The present invention relates to laminates consisting of a thermoplastic film, a polyurethane layer, a color layer, if appropriate a second polyurethane layer and a thermoplastic layer and a process for their production.

The present invention relates to laminates with a thickness of 0.5 mm to 20 
mm, consisting of 
1. a 0.02 mm to 0.8 mm thick film of a thermoplastic, 
2. a polyurethane layer which is tack-free at room temperature, 
3. a colour layer, if appropriate 
4. a second polyurethane layer which is tack-free at room temperature and 
5. a thermoplastic layer with a thickness of 0.4 mm to 19 mm. 
Films of thermoplastics which are suitable according to the invention are 
those of known thermoplastic aromatic polycarbonates with weight-average 
molecular weights Mw of 25,000 to 200,000, preferably 30,000 to 120,000 
and in particular 30,000 to 80,000 (Mw determined via .eta..sub.rel in 
CH.sub.2 Cl.sub.2 at 20.degree. C. and a concentration of 0.5 g per 100 
ml); films of thermoplastics which are suitable according to the invention 
are also preferably those of known thermoplastic polyaryl sulphones, which 
can be linear (see DE-OS (German Published Specification) No. 2,735,144) 
or branched (see DE-OS (German Published Specification) No. 2,735,092 and 
DE-OS (German Published Specification) No. 2,305,413). 
Suitable linear polyaryl sulphones are all the known aromatic polysulphones 
or polyether-sulphones with an Mw (weight-average molecular weight 
measured, for example, by means of light scattering) of between about 
15,000 and about 55,000, preferably between about 20,000 and about 40,000. 
Such polyaryl sulphones are described, for example, in DE-OS (German 
Published Specification No. 1,719,244 and U.S. Patent Specification No. 
3,365,517. 
Suitable branched polyaryl sulphones are, in particular, the branched 
polyaryl ether-sulphones according to DE-OS (German Published 
Specification) No. 2,305,413 and U.S. Pat. No. 3,960,815, the Mw of which 
(weight-average molecular weight, measured, for example, by means of light 
scattering) are between about 15,000 and about 50,000, preferably between 
about 20,000 and 40,000. (For further details in this context, see DE-AS 
(German Published Specification) No. 3,010,143 (Le A 20 254)). 
Thermoplastics which are suitable for the films according to component 1 
are preferably also thermoplastic cellulose esters, thermoplastic 
polyvinyl chlorides and thermoplastic styrene/acrylonitrile copolymers. 
Cellulose esters which are suitable according to the invention are obtained 
by customary processes by esterification of cellulose with aliphatic 
monocarboxylic acid anhydrides, preferably acetic and butyric or acetic 
and propionic anhydride. The hydrolysis, which is to be carried out in the 
crude solution, is controlled by a slight excess of water so that a low 
hydroxyl content (4 to 25) is obtained. The oxidative bleaching of the 
cellulose ester isolated from the solution must be carried out so that 
oxidizing agent is no longer detectable in the end product; if 
appropriate, after-treatment with reducing agents must be carried out. To 
determine the OH number, the free hydroxyl groups of the cellulose ester 
are esterified with acetic anhydride in pyridine and the excess anhydride 
is reacted with water and back-titrated [Instructions: C. J. Mahn, L. B. 
Genung and R. F. Williams, Analysis of Cellulose Derivatives, Industrial 
and Engineering Chemistry, Volume 14, No. 12, 935-940 (1942)]. 
The viscosity of the cellulose esters should be 0.3 to 0.5 poise, measured 
as a 20% strength by weight solution in acetone. Cellulose esters which 
are preferably to be used have, in the case of the acetobutyrates, an 
acetic acid content of 17 to 23% by weight and a butyric acid content of 
45 to 50% by weight and, in the case of the acetopropionates, a propionic 
acid content of 61 to 69% by weight and an acetic acid content of 2 to 7% 
by weight. The OH numbers are usually between 4 and 25. The mean 
weight-average molecular weights Mw are between 10,000 and 1,000,000, 
preferably between 100,000 and 500,000. 
Thermoplastic polyvinyl chlorides which are suitable according to the 
invention are, for example, the commercially available grades of PVC. 
Thermoplastic styrene/acrylonitrile copolymers which are suitable according 
to the invention are copolymers of styrene with, preferably, acrylonitrile 
which are obtained, for example, with an mw of 10,000 to 600,000 (Mw is 
measured in dimethylformamide at C=5 g/l and 20.degree. C.) from the 
monomers or mixture of monomers by suspension polymerization in the 
presence of catalysts. For literature in this context, see Beilsteins 
Handbuch der organischen Chemie (Beilstein's Handbook of Organic 
Chemistry), fourth edition, Duttes supplement B 1.5, pages 1163-1169, 
Springer Verlag 1964 and H. Ohlinger, Polystyrol 1. Teil, 
Herstellungsverfahren und Eigenschaften der Produkte (Polystyrene Part 1, 
Preparation processes and properties of the products), Springer Verlag 
(1955). 
Reference may be made to DE-OS (German Published Specification) No. 
2,517,033 (Le A 16 244), or to DE-OS (German Published Specification) No. 
2,531,240 (Le A 16 536) for the known production of the films according to 
component 1. 
The films according to component 1 are matted on one side or structured on 
one side, which is effected in a known manner by pressing the melt of the 
thermoplastic through a flat sheet die and taking off the melt strand over 
a matted or structured cooling roll. 
The films can also be polished on one side and matted on one side. 
The thickness of the films is preferably between and 0.05 and 0.8 mm. 
Both aqueous dispersions, which dry to give transparent films, of 
preferably linear polyester-polyurethanes and organic solutions, which dry 
to give transparent films, of preferably linear polyester-polyurethanes, 
which optionally contain a polyisocyanate of higher functionality as a 
crosslinking agent, can be used to produce the polyurethane layers 
according to components 2 and 4 which are suitable according to the 
invention. Suitable polyurethane dispersions are, for example, those based 
on linear polyester-diols, aromatic or aliphatic diisocyanates and, if 
appropriate, the customary chain-lengthening agents, which have been 
prepared co-using ionic build-up components in accordance with the 
doctrine of U.S. Pat. No. 3,479,310 or DE-AS (German Published 
Specification) No. 1,495,847. The aqueous dispersions of preferably linear 
polyesterpolyurethanes containing carboxylate and sulphonate groups, such 
as can be obtained according to DE-OS (German Published Specification) No. 
2,804,609, are also particularly suitable. If organic solutions of 
preferably linear polyester-polyurethanes are used, solutions of non-ionic 
linear polyester-polyurethanes in suitable solvents are preferred. These 
polyurethanes are preferably reaction products of (i) aromatic 
diisocyanates, such as 2,4- and/or 2,6-diisocyantotoluene, 
4,4'-diisocyanatodiphenylmethane, hexamethylene diisocyanate, isophone 
diisocyanate or 1,5-diisocyanatonaphthalene or mixtures thereof, with (ii) 
polyester-diols in the molecular weight range (m w) of 1,000 to 4,000, in 
particular those based on adipic acid and suitable glycols, such as 
ethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane and mixtures 
thereof, and, if appropriate, (iii) chain-lengthening agents, for example 
the lastmentioned glycols, the reaction partners being used with an NCO/OH 
equivalent ratio of 0.9:1 to 1:1.1, preferably 0.95:1 to 1:1, being 
maintained, and, if appropriate, 0.1 to 2 moles of chain lengthener or 
chain lengthener mixture being used per mole of polyester-diol. Suitable 
solvents for such polyester-polyurethanes are, for example, ethyl acetate, 
butyl acetate, methyl ethyl ketone, methyl isobutyl ketone or mixtures 
consisting of such solvents. The dispersions or solutions are in general 
used with a solids content of 10-40% by weight. It can frequently be 
advantageous to incorporate minor amounts of a polyisocyanate of higher 
functionality, for example tris-(6-isocyanatohexyl)-biuret, into the 
solutions mentioned, in order to improve the mechanical properties of the 
polyurethane film finally obtained. 
The intermediate layer according to component 2 can be applied either 
continuously to the film by the roll coater or doctor blade process, or by 
the screen printing process before the decoration is printed. The amount 
of dispersion or solution is in general chosen so that dry film 
thicknesses of 2-80 .mu.m, preferably 15-30 .mu.m, result. 
The intermediate layer according to component 4 is printed onto the 
decorative colour layer 3 by the screen printing process. 
The intermediate layers according to components 2 and 4 are completely 
tack-free thermoplastic layer ends at room temperature. 
The screen printing process according to the present invention is 
understood as pressing paints or lacquers through a sieve fabric clamped 
in a frame, the mesh of which is partly closed in accordance with the 
print master. The openings which remain in the sieve fabric correspond to 
the print image. 
The thickness of the polyurethane layer 4 is 2 to 80 .mu.m, preferably 15 
to 30 .mu.m. 
Suitable colour layers according to component 3 consist of lacquers based 
on polyacrylates or mixtures of polyacrylate and cellulose acetobutyrate, 
or a PVC copolymer, containing pigments and/or dyestuffs. 
The colour layers 3 are applied to the polyurethane layer 2 by the screen 
printing process. 
The thickness of the colour layers is between 5 and 50 .mu.m. 
The thermoplastic layer according to component 5 are preferably of 
thermoplastic polymethyl methacrylate, thermoplastic 
acrylonitrile/butadiene/styrene copolymers, thermoplasit polystyrene, 
thermoplastic polycarbonate, thermoplastic styrene/acrylonitrile 
copolymers and thermoplastic cellulose esters, the last three 
thermoplastics mentioned already being defined under component 1. 
Thermoplastic polymethyl methacrylates are, for example, the commercially 
available grades of Plexiglas. 
Thermoplastic acrylonitrile/butadiene/styrene copolymers are, in 
particular, mixtures of (a) 50 to 70% by weight of one or more grafted 
products and (b) 95 to 30% by weight of one or more thermoplastic resins. 
Grafted products (a) are preferably polymers obtained by polymerization of 
grafting monomers in the presence of a rubber as the graft base. The 
rubber content is preferably 5 to 80% by weight, and also depends on the 
polymerization process. 
Possible graft bases are, in particular, polybutadiene, natural rubber, 
butadiene/acrylonitrile copolymers and butadiene/styrene copolymers and 
block polymers. Acrylic ester/vinyl ether polymers and EPDM terpolymers 
can also be used grafting monomers are chiefly styrene mixtures of styrene 
and acrylonitrile, preferably in a weight ratio of 90:10 to 50:50. 
Mixtures of styrene and methyl (meth)acrylate, preferably in a weight 
ratio of 5:95 to 95:5, and styrene/acrylonitrile/methyl (meth)acrylate 
mixtures. 
The preparation of such grafted products is known per se. The grafting 
monomers can be polymerized in the presence of a rubber latex in emulsion. 
The grafting reaction is then started with a free radical initiator. If 
the rubber is partly crosslinked and certain ratios of the amounts of 
grafting monomer and graft bases are maintained during the grafting 
reaction, the size of the rubber particles in the latex determines the 
particle size of the resulting graft polymer. The grafted-on shell of 
chains of the polymer of the grafting monomer bonded chemically to the 
rubber particles is relatively thin and does not substantially change the 
size of the rubber particle. Size here is understood as the d.sub.50 
value, that is to say the diameter above which and below which in each ase 
50% of the diameters of the particles lie. The grafting reaction is 
incomplete, so that its product is called the grafted product. In addition 
to the actual graft polymer, it also contains non-grafted copolymers of 
the grafting monomers. 
The graft polymers can also be prepared by bulk/solution or bulk/suspension 
polymerization, preferably from monomer-soluble rubber. The size of the 
grafted rubber particles is then determined in the phase inversion stage 
and can be influenced mechanically (by stirring) and by chemical 
influencing of the phase equilibrium (addition of dispersing agents). In 
general, particles of 1 .mu.m diameter or larger are obtained in 
bulk/solution grafting processes. The rubber content of the grafted 
product is limited to not more than 25%. 
Products in which the particles have a size of 0.05 to 20 .mu.m and those 
in which a considerable portion of the grafting monomers is included as 
homo- or copolymer inside the rubber particles can be used according to 
the invention. Preferred particle sizes are 0.05 to 1.2 .mu.m, in 
particular 0.05 to 0.6 .mu.m. It is also possible to use several different 
grafted products side by side, for example two grafted products which 
differ in the degree of grafting (or in the grafting density), the 
particle size or in both simultaneously. A mixture of a grafted product 
with particles with a size d.sub.50 of 0.35 to 10 .mu.m and a grafted 
product with particles with a size d.sub.50 of 0.05 to 0.32 .mu.m, for 
example, is particularly suitable (ABS polymers thus prepared are also 
called bimodal systems). 
The grafted products preferably contain 35 to 80% by weight, in particular 
40 to 70% by weight, of rubber and have particle sizes d.sub.50 of 0.1 to 
0.5 .mu.m. They are employed in an amount such that the finished ABS 
polymer contains 5 to 25% by weight, preferably 5 to 20% by weight, of 
rubber. 
The thermoplastic resin (b) which forms the second constituent of the ABS 
polymer is the continuous matrix and is a polymer or copolymer of styrene, 
.alpha.-methylstyrene/acrylonitrile/methyl (meth)acrylate or maleic 
anhydride. Polystyrene, styrene/acrylonitrile copolymers with an 
acrylonitrile content of 20 to 35% by weight and 
.alpha.-methylstyrene/acrylonitrile copolymers with an acrylonitrile 
content of 20 to 31% by weight are preferred. The weight-average of the 
molecular weight of these resins is 50,000 to 550,000; the molecular 
heterogeneity H. 
EQU (M/M-1=H) is 1.0-3.5 
If a single grafted product is used, it is advantageous for the 
quantitative composition of the grafting monomers and that of the resin to 
be similar or identical. If a mixture of two grafted products of different 
particle sizes is used, it is advantageous for the quantitative 
composition of the grafting monomers of the grafted product with the 
coarser particles to differ from the composition of the resin. 
.alpha.-Methylstyrene in combination with acrylonitrile cannot be grafted, 
and can only be used in the resin. 
The thermoplastic resins, for example styrene/acrylonitrile or 
.alpha.-methylstyrene/acrylonitrile copolymers, can be prepared by known 
processes, for example by bulk polymerization, solution polymerization, 
suspension polymerization and emulsion polymerization. 
The grafted product and thermoplastic resin are frequently prepared 
separately, in both cases usually by emulsion polymerization. If the 
components are obtained in latex form, the latices can be mixed and 
precipitated together. 
Thermoplastic polystyrenes which are suitable for preparing the layer of 
plastic 5 are homopolymers of styrene or copolymers of styrene with, 
preferably, acrylonitrile and/or butadiene, and/or maleic acid esters, 
which are obtained, for example, with an Mw of 10,000 to 600,000 (Mw is 
measured dimethylformamide at c=5 g/l and 20.degree. C.) from the monomers 
or mixture of monomers by suspension polymerization in the presence of 
catalysts. (For literature in this context, see: Beilsteins Handbuch der 
Organischen Chemie (Beilstein's Handbook of Organic Chemistry), fourth 
edition, third supplement, Volume 5, pages 1163-1169, Springer Verlag 1964 
and H. Ohlinger, Polystyrol, 1. Teil, Herstellungsverfahren und 
Eigenschaften der Produkte (Polystyrene, Part 1, Preparation processes and 
properties of the products), Springer Verlag 1955). 
The layer of plastic 5 is introduced and the laminate according to the 
invention is thus produced by injecting the layer 5 under the layers 
1+2+3or 1+2+3+4 by known processes (in this context, see, for example, 
DE-OS (German Published Specification) No. 2,755,088 (Le A 18 549). 
The thickness of the layer of plastic 5 is preferably between 0.4 and 19 
mm. 
The present invention furthermore relates to a process for the production 
of the laminates according to the invention from layers 1+2+3 +5 and, if 
appropriate, 4, which is characterized in that films of thermoplastics are 
coated with polyurethanes and then coated with a colour layer and, if 
appropriate, with a second polyurethane layer by the screen printing 
process and, finally, a thermoplastic layer is injected under the other 
layers in a known manner. 
Laminated films with polyurethane adhesion are known. (See, for example, 
DE-OS (German Published Specification) No. 2,517,032 and DE-AS (German 
Published Specification) No. 3,010,143). 
Injection of the thermoplastics under thermoplastic films is likewise known 
(see DE-OS (German Published Specification) No., 2,755,088). 
However, no intermediate colour layer is mentioned in this literature. 
Laminates of polycarbonates and glass which contain polyurethane 
intermediate layers of preferably thermoplastic polyurethanes are known 
from DE-OS (German Published Specification) No. 1,594,164. These laminates 
can be used, for example, as windscreens for motor vehicles. Coloration of 
these laminates is not referred to in DE-OS (German Published 
Specification) No. 1,594,164. 
The object of the present invention was thus to provide laminates 
containing printed images in a simple manner. The advantages of these 
laminates are 
1. Components which are ready for installation, i.e. provided with the 
final decoration, are removed from the injection moulding machine. 
2. The printed decoration is protected from wiping off and wear, since it 
is between the front film and the carrier layer. 
3. The laminates can be produced particularly easily. 
4. By suitable choice of the components, the values of the properties can 
be varied within a wide range.

The laminates according to the invention are used, for example, for screens 
for domestic, phonographic and TV appliances. 
EXAMPLE 1 
A 200 .mu.m thick film, structured on one side and matt on one side, of 
thermoplastic diphenol A homopolycarbonate (.eta..sub.rel =1.31, measured 
in CH.sub.2 Cl.sub.2 at 25.degree. C. and at a concentration of 0.5 g/100 
ml) is printed on the matt side with an aqueous, commercially available 
dispersion of a linear polyester-polyurethane based on polyethylene 
adipate with a molecular weight of Mw 2,000 and toluylene diisocyanate by 
the screen printing process, a screen with 43 threads/cm being used. The 
thickness thus obtained for the polyurethane layer is 20 .mu.m. After 
drying the layer (2 minutes at 80.degree. C.), the colour decoration is 
printed onto the polyurethane intermediate layer by the screen printing 
process in a manner which is known per se. A commercially available 
PVC-based paint is used as the colour. The film thus printed is punched in 
accordance with the shape of the finished article and laid in the opened 
injection mould for the carrier material so that the structured side of 
the polycarbonate film is opposite the injection point for the 
thermoplastic. 
If fixing of the film is necessary, this can be effected by means of 
electrostatic charging of the film or by a vacuum. After closing the 
mould, the injection process is carried out in a manner which is known per 
se, with a thermoplastic of an acrylonitrile/butadiene/styrene 25 
copolymer with a .eta..sub.rel of 1.4, which has been obtained by 
copolymerization of 50% by weight of acrylonitrile, 20% by weight of 
butadiene and 30% by weight of styrene in accordance with DAS (German 
Published Specification) No. 2,827,594. 
The total thickness of the laminate is 6 mm. 
EXAMPLE 2 
Example 1 is repeated, the aqueous dispersion of a polyurethane used being 
such a dispersion based on polybutylene adipate with a molecular weight Mw 
of 4,000 and a mixture of hexamethylene diisocyanate and isophorone 
diisocyanate. A resin mixture of polyacrylate and cellulose acetobutyrate 
was used as the colour for applying the coloured decoration, and the total 
thickness of the laminate is 3 mm. 
EXAMPLE 3 
Example 1 is repeated, a polycarbonate film, polished to a high gloss on 
one side and matt on one side, of the bisphenol A homopolycarbonate of 
Example 1 with a thickness of 200 .mu.m being employed. 
After printing-on the coloured decorative layer, a second polyurethane 
layer is applied from.the polyurethane dispersion by the screen printing 
process. 
Thermoplastic polystyrene with a Mw of 40,000 is injected under the layer 
of four components. 
The total thickness of the laminate is 8 mm.