably 6 to 12 carbon atoms 
such as for example, 1,2-ethylenediamine, 1,2- and/or 
1,3-propylenediamine, 1,4-butylenediamine, 
4-methyl-pentamethylene-1,5-diamine, 1,5-pentamethylene-diamine, 
2,2,4-trimethyl-hexamethylene-1,6-diamine, 1,6-hexamethylene-diamine, 
1,8-octamethylenediamine, 1,10-decamethylene-diamine and 
1,12-dodecamethylene-diamine; cycloaliphatic diamines having 6 to 10 
carbon atoms such as for example, cyclohexane-diamines as well as optional 
mixture of the isomers, 2,4- and/or 2,6-hexahydrotoluylenediamine and 
isophorone diamine; cycloaliphatic-aliphatic diamines having 8 to 32 
carbon atoms, more preferably, 13 to 21 carbon atoms such as for example, 
1,4-hexahydroxylxylylene diamine, 4,4'-,2,4'-, and 
2,2'-dicyclohexylmethane diamine as well as optional mixtures of the 
isomers, 3,3'-dialkyl- and 3,3',5,5'-tetraalkyl-4 4'-dicyclohexylmethane 
diamines having from 1 to 4 carbon atoms in a linear or branched alkyl 
radical such as, for example, 3,3'-dimethyl-, 3,3'-isopropyl-, 
3,3',5,5'-tetramethyl-, 3,3',5,5'-tetraethyl- or 
3,3',5,5-isopropyl-4,4'-diaminodicyclohexylmethane; aromatic diamines 
having 6 to 12 carbon atoms such as, for example, phenylenediamines, 2,4- 
and 2,6-toluylenediamine and the corresponding isomeric mixtures and 
naphthalenediamines and aromatic-aliphatic diamines having 8 to 32 carbon 
atoms, more preferably, 13 to 21 carbon atoms such as, for example, 
xylylenediamine, 4,4'-, 2,4'- and 2,2'-diamino-diphenylmethane, 
3,3'-dialkyl- and 3,3',5,5'-tetraalkyl-4,4'-diamino-diphenylmethane, 
having 1 to 4 carbon atoms in a linear or branched alkyl radical such as, 
for example, 3,3'-dimethyl-, 3,3'-diethyl-, 3,3',5,5'-tetramethyl-, 3,3 
',5,5'-tetraethyl-, 3,3',5,5'-tetraisopropyl-, 
3,5-dimethyl-3',5'-diethyl-, and 
3,5-dimethyl3',5'-diisopropyl-4,4'-diamino-diphenylmethane and 4,4'- 
diaminodiphenyl-2,2-propane. The aforementioned organic primary diamines 
can be used individually or in the form of mixtures. Preferably used are 
aliphatic, cycloaliphatic or cycloaliphatic-aliphatic primary diamines 
having 6 to 21 carbon atoms. 
Aromatic monocarboxylic acid or their anhydrides are examples of organic 
monocarboxylic acids having at least 6 carbon atoms, more preferably 12 to 
36 carbon atoms, such as for example, benzoic acid, o-, m-, p-toluic acid 
and/or anisic acid. The aromatic monocarboxylic acids can optionally be 
substituted partially or completely by an equivalent quantity, with 
respect to the carboxyl groups, of a polycarboxylic acid such as for 
example, phthalic acid, trimellitic acid or pyromellitic acid or their 
anhydrides. 
However, most preferred are aliphatic or cycloaliphatic, saturated or 
unsaturated carboxylic acids or their anhydrides having preferably at 
least 12 to 36 carbon atoms and most preferably 12 to 18 carbon atoms. 
Typical examples are natural or synthetic monocarboxylic acids and/or 
natural fatty acid mixtures such as for example, abietic acid, palmitic 
acid, stearic acid, oleic acid, elaidic acid, linoleic acid, ricinoleic 
acid, linolenic acid or even commercially produced fatty acid mixtures 
such as sperm oil fatty acid, fish oil fatty acid, tallow fatty acid, 
soybean oil fatty acid, palm nut oil fatty acid, peanut oil fatty acid or 
talloleic fatty acid. Preferred -are stearic acid and/or fatty acids 
liquid at room temperature, most preferably, oleic acid or industrial 
fatty acid mixtures containing oleic acid. 
Aryl sulfonic acids such as, for example, benzene sulfonic acids and/or 
toluene sulfonic acids are also examples. 
The reaction products used as the deactivating agent preferably are present 
as salts. However, also suitable are carboxylic acid amides prepared from 
the diamines and monocarboxylic acids and the carboxylic acid amides 
containing salt residues and mixtures from the previously mentioned 
carboxylic acid amides and salts whereby the quantity ratios of the 
individual components can be varied over a broad range. 
Reaction products which have been used successfully and are therefore 
preferred as the deactivating agent are prepared from 1 mole of 
3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and from about 2 moles of 
stearic acid and/or most preferably, oleic acid. 
The storage stable, heat curable compositions contain other compounds which 
are reactive with the isocyanate groups and they are chain extending agents 
and/or crosslinking agents (iii) having an average molecular weight of 62 
to 500, more preferably, 62 to 300 and having a functionality of 2 to 4, 
more preferably 2 to 3 and efficaciously they have either hydroxyl groups 
in bonded form on the aliphatic and/or cycloaliphatic radicals, and/or 
amino groups in bonded form on the aromatic radicals. Typical examples of 
such chain extending agents or cross linking agents are: multivalent 
alcohols with primary and/or secondary hydroxyl groups in bonded form on 
the aliphatic or cycloaliphatic radical such as, for example, 1,2 
ethanediol, 1,2- and 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 
1,3-,1,4- and 2,3-butanediol, 1,5- and 2,5-pentanediol, 1,6-hexanediol, 
1,4-bis-(hydroxymethyl)-cyclohexane, 1,4-dihydroxycyclohexane, 
1-hydroxymethyl-4-hydroxycyclohexane, 4,4'-dihydroxy-dicyclohexylmethane, 
4,4'-(dihydroxy-dicyclohexyl)-2,2-propane, 
1,4-dihydroxyethyl-hydroquinone, trimethylolethane, trimethylolpropane, 
1,2,6-hexanetriol, glycerin and pentaerythritol. Also suitable are 
multivalent alcohols containing tertiary amino groups in bonded form such 
as, for example, N-alkyl-dialkanolamines, N-methyldiethanolamine and 
triethanolamine and N,N'-bis-hydroxyethylpiperazine. Preferably used are 
divalent and trivalent alcohols such as 1,2-ethanediol, 1,4-butanediol, 
1,6-hexanediol, glycerin and trimethylolpropane and lower molecular weight 
hydroxyl group containing polyoxyalkylene polyethers based on ethylene 
oxide and/or 1,2-propylene oxide, and the aforementioned multivalent 
alcohols or aliphatic diamines having molecular weights from 60 to 116 as 
an initiator molecule. 
Aromatic polyamines are also suitable as starting component (iii) as well 
as amino group containing heterocycles whose heterocyclic radical 
possesses an aromatic character. 
Primary aromatic diamines are preferably used as the aromatic amine in 
preparing the composition of the present invention. 
Efficaciously, one uses aromatic diamines whose primary amino groups do not 
demonstrate a reduced reactivity to polyisocyanates caused by 
electron-withdrawing substitutents and advantageously such aromatic 
diamines are those having primary amino groups which are sterically 
hindered. Most preferred of the aforesaid type are primary aromatic 
diamines which are liquid at room temperature and which are entirely or at 
least partially miscible with the compounds (ii) under processing 
conditions. Preferred are, for example, meta-phenylenediamine and/or more 
preferably, alkyl substituted meta-phenylene diamines having the following 
structural formula: 
##STR3## 
in which R.sup.1 is a hydrogen atom or a linear or branched alkyl radical 
having from 1 to 10 carbon atoms, preferably from 1 to 6 carbon atoms, and 
R.sup.2 and R.sup.3 are identical or different linear or branched alkyl 
radicals having from 1 to 3 carbon atoms, such as the methyl, ethyl, 
propyl, or isopropyl. Preferred are those alkyl radicals R.sup.1 where the 
branching point is at the C.sub.1 carbon atom. In addition to hydrogen, the 
following R.sup.1 alkyl radicals are typical: methyl-, ethyl-, n-propyl-, 
isopropyl-, butyl-, hexyl-, octyl-, decyl-, 1-methyloctyl-, 
2-ethyl-octyl-, 1-methyl-hexyl-, 1,1-dimethylpentyl-, 
1,3,3-trimethylhexyl-, 1-ethylpentyl-, 2-ethylpentyl-, and preferably the 
cyclohexyl-, 1-methyl-n-propyl-, tert-butyl-, 1-ethyl-n-propyl-, 
1-methyl-n-butyl-, and 1,1-dimethyl-n-propyl. 
Typical alkyl substituted m-phenylenediamines which may be used are: 
2,4-dimethyl-, 2,4-diethyl-, 2,4-diisopropyl-, 2,4-diethyl-6-methyl-, 
2-methyl-4,6-diethyl-, 2,4,6-triethyl-, 2,4-dimethyl-6-cyclohexyl- 
2-cyclohexyl-4,6-diethyl-, 2-cyclohexyl-2,6-diisopropyl-, 
2,4-dimethyl-6-(1,1-dimethyl-n-propyl)-, and 
2-(1-methyl-n-butyl)-4,6-dimethyl-1,3-phenylenediamine. 
Diaminodiphenylmethanes have also been used successfully, for example, 
4,4'- and/or 2,4'-diaminodiphenylmethane, 3,3'-di- and 
3,3',5,5'-tetra-n-alkylsubstituted 4,4'-diamino diphenylmethanes such as 
3,3'-diethyl-, 3,3',5,5'-tetraethyl- and 
3,3',5,5'-tetra-n-propyl-4,4'-diaminodiphenylmethane. 
Preferably used are diaminodiphenylmethanes of the formula: 
##STR4## 
in which R.sup.4, R.sup.5, R.sup.6 and R.sup.7 are identical or different 
and are a methyl, ethyl, propyl, isopropyl, sec-butyl, or tertbutyl 
radical, and whereby at least one of the radicals must be an isopropyl or 
sec-butyl radical. The 4,4'-diaminodiphenylmethanes may also be used in 
mixtures with isomers of formulas: 
##STR5## 
whereby R.sup.4, R.sup.5, R.sup.6, and R.sup.7 have the meaning stated 
above. 
Typical examples are: 
3,3',5-trimethyl-5'-isopropyl-diamino-diphenylmethane, 3,3',5-triethyl-5'- 
isopropyl-diamino-diphenylmethane, 
3,3',5-trimethyl-5-sec-butyl-diamino-diphenylmethane, 
3,3',5-triethyl-5'-sec-butyl4,4'-diamino-diphenylmethane, 
3,3'-dimethyl-5,5'-diisopropyl-diamino-diphenylmethane, 
3,3'-diethyl-5,5'-diisopropyl-diamino-diphenylmethane, 
3,3'-dimethyl-5,5'-di-sec-butyl-diamino-diphenylmethane, 
3,3'-diethyl-5,5'-di-sec-butyl-diamino-diphenylmethane, 
3,5-dimethyl-3',5'-diiso-propyl-diamino-diphenylmethane, 
3,5-diethyl-3',5'-diisopropyl-, 
3,5'-dimethyl-3',5'-di-sec-butyl-diamino-diphenyl-methane, 
3,5-diethyl-3',5'-di-sec-butyl-diamino-diphenylmethane, 
3,5'-diamino-diphenylmethane, 5',3'-triisopropyldiamino-diphenylmethane, 
3-ethyl-3',5,5'-triisopropyldiamino-diphenylmethane, 
3-ethyl-3',5,5'-triisopropyldiamino-diphenylmethane, 
3-methyl-3',5,5'-tri-sec-butyldiamino-diphenylmethane, 
3-ethyl-3',5,5'-tri-sec-butyl-4,4'-diaminodiphenylmethane, 
3,3'-diisopropyl-5,5'-di-sec-butyldiamino-diphenylmethane, 
3,5-diisopropyl-3',5'-di-sec-butyldiamino-diphenylmethane, 
3-ethyl-5-sec-butyl-3',5'-diisopropyldiamine-diphenylmethane, 
3-methyl-5-tert-butyl-3',5'-diisopropyl-diamino-diphenylmethane, 
3-ethyl-5-secbutyl-3'-methyl-5'-tert-butyl-diamino-diphenylmethane, 
3,3',5,5'-tetraisopropyl-diamino-diphenylmethane, and 
3,3',5,5'-tetra-sec-butyl-4,4'-diaminodiphenylmethane. 
Preferably used are the following primary aromatic alkyl substituted 
phenylene diamines and diamino-diphenylmethanes: 2,4-diethyl-, and 
2,4-dimethyl-1,3-phenylenediamine; 2,4-diethyl-6-methyl-, and 
2-methyl-4,6-diethyl1,3-phenylenediamine; 
2,4,6-triethyl-1,3-phenylenediamine, 
2,4-dimethyl-6-tert-butyl-1,3-phenylenediamine, 
2,4-dimethyl-6-isooctyl-1,3-phenylenediamine, and 
2,4-dimethyl-6-cyclohexyl-1,3-phenylenediamine, as well as 
3,5-dimethyl3',5'-diisopropyl-and 
3,3',5,5'-tetraisopropyl-4,4'-diaminodiphenylmethane. 
The primary aromatic diamines may be used individually or in the form of 
mixtures, for example, mixtures of optionally alkyl-substituted 
1,3-phenylenediamines, diaminodiphenylmethanes, 3,3'-di- and/or 
3,3',5,5'-tetra-alkylsubstituted 4,4'-diaminodiphenylmethanes. 
Examples of secondary aromatic diamines are: N,N'-dialkyl-substituted 
aromatic diamines which optionally can be alkyl substituted on the 
aromatic ring, having 1 to 20, more preferably, 1 to 4 carbon atoms in the 
N-alkyl radical such as N,N'-diethyl-, N,N'-di-sec-pentyl-, 
N,N'-di-sec-hexyl-, N,N'-di-sec-decyl-, N,N'-di-cyclohexyl-p- and/or 
-m-phenylenediamine, N,N'-dimethyl-, N,N'-diethyl-, N,N-diisopropyl-, 
N,N'-di-sec-butyl-, N,N'-dicyclohexyl-4,4'-diamino-diphenylmethane and 
N,N'-di-sec-butyl-benzidine. 
Preferred as chain extending agents and/or cross linking agents (iii) are 
the industrially readily available alkanediols having 2 to 6 carbon atoms; 
alkanetriols having 3 to 6 carbon atoms, dialkylene glycol ethers having 4 
to 8 carbon atoms, alkyl substituted phenylenediamines, 3,3'-di-and/or 
3,3', 5,5'-tetraalkyl-substituted 4,4'-diaminodiphenylmethanes. 
The following have been used successfully and are therefore most preferred 
as the (iii) component: 2,4-diethyl-6-methyl-1,3-phenylenediamine, 
mixtures of 2,4-diethyl-6-methyl- and 
2-methyl-4,6-diethyl-1,3-phenylenediamine, and mixtures of 
methyl-diethyl-1,3-phenylenediamines and at least one compound selected 
from the group consisting of alkanediols having 2 to 6 carbon atoms 
dialkyleneglycolether having 4 to 8 carbon atoms, glycerin and 
trimethylolpropane. 
The chain extending agents and/or cross linking agents (iii) or their 
mixtures are used in the following quantities in the preparation of the 
foam compositions: 0.5 to 25 parts by weight, more preferably, 5 to 20 
parts by weight and most preferably, 8 to 18 parts by weight, based on 100 
parts by weight of at least one compound having 2 hydrogen atoms reactive 
to isocyanate groups. 
Catalysts (iv) are added to the storage stable, heat curable compositions 
in order to accelerate the reaction of urethane formation of the hydroxyl 
group containing starting components (ii) and (iii) and the deactivated 
organic polyisocyanates (i). Most preferred as catalysts are metal salts 
and metal acetyl acetonates. Individual example are: lead naphthenate, 
bismuth(III) stearate, zinc stearate, lead(II)octanoate, tin octanoate, 
phenylmercury octanoate, iron(III)acetyl acetonate, iron(II)acetyl 
acetonate, cobalt(II)acetyl acetonate, zinc(Il)acetyl acetonate; manganese 
acetyl acetonate, cerium(IV)acetyl acetonate, titanium(IV)acetyl acetonate, 
zirconium(IV)acetyl acetonate, bis-lauryltin dimercaptide, 
2,3,4,6,7,8,9,10-octahydro-pyramido-1,2-azepine or mixtures of at least 
two of the aforesaid catalysts whereby preferably used is a combination of 
lead naphthenate and bismuth (III)stearate efficaciously in a weight ratio 
2 to 1:1. Normally used is 0.1 to 3 weight percent, more preferably 0.3 to 
1 weight percent of catalyst based on the total weight of the component 
(ii). 
Auxiliaries and/or additives may also be incorporated into the compositions 
of the present invention. Typical examples are: pigments, dyes, agents to 
protect against hydrolysis, ultraviolet stabilizers, antioxidants and 
plasticizers. 
Typical pigments are those conventional ones known for polyisocyanate 
addition polymerization products. Individual examples are: black paste, 
copper, aluminum and iron powder, zinc dust, iron oxide, cadmium sulfide, 
etc. 
Most preferred as plasticizers are those containing in bonded form NCO 
group reactive radicals. Individual examples are: 
1,4-butanediol-1,6-hexanediolpolyadipates, ketone zesins prepared from 
cyclohexanone and formaldehyde and dissolved in castor oil, for example, 
those having a hydroxyl number of about 165; polycondensation products 
prepared from phthalic anhydride, adipic acid, oleic acid, ethylene glycol 
and glycerin, for example, having a hydroxyl number of 370, or prepared 
from phthalic acid anhydride, adipic acid, oleic acid and 
trimethylolpropane; and alkyl epoxy stearates. The plasticizers are 
ordinarily used in quantities of 0.5 to 10 weight percent, more preferably 
1 to 6 weight percent based on the total weight of the composition. 
Further information on the above-mentioned auxiliaries and/or additives and 
on other auxiliaries and/or additives may be found in the technical 
literature, for example, the monograph of J. H. Saunders and K. C. Frisch 
High Polymers Vol. XVI, Polyurethanes parts 1 and 2, Verlag Interscience 
Publishers 1962 and/or 1964; or in the Plastics Handbook, Vol. VII, 
Polyurethanes first edition 1966 or second edition 1983, Carl Hanser 
Verlag, Munich. 
Preparing the compositions occurs following known conventional processes, 
for example, disclosed in EP-A-062 780, EP-A-100 507 or EP-A-100 508, 
efficaciously while using ordinary dispersing and mixing equipment. The 
organic polyisocyanate (i) is advantageously dispersed at temperatures 
below 40.degree. C., more preferably at temperatures of from 0.degree. C. 
to 25.degree. C. in a mixture of starting components (ii) through (iv) or 
(ii) and/or (iii), or preferably in at least one compound having two 
hydrogen atoms (ii) reactive to isocyanate groups, whereby the composition 
of starting component (ii) either already contains the total amount of one 
or more deactivating agents o shortly after the dispersing procedure, at 
least one of the deactivating agents is added to the compositions or 
starting component (ii). Both modes of processing can be combined with one 
another whereby starting components (ii) and/or (iii), for example, can 
contain a portion of the deactivating agent while another portion of the 
same or another deactivating agent is added to the composition after 
dispersing the polyisocyanate. If only starting component (ii) or a 
mixture of (ii) and (iii) are used as a coherent phase for dispersing the 
polyisocyanate then the remaining starting materials are incorporated into 
the composition, for example, starting component (iv), subsequent to the 
resulting dispersion. Understandably, the polyisocyanate dispersion can 
also be mixed with the starting components (ii) and/or (iii) used in its 
preparation. 
In preparing the compositions, the quantity ratios of starting components 
(i) through (iii) can be varied over a broad range, for example, in ratios 
from 0.8 to 2.5:1 of free isocyanate groups to hydroxyl, amino groups or to 
the total of the hydroxyl and amine groups. Compositions which contain the 
deactivated polyisocyanates in high concentrations, for example, in NCO:OH 
and/or NH.sub.2 and/or OH-plus NH.sub.2 group ratios of 10:1 to 3:1, more 
preferably 5:1 to 3:1, they can be used as a so-called masterbatch and 
diluted before processing with components (ii) and/or (iii). 
In preparing the urethane and/or urea group containing films of the middle 
layer, compositions are preferably used in which the ratio of NCO:OH 
and/or NH.sub.2 groups is 0.8 to 2.5:1, more preferably 0.9 to 1.2:1. 
The compositions are efficaciously flowable and at 23.degree. C. have a 
viscosity of 500 to 20,000 mPas, more preferably 1000 to 10,000 mPas. 
The textured polyurethane molded articles containing multiple sheet layers 
of this invention comprise noncellular or cellular polyurethane as backing 
layer (c) and as support material, whereby preferably used is flexible, 
semi-rigid or rigid polyurethane foam. Processes for the preparation of 
non-cellular or cellular polyurethanes particularly polyurethane foams are 
adequately known in the literature and in patents so that further 
information will not be presented here. Examples are however, as 
previously cited High Polymers Vol. XVI, Polyurethanes; The Plastics 
Handbook, Vol. VII, Polyurethanes; and Federal Republic of Germany 
Application 31 27 914 or Federal Republic of Germany Application 27 32 
292. 
For particular applications, it may be advantageous if backing layer (c) 
made from non-cellular or cellular polyurethane also contains an insert 
and/or reinforcing material. 
Typical inserts are made from metallic materials such as, for example, 
aluminum, copper, brass or sheet steel; or plastic such as, for example, 
polyamide, polybutyleneterephthalate, or mixtures of polymers, polyamides 
and/or polyesters. 
Typical reinforcing materials are: short or long fibers such as, for 
example, glass fibers, carbon fibers, organic synthetic fibers or natural 
fibers such as aromatic polyamide, polyester fibers or cellulose fibers as 
well as woven materials, mats or non-wovens of such fibers. 
In preparing said textured polyurethane molded articles having multiple 
sheet layers, a coating for forming coating layer (a) is, for example, 
applied and/or sprayed on to a textured mold optionally sprayed with 
internal release agent and heated to 60.degree. C. to 150.degree. C., more 
preferably 80.degree. C. to 130.degree. C. The mold may be from a number of 
materials such as for example, epoxide polyester resin compositions or 
preferably from metallic materials such as aluminum, cast iron, steel or 
stainless steel. After the coating layer exhibits a sufficiently high 
viscosity, i.e. no longer flowable and is partially or completely dried, 
this is then coated at a temperature within a range previously cited with 
a composition to form the urethane and/or urea group containing film of 
middle layer (b). The composition cures on the mold's internal surface and 
with the coating layer forms a sufficiently bonded composite film which can 
be easily removed from the surface of the mold. 
The composition can be applied to the tempered, mold surface possessing a 
coating layer using known methods such as for example, by coating, 
brushing or spraying. According to preferred embodiments, the heat curable 
composition is either sprayed onto the heated mold surface or most 
preferably, the heated mold is submerged in a bath of the composition. 
However, the coating methods cited above can also be combined with one 
another whereby efficaciously at least two of the methods are used. For 
example, a film having a uniform thickness layer can be prepared by 
submerging the heated mold in a bath of the composition which preferably 
has a temperature of 80.degree. C. to 150.degree. C., more preferably 
90.degree. C. to 130.degree. C. for a certain time period. As soon as the 
cured composition on the heated mold surface has achieved the desired 
thickness then the mold is removed from the bath and the excess non-cured 
composition is removed and the composite film formed is removed from the 
mold. However, it is also possible to remove the mold with the composite 
film layer formed from the bath and to increase and optionally modify the 
thickness layer of the film in certain areas, for example, by spraying 
with the same or with another composition. Following the methods 
described, for example, from an urea group forming composition, a film 
containing urea-forming groups can be prepared and this film can be 
completely or partially coated with a urea and urethane group forming 
composition and in this manner, the mechanical properties of the film 
prepared can be varied. Obviously, the heated mold, for forming a multiple 
sheet film, can be submerged sequentially in multiple baths with different 
types of compositions. Depending on the desired type of modification of 
the film, one can use different compositions in any sequence successfully. 
As already stated, after the composition cures on the mold, the composite 
film formed can be removed without difficulty. 
The films suitable as middle layer (b) and prepared according to the 
processes described preferably have a thickness of 10 to 20,000 microns, 
more preferably 800 to 3,000 microns. Such film thicknesses can be 
achieved, for example, by spraying with the required quantity of 
composition, efficaciously with a quantity of 15 to 30,000 g/m.sup.2, more 
preferably 1,500 to 6,000 g/m.sup.2. According to a preferred process, the 
heated mold is submerged in a bath of the composition as a function of 
mold temperature, coating layer (a), composition temperature and desired 
film thickness, for a certain time, for example, from 0.5 to 5 minutes, 
more preferably 1 to 4 minutes, and the composition is allowed to cure on 
the surface of the mold. 
The film with a coating as covering layer (a) and with middle layer (b) 
comprising urethane and/or urea groups, which also can be designated as a 
composite film, can be treated directly after its preparation in the mold 
under the aforesaid reaction conditions with a reactive, blowing agent 
free or preferably blowing agent containing mixture to form the 
polyurethane. The polyurethane forming reaction mixture here is filled or 
sprayed under pressure into the hollow space of the mold whose interior 
surface is coated with the composite film and in this heated mold, which 
can remain open or closed after filling, the mixture cures. 
According to a preferred process, the film containing cured multiple sheet 
layered composite film of coating layer and urethane and/or urea groups is 
removed from the mold and subsequently is either directly or after interim 
storage in a separate processing step poured in place in a conventional 
fashion with a reactive foaming mixture to form the polyurethanes, or is 
treated with a blowing-agent-free reaction mixture, for example, by 
filling the hollow cavity of the composite film, and the reaction mixture 
is allowed to cure. 
The textured multiple sheet-layer-containing polyurethane molded articles 
are used as construction elements in different industrial areas. Said 
articles are particularly suited as construction elements in 
transportation, for example, as instrument panels or as coverings for 
doors or as compartment shelves in automobiles. 
EXAMPLE 
Preparation of a Storage Stable Heat Curable Composition 
37 parts by weight of dimeric uretdione group-containing 2,4-toluene 
diisocyanate was dispersed in a mixture of: 
39.48 parts of a polyoxypropylene(81.5 weight 
percent)-polyoxyethylene-(18.5 weight percent)glycol having an average 
molecular weight of 3,500; 
20.00 parts by weight of a trifunctional polyether polyol having an average 
molecular weight of 4,800 prepared by the addition polymerization of 
1,2-propylene oxide on trimethylolpropane and the subsequent addition 
polymerization of ethylene oxide on the resulting 
trimethylolpropane-polyoxypropylene-adduct; and 
9.41 parts by weight of a trifunctional polymer modified polyether polyol 
having an average molecular weight of 4,000 prepared by the addition 
polymerization of 1,2-propylene oxide (86 weight percent) on glycerin as 
an initiating molecule, the subsequent addition polymerization of 14 
weight percent ethylene oxide to the resulting glycerin 
polyoxypropylene-adduct, and by dispersing a synthetically prepared 
magnesium aluminum silicate (Transpafill.RTM. from the Degussa Company) as 
a filler in a weight ratio of polyoxypropylene-polyoxyethylene-triol to 
filler of 85:15; 
at 23.degree. C. with the help of a stirrer at 1,000 rpm for 5 minutes. 
Over 2 minutes the following was dispersed into the aforesaid resulting 
dispersion: 0.96 parts by weight of a 50 weight percent solution in 
ethylene glycol of a reaction product prepared by reacting 1 mole of 
3,3'-dimethyl-4,4'-diamino-dicyclohexylmethane with 2 moles of oleic acid 
at 23.degree. C. 
An easily flowing dispersion was obtained and while stirring at 23.degree. 
C., the following were incorporated into the dispersion: 
1.0 part by weight of trimethylolpropane; 
3.62 parts by weight of ethylene glycol; 
0.52 part by weight of a 24 weight percent solution of lead(II)naphthenate 
in naphthenic acid; 
20.0 parts by weight of polyoxypropylene glycol having a molecular weight 
of 600; and 
5 parts by weight of 1-methyl-3,5-diethyl-2,4-diaminobenzene. 
The resulting composition was storage stable for more then 12 months and at 
23.degree. C. had a viscosity of 2775 mPas. 
Preparation of a Polyurethane Semi-Rigid Foam for Pouring in Place Foaming 
of the Multiple Layer Film 
i Component: a mixture comprising: 
84 parts by weight of a polyoxypropylene(86 weight 
percent)-polyoxyethylene(14 weight percent)-triol, initiated with 
glycerin, having a hydroxyl number of 28; 
5 parts by weight of a graft polyether polyol prepared by in situ 
polymerization of 20 parts by weight of a mixture of styrene and 
acrylonitrile in a weight ratio of 1:1 in a polyoxypropylene(86 weight 
percent)-polyoxyethylene(14 weight percent)-triol, initiated with 
glycerin, having a hydroxyl number of 28; 
0.5 parts by weight of triethanolamine; 
2.5 parts by weight of water; 
5.0 parts by weight of a polyether polyol having a hydroxyl number of 768 
prepared from ethylene diamine as an initiator and 1,2-propylene oxide; 
0.4 parts by weight of a foam stabilizer based on a silicon (Tegostab.RTM. 
B4690 from Goldschmidt AG, Essen West Germany); and 
0.6 parts by weight of a 40 weight percent aqueous potassium acetate 
solution. 
ii Component: A mixture of diphenylmethanediisocyanates and 
polyphenyl-polymethylene-polyisocyanates (polymeric MDI) having an NCO 
content of 31 .+-.1 weight 
In preparing the semi-rigid polyurethane foam for pouring in place, the A 
and B components were intensively mixed together at 23.degree. C. in a 
weight ratio of 100:55 and then the reaction mixture was applied to the 
backside of the film coated with the polyurethane coating and was allowed 
to cure there. 
Preparation of the Molded Article 
An electrically heatable mold made of cast iron in the shape of an 
automobile glove compartment at a mold temperature of 110.degree. C. and 
having a textured mold surface was sprayed with a wax dissolved in a 
hydrocarbon (Acmos.RTM. 180 ST-5 from the Acmos Company) as a release 
agent. 
Subsequently, the surface of the mold was sprayed at 6 g/m.sup.2 with a 
light-resistant polyurethane coating based on an aromatic polyester polyol 
and a modified hexamethylene diisocyanate (Commercial product: a dual 
component polyurethane coating No. GG 01-8101 from BASF-Farben and Lacke 
AG) at a pressure of 3 bar. 
After drying for 60 seconds, the composition was poured into the hollow 
cavity of the mold as per Example 1a and it uniformly distributed itself 
over the internal surface of the mold coated with the polyurethane 
coating. 
Excess composition was removed after 20 seconds by pouring from the hollow 
cavity of the mold. 
After curing for 60 seconds, the film coated with the polyurethane coating 
was removed from the mold and poured in place with the reactive mixture of 
Example lb to form the polyurethane foam.