BE880819A - METAL-THERMOPLASTIC MATERIAL-METAL LAMINATE - Google Patents

Description

       

  Laminate of the metal-thermoplastic-metal type.

  
  <EMI ID = 1.1>

  
The present invention relates to laminates and a manufacturing method. More specifically, the invention relates to laminates of the metal-thermoplastic-metal type having an improved combination of critical properties required for construction applications,

  
Laminates of the metal-thermoplastic-metal type and manufacturing methods are known, see for example US Pat. Nos. 3,382,136, 3,353,742, publication "Modern Plastics", 41 (March 7) 119-124 (1964) , and the publication "Chemical Economy & Engineering Review", volume 2, number 10 (October) 51-53, 57 (1970).

  
The laminates described in the above publications as well as other laminates known in the art, however, are generally limited with respect to their applications, particularly when contemplating their use as building panels where a combination of properties low thermal expansion (low coefficient of linear thermal expansion) and good recovery after deviations due to bending (low inelastic ratio) are the necessary properties of laminates.

  
It is a main object of the present invention to produce a laminate of the metal-thermoplastic metal type having an improved combination of properties considered important and critical for the applications envisaged.

  
  <EMI ID = 2.1>

  
exterior and interior, application panels, panels for transport vehicles, for example automobiles, ships and airplanes.

  
It is another object of the present invention to produce a laminate for building panels characterized among other properties, by a combination of low coefficient of linear thermal expansion, a low inelastic ratio (where a high elasticity in bending) and a-very good resistance to bending.

  
It is another object of the present invention to produce such a laminate which, in addition to the critical properties considered necessary for applications

  
in building, also has a wide range of other desirable properties, for example, a high heat distortion temperature, excellent stamping,

  
  <EMI ID = 3.1>

  
It is another object of the invention to produce a laminate having a thickness ratio specially chosen from the total thicknesses of the metal layers / thickness

  
of the central layer to obtain an optimum combination of properties.

  
It is yet another object of the invention to produce a laminate which is particularly suitable for applications in the. -automobile domain.

  
Another object of the invention is to implement a method for manufacturing the metal-thermoplastic-metal laminates mentioned above.

  
The objects and advantages of the invention will appear more readily to these specialists in the field on reading the description and the following claims.

  
These above goals are successfully achieved by the pre-

  
  <EMI ID = 4.1>

  
having the following properties in combination:

  
  <EMI ID = 5.1>

  
a thermal coefficient of linear expansion

  
  <EMI ID = 6.1>

  
flexural stiffness of at least 52.53 x 10 <3> N / m, and

  
a maximum weight not exceeding 9.76 kg / m <2>, these laminates comprising:

  
a core layer of thermoplastic material and a metal layer applied to each side of the core layer of thermoplastic material, each metal layer having a minimum thickness of about 0.00127 cm, provided that the aluminum is not the metal layer on both sides of the laminate when the core layer of thermoplastic material is high density polyethylene and also provided that) when polypropylene is the core of thermoplastic material and aluminum is the applied metal coating on each side of the nucleus,

  
the laminate has a maximum point of 5.37 kg / m <2>, where the thickness ratio of the sum of the thicknesses of the layers

  
of metal to the thickness of the layer - core thermoplastic material is described by the numerical overlap region

  
  <EMI ID = 7.1>

  
  <EMI ID = 8.1>

  
the lower limit of these areas being defined by the equation of a straight line

  
y = mx + b

  
  <EMI ID = 9.1>

  
the parameter of the x axis of TR (YSm / TSc), m is the slope of the straight line and b is the intersection of the y axis with the condition that:

  
when there is IR. , m equals 108 and b equals zero (0) for the values of x from 0 to 0.65, and m equals zero and b

  
  <EMI ID = 10.1>

  
45x 10-6 for values of x from zero (0) to 0.1, and

  
  <EMI ID = 11.1>

  
res at 0.1, and the upper limit of these areas is defined by the equation of the straight line defined above with the conditions that

  
  <EMI ID = 12.1>

  
values of x from zero (0) to 0.25, and m equals zero (0) and b equals 100 for values of x greater than 0.25, and

  
  <EMI ID = 13.1> x from 0.05 to 0.26, and m equals zero (0) and b equals 45 x

  
  <EMI ID = 14.1>

  
or:

  
IR &#65533; is the inelastic ratio of the laminate measured

  
  <EMI ID = 15.1>

  
external to the place of maximum deviation,

  
CLTE &#65533; is the coefficient of linear thermal expansion of the laminate,

  
TR is the thickness ratio ^ of the sum of the thicknesses of; metal layers to the thickness of the core layer of thermoplastic material,

  
YSm is the creep resistance for an average weight thickness of two layers of metal with a limit elongation of 5%, and

  
TS is the tensile strength of the layer

  
vs

  
core of thermoplastic material.

  
Expressed in another way, the ratio of thicknesses of the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material is described by the numerical overlap region of the

  
  <EMI ID = 16.1>

  
based on TR (YSm / TSc) and CLTE &#65533; as a function of TR (YSm / TS) as shown respectively in the figures

  
  <EMI ID = 17.1>

  
TS are defined as above.

  
The conditions of the process according to the invention are obtained when the process consists in:
a) placing a layer of metal on each side of a core layer of thermoplastic material, the thickness ratio of the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material is determined as described above, b) laminating the core layer of thermoplastic material and the metal layers by subjecting the assembly to high temperatures and to a pressure sufficient to maintain contact and adhesion, and c) cooling to room temperature.

  
So that the invention can be better understood, reference is made to the following figures where:
Figure 1 is a graph showing the <EMI ID = 18.1>

  
for laminates belonging to or outside the limits of the present invention, Figure 2 is a graph showing the relationship between the coefficient of linear thermal expansion

  
  <EMI ID = 19.1>

  
limits and outside the limits of the present invention, and Figure 3 is a graph showing a standard heat distortion temperature (HDT) variable <EMI ID = 20.1> laminates both within and outside the limits of the present invention.

  
1. Critical properties of use:

  
The metal-thermoplastic-metal laminates according to the invention are produced by means of a core layer of thermoplastic material and two layers of metal, each laminated on each side of the core layer of thermoplastic material. Laminates are characterized by a combination of critical properties of use - low coefficient of linear thermal expansion, low inelastic ratio (good elasticity in bending), and very good bending rigidity,
- as well as other desirable properties which make them excellent for use as building boards.

  
Low coefficient of linear thermal expansion

  
  <EMI ID = 21.1>

  
critical property of the metal-thermoplastic-metal laminates according to the invention because of the applications envisaged

  
  <EMI ID = 22.1>

  
parts due to temperature variations must be reduced to the minimum in order to minimize the possibility of warping and gaps between the metal and concrete components and the parts made with the laminates according to the invention. The coefficient of linear thermal expansion is measured according to the method of test ASTM D 696-70 for plastics. It can also be determined by measuring the distance between two thin parallel lines on the surface of the sample using

  
a calibrated mobile microscope or a cathetometer. The sample is located in a rectangular cavity in a heavy block of copper which can be thermostatically adjusted to various temperatures far apart from each other.

  
The rectangular cavity in the copper block is only slightly larger than the cross section of the sample, and the fine lines on the surface of the samples are visible through a narrow slot machined in the copper block.

  
Although some plastic materials are light and have a high energy absorption capacity (high impact resistance) making them suitable for use as building panels, they suffer from the disadvantage that their coefficients of linear thermal expansion are 4 to 5 and even 10 times higher than those of most metallic and glassy building materials, for example, aluminum, steel and concrete. Their use as construction panels on metal frames

  
or concrete is often prevented by the large differential thermal expansion which leads to fixing problems and, moreover, by invisible spaces which occur between panels at low temperatures and / or curl of panels at high temperatures.

  
The normal process of lowering the coefficient of linear thermal expansion of plastics is to incorporate glass fibers. Usually 30 to 40%

  
enough glass to reduce the coefficient of linear thermal expansion of a plastic material until it is equivalent to that of aluminum, (approximately 23.4 x 10-6

  
  <EMI ID = 23.1>

  
resistant but brittle material having only a small elongation before breaking. This means that the composite materials rupture at very low impacts whether the plastic itself is a resistant resin but brittle or not, such as a thermosetting polyester or a resistant polymer which is easily extensible with a high elongation before rupture such that nylon 6,6. He must be

  
  <EMI ID = 24.1>

  
reduced glass-filled plastics do not prevent the use of glass fibers for materials

  
of the core layer of thermoplastic material according to the invention in which laminating the suitable metal layers / on this core layer as described above tends to change (at least in part) the undesirable properties of the thermoplastic materials loaded by glass fibers.

  
Metals of course do not suffer from the disadvantage of high coefficients of linear thermal expansion like plastics. However, they are generally heavy, especially for sufficient thicknesses necessary for use as construction panels.

  
  <EMI ID = 25.1>

  
metal according to the invention have the best properties of the two types of materials. That is to say, not only they have a maximum weight not exceeding 9.76 kg / m2 but also they are characterized by a combination of

  
  <EMI ID = 26.1>

  
very good bending stiffness, and low coefficients of linear thermal expansion. The coefficient

  
linear thermal expansion must be less

  
  <EMI ID = 27.1>

  
are large enough for the applications envisaged in the building.

  
An example of the low coefficient of linear thermal expansion presented by the laminates according to the invention is as follows. A laminate (Example 2) consisting of two layers of aluminum 1100-0 0.0127 cm thick applied on each side of a 0.157 cm polypropylene layer had a coefficient of expansion

  
  <EMI ID = 28.1>

  
A low inelastic ratio (IR &#65533;) (good flexural elasticity) (less than 93%) is a typical property

  
metal-thermoplastic-metal laminates. Inelastic relationship characterizes elastic recovery

  
such laminate panels after having undergone sufficient deflection to produce a substantial tension (for example 5%) in the outer layers of metal at the location of the maximum deflection. It is measured according to a modification

  
r specific to the ASTM D 790-71 test. The process can be described as follows:

  
A sample sheet having a rectangular cross section with a width b = 1.27 cm, a thickness

  
  <EMI ID = 29.1>

  
is the spacing of the bending test in cm and [pound] greater than 1.27 cm, is arranged horizontally on a device for fixing a bending test in three points (i.e. with the width of 1.27 cm arranged horizontally and the depth d arranged vertically) and is bent with a bending speed D of 0.0212 cm / s up to a

  
  <EMI ID = 30.1>

  
of the external surface of the sample, i.e., unless noted otherwise, of 5% and calculated in% by the formula r = 600 dDo / L <2>. The spacing L used is approximately

  
16 times the depth d, except for the thicknesses

  
  <EMI ID = 31.1>

  
the spacing used is 2.54 cm. After bending the specimen to the specified bending D, the bending load is immediately removed at a rate of 0.846 cm / s. Then the sample is immediately removed from the bending test fixture, placed on its edges on a flat surface and allowed to

  
relax freely. Periodically, the sample is placed in the fixing device with the same spacing and configuration used to flex it, and its

  
  <EMI ID = 32.1>

  
  <EMI ID = 33.1>

  
inelastic ratio is calculated according to the formula IR = 100

  
  <EMI ID = 34.1>

  
  <EMI ID = 35.1>

  
and constantly before a week.

  
As noted above, the report

  
  <EMI ID = 36.1>

  
elastic recovery of the laminate panels after they have undergone sufficient deflection to produce substantial stress in the exterior surface.

  
  <EMI ID = 37.1>

  
degree of recovery of the stratified to re-obtain their original form after undergoing substantial stress and the capacity of the stratified to fully recover their initial form after undergoing bending

  
during their use with a somewhat lower degree of constraint, will be inadequate for the conditions of use requested. And, since one of the main objects of the present invention is the realization

  
of a metal-thermoplastic-metal laminate having

  
  <EMI ID = 38.1>

  
In general, materials with an inelastic ratio greater than 93% are too inelastic and / or too weak to be used as construction panels under the conditions required or requiring elasticity
(more specifically elastic recovery). The upper limit of the inelastic ratio of the laminates according to the present invention is therefore 93%. In addition, laminates having inelastic ratios in the following ranges, determined with a stress of 5%, in the outer layers of metal at the point of maximum deflection as described above, are as follows:
Inelastic report, Quality

  

  <EMI ID = 39.1>


  
Given that both the degree of recovery of the laminates to obtain their original shape after undergoing substantial stress and the ability of the laminates to recover fully without undergoing

  
  <EMI ID = 40.1>

  
When the inelastic ratio decreases, the lower the inelastic ratio becomes, and the more desirable the laminate becomes for building applications. So,

  
laminates with inelastic relationships in the

  
r &#65533;

  
good and excellent areas that is to say less than

  
75% are preferred.

  
It must however be admitted of course that,

  
although IR as used here is determined

  
(except when noted otherwise) for a stress r of 5%, other stress values either lower or higher can be used. However, the IR values determined for constraints other than 5% generally will differ from those determined at

  
5%. For example, an IR value determined for a stress lower than 5% (such as 1.5%) will generally be lower than that determined for 5%. Conversely, an IR value determined for a stress greater than 5% (such as 8%)

  
in general is greater than that determined at 5%.

  
It will be noted that the inelastic ratio for the laminates within the limits of the present invention surprisingly, is constantly lower than that of the materials of the layers of metal alone which have an inelastic ratio

  
  <EMI ID = 41.1>

  
sweet 1145-0). For example, a laminate (Example 2) comprising two layers of aluminum 1100-0 of 0.0127 cm thickness and a core layer of polypropylene of 0.0157 cm thickness, placed between the layers of metal had a inelastic ratio of only 72% compared to the very high inelastic ratios of 94% obtained for aluminum sheets 1100-0 alone.

  
As another example, a laminate (example 26) comprising two layers of aluminum 1100-0 of 0.0127 cm thick and a layer of nylon 6.6 of 0.180 cm disposed between the layers of aluminum and having good adhesion had an inelastic ratio of only 27% compared to the very high inelastic ratio of 94% of 1100-0 aluminum sheets alone.

  
Good elasticity (low IR) is therefore good recovery during the formation of

  
and therefore an essential property of the laminates according to the invention, in particular in comparison with the usual construction panels made of metal alone.

  
Excellent flexural rigidity (as well as a high flexural modulus, a measure of the flexural rigidity unit) is a highly desirable property that

  
laminates must possess. This requirement is necessary because the laminates must be rigid enough to minimize the need for structural framing and / or to minimize deflection of bending of laminate panels due to wind, due to forces hydraulic and other loads The ability of laminates to withstand wind pressures

  
and at hydraulic pressures is particularly significant

  
  <EMI ID = 42.1>

  
  <EMI ID = 43.1>

  
exterior panels for construction in the building.

  
The bending stiffness is measured according to a specific version of ASTM D 790-71, this specific embodiment can be described as follows:

  
A sample sheet has a rectangular cross section of width b = 7 cm, a thickness

  
  <EMI ID = 44.1>

  
cm, is arranged horizontally s n device for fixing the three-way bending test; ints (i.e. with the width of 1.27 cm arranged horizontally and the depth d arranged vertically) is bounded according to a speed

  
  <EMI ID = 45.1>

  
when the deviation D in cm increases at a constant specified speed. For thicknesses or depths d less than 0.165 cm, the spacing L is 2.54 cm. Otherwise, the spacing is about 16 times the thickness or depth of the sheet sample. The module

  
  <EMI ID = 46.1>

  
initial linear part of the load as a function of the

  
  <EMI ID = 47.1>

  
unless otherwise specified, this resistance is calculated as the voltage at which the stress on the outer surface of the central part of the sample

  
  <EMI ID = 48.1> by the formula m = 4bd <3> EB / L <3> for the specific case where b = 2.54 cm and L = 2.54 cm.

  
Flexural stiffness of 52.53 x 10 <3> N / m is the lowest value that can be used for panels in most building applications, even if a maximum of framework is used. and the requirements for deflection, bending for the panels are minimal.

  
  <EMI ID = 49.1>

  
0.0508 cm thick aluminum 5052-0 relatively

  
weak and inelastic weighing 1.37 kg / m <2>. This rigidi-

  
  <EMI ID = 50.1>

  
N / m, is easily achieved with laminates according to the present invention. For example, as shown in the

  
  <EMI ID = 51.1>

  
0.127 cm thick layers of aluminum 5052-0 appliedl on each side of a nylon 6.6 layer of 0.0711 cm had a flexural stiffness of 161.44 x 10 <3> N / m (flexural module of 28.95 x 109 N / &#65533; 12) and a weight of 1.49 kg / m <2> compared to a stiffness of 38.00 x 10 <3> N / m for a nylon sheet 6.6 of 0.133 cm thick alone weighing 1.51 kg / m <2>.

  
So the laminates give more rigidity

  
slightly lower weight than aluminum and even higher stiffness per unit area

  
compared to that of a thick sheet a lot

  
larger nylon 6.6 alone with equivalent weight

  
per unit area.

  
Similarly, also shown in the following table, a laminate (Example 2) comprising two layers of 0.0127 cm thick of aluminum 1100 -0

  
(which is even softer and more inelastic than aluminum

  
  <EMI ID = 52.1>

  
thick polypropylene had a bending stiffness of 329.19 x 10 <3> N / m (flexural modulus of 8.26 x 109 N / m <2>) and a weight of 2.10 kg / m <2> compared to a rigidity of 24.86 x 10 <3> N / m for a single polypropylene sheet having a thickness of 0.244 cm and weighing 2.20 kg / m <2>.

  
Thus it can easily be seen that the laminate gives a higher rigidity than the aluminum sheet having a weight per unit of surface area substantially equivalent and even a higher rigidity compared to that

  
a sheet of a single polypropylene which is 1.3 times thicker and having substantially the same weight per unit area.

  

  <EMI ID = 53.1>
 

  

  <EMI ID = 54.1>


  
  <EMI ID = 55.1>

  
thickness (cm), metal layer i layer

  
  <EMI ID = 56.1>

  
c value calculated from the thicknesses of the layers of

  
components and densities.

  
d value obtained for the same type of thickness panels

  
different.

  
taken from: "Materials Engineering / Materials Selector

  
'78 ", Reinhold Publishing Co ,. Stamford, Nov, 1977.

  
  <EMI ID = 57.1>

  
volume II, CRC Press, Cleveland, 1975.

  
As shown in the table above,

  
a laminate (example 59) comprising two layers of aluminum
6061-T6 0.122 cm thick on each side of a layer

  
  <EMI ID = 58.1>

  
bending of 606.72 x 10 N / m (an effective bending module of 27.64 x 109 N / m <2> and a weight of 2.21 kg / m compared to:
(a) flexural rigidity of 443.00 x 10 <3> N / m and a weight of 6.34 kg / m <2> for a 0.0813 cm thick automotive steel panel, <EMI ID = 59.1> weight of 2.20 kg / m <2> for aluminum sheet 6061 -T6

  
0.0813 cm thick alone.

  
(c) a bending stiffness of 434.25 x 10 <3> N / m and a weight of 2.75 kg / m <2> a 0.102 cm thick 6061-T6 aluminum panel alone, and
(d) flexural stiffness of 117.84 x 10 <3> N / m and a weight of 2.20 kg / m <2> for a single nylon sheet of 0.194 cm thick.

  
  <EMI ID = 60.1>

  
and 65% lighter per unit area than a 0.0813 cm steel panel. The laminate is more than 2.5 times

  
  <EMI ID = 61.1>

  
for an equivalent weight per unit area and 37% more rigid than 6061-T6 aluminum alone, having a weight

  
per unit area more than 20% higher than laminate.

  
And the laminate is more than 5 times stiffer than

  
nylon 6.6 alone having substantially the same weight per

  
unit of area.

  
Note that in applications requiring

  
  <EMI ID = 62.1>

  
panels of self-propelled vehicles etc., rigidity

  
bending of at least 262.65 x 10 <3> N / m is preferred,

  
with values of at least 437.75 x 10 <3> N / m or higher being even better.

  
It will be understood, of course, that all things being equal, with respect to the combination of the critical use properties possessed by the laminates of the present invention, the more the laminate / light, the more desirable it becomes. In the construction industry, certain applications requiring strength and rigidity

  
very high such as in these parts of self-propelled vehicles and in certain building surfaces, steel panels weighing up to 9.76 kg / m <2> are used. The maximum weight of the laminates according to the invention is therefore 9.76 kg / m <2>, values significantly lower than this weight being preferred. Values less than 6.34 kg / m <2> are preferred, however, values below 4.88 kg / m <2> being even better, especially in automotive applications. When polypropylene is the thermoplastic core and aluminum is the metal layer applied to each side of the core, the laminates according to the invention have a maximum weight of approximately 5.37 kg / m <2>.

  
Although each of the critical properties - low coefficient of linear thermal expansion (less than

  
  <EMI ID = 63.1>

  
93%) and excellent flexural rigidity (at least 52.53 x
10 <3> N / m) - is highly desirable, each taken alone is not sufficient. They must exist in combination. That is to say, in order to be suitable in a wide range of construction applications, metal-thermoplastic-metal laminates must have in combination a coefficient of linear thermal expansion

  
  <EMI ID = 64.1>

  
(IR inférieur) less than 93%, and a flexural rigidity of at least 52.53 x 10 <3> N / m.

  
2. Relations between the critical properties of use and the thickness ratio

  
Critical and immnorting properties of use

  
  <EMI ID = 65.1>

  
ratio of the thicknesses of the layers of the components of the laminates by means of the product of the ratio of the thickness of the sum of the thicknesses of the layers of metal to the thickness of the layer - core of thermoplastic material times the ratio of the resistances of the components of the laminate layers, i.e. via the following dimensionless parameter:

  

  <EMI ID = 66.1>
 

  
where TR is the thickness ratio, from the sum of the thicknesses of the metal layers to the thickness of the thermoplastic core.

  
YSm is the creep tensile strength for a

  
  <EMI ID = 67.1>

  
say, the sum of the products of the thickness of each layer of metal times its creep resistance with an elongation limit of 5% divided by the sum of the thicknesses of the layers of metal, or expressed in mathematical symbols,

  
  <EMI ID = 68.1>

  
or:

  
t., t .., ys-, and ys .. are defined below, Tm is the sum of the thicknesses of the metal layers where

  
  <EMI ID = 69.1>

  
and TS is the tensile strength of the thermo-material

  
vs

  
core plastic.

  
The creep resistance with a limit elongation of 5% for the metal layers (ys) is determined according to test ASTM D 638-72 entitled "Standard Method of Test for

  
  <EMI ID = 70.1>

  
used and the test speed is 5.0 mm per minute.

  
Samples of the metal to be tested are preconditioned

  
at 23 [deg.] C, with a relative humidity of 50% lasting at least
18 hours and the tests are carried out at 23 [deg.] C and

  
50% relative humidity. The value of ys is that of the metal after it has been subjected to thermal conditions

  
rolling. In many cases, this value ys will not differ significantly from that of the metal before rolling, since for many metals no change. Significantly of ys does not occur under typical thermal lamination conditions. In these cases where the value of ys must be determined on the metal after being subjected to thermal lamination conditions, the metal can be separated from the core of the laminate for a determination. for example, the thermoplastic core can be dissolved and the metal layers isolated for such determination.

  
It is recognized that certain layers of metal can undergo rupture before reaching the elongation of 5% limit. For such metals, the maximum tensile strength of the material should be used as the value for ys.

  
The tensile strength of a core of thermoplastic material (TS) is also determined according to the test of ASTM D638-72. Type I test samples are used and the test speed is 5.0 mm per minute. Samples were preconditioned at 23 [deg.] C for at least 18 hours. All unlaminated polyamide samples were kept dry, wetted in sealed containers with anhydrous magnesium perchlorate or anhydrous calcium sulfate as desiccants for

  
the preconditioning period and all other samples were preconditioned with 50% relative humidity. The tensile strength of thermoplastic materials is considered as elongation tension or in the absence of an apparent stretch limit, the tensile strength.

  
The value for TSC is that of the core after being subjected to the thermal conditions of rolling, which in general will be the same as that of the thermoplastic material before rolling. In cases where the thermoplastic material is such

  
  <EMI ID = 71.1>

  
  <EMI ID = 72.1>

  
can be determined for example, by subjecting a representative sample of the thermoplastic material alone, to the thermal conditions of the lamination and by making a measurement on the resulting material.

  
The thickness ratio (TR) is described by the numerical overlap region of the parameter TR (YSm / TSc) determined in the zones defined by the relationships of TR (YSm /

  
  <EMI ID = 73.1>

  
final cation planned for the laminate requires a temperature

  
  <EMI ID = 74.1>

  
(figure 3). The lower limit of these areas is defined by the equation of a straight line y = mx + b

  
where y represents the parameters of the -y axis (vertical axis)

  
  <EMI ID = 75.1>

  
\ on the y-axis.

  
  <EMI ID = 76.1>

  
values of x from 0 to 0.65, and m equals 0 and b equals -70 for values of x greater than 0.65.

  
  <EMI ID = 77.1>

  
10-6 for values of x from 0 to 0.1 and m equalO

  
  <EMI ID = 78.1>

  
  <EMI ID = 79.1>

  
and b equals -0.45 for x values from 0.05 to 0.12, and m equals 0 and b equals 0.75 for x values greater than 0.12.

  
The upper limit of the areas defined by the rela-

  
  <EMI ID = 80.1>

  
ment defined by the equation of the straight line defined above for the lower limit values of these zones.

  
  <EMI ID = 81.1>

  
of x from 0 to 0.25, and mega 0 and b equals 100 for values of x greater than 0.25.

  
  <EMI ID = 82.1>

  
216 x 10-6 for values of x from 0 to 0.05, m equal <EMI ID = 83.1>

  
0.004 to 0.04, and m equal. 0 and b equals 1 for values of x greater than 0.04.

  
If we refer to figure 1, we can easily see that all the values fall in a band defined by the external limits of curves 1 and 2 which are, respectively the upper and lower limits of the zones defined by the relations of TR (YS / TS) to IR &#65533;. So when it is desirable to have a laminate

  
  <EMI ID = 84.1>

  
the maximum value of 93% noted above), the thickness ratio of the laminate is easily determined in drawing

  
) <EMI ID = 85.1>

  
at the point of intersection on curve 1 (and of the curve

  
2 if possible), which value (s) can be read on the TR axis (YS / TS). The point of intersection with curve 1 (for

  
  <EMI ID = 86.1>

  
for the dimensionless parameter. TR itself can be easily determined by replacing the known values

  
  <EMI ID = 87.1>

  
and core. thermoplastic in dimensionless parameter.

  
If the same horizontal line drawn to intersect curve 1 also intersects curve 2, then an upper limit for TR (YS / TS) as well as TR alone can also be determined in the same way as described above for the lower limits. In such a case, a range of values for TR (YS / TS) and therefore TR will be established. On the other hand, when the horizontal line drawn to intersect curve 1 does not intersect curve 2, then depending on the weight and thickness limitations discussed above, there is no upper limit

  
  <EMI ID = 88.1>

  
If we refer to figure 2, we can easily see that all the values also fall in a defined band farces external limits by the curves 3 and 4, the upper and lower limits respectively

  
  <EMI ID = 89.1>

  
In a similar way to that described for figure 1, as soon as a desired value for CLTE &#65533; is chosen (inf-

  
  <EMI ID = 90.1>

  
TR (YSm / TSc) and therefore of TR itself can easily be determined.

  
When the temperature of thermal distortion of the laminates is a factor to be taken into account for the envisaged final application, with reference

  
  <EMI ID = 91.1>

  
values of laminates having layers of partially crystallized thermoplastic material - fall

  
  <EMI ID = 92.1>

  
5 and 6 which are the upper and lower limits, respectively, of the area defined by the relation between TR (YS / TS) to (HDT &#65533; -HDT) / (T -HDT). As soon as a

  
m c

  
desired value for HDT is specified, values

  
  <EMI ID = 93.1>

  
partially crystallized can be replaced in the normalized variable HDT,

  
  <EMI ID = 94.1>

  
determined, as described in Figures 1 and 2 by drawing a horizontal line from the value under

  
  <EMI ID = 95.1>

  
  <EMI ID = 96.1>

  
section on curve 5 (and curve 6 if possible).

  
Note that the thermal distortion temperature for laminates having layers of amorphous thermoplastic core is substantially the same as that of a layer of thermoplastic core alone.

  
This means that the application of the metal layers on both sides of an amorphous thermoplastic core layer has little effect, if any, in increasing the thermal distortion temperature,

  
So the optimum domain is preferred to TR for all

  
  <EMI ID = 97.1>

  
CLTE &#65533; (and HDT)) can easily be obtained by means of the linked values of TR (YSm / TSc) obtained from FIGS. 1 and 2 (and 3) by determining the region of the numerical overlaps of these values. In general, since

  
  <EMI ID = 98.1>

  
high under the conditions thus required) is preferred,

  
a TR (YS / TS) in the range of 0.08 and 0.6 is preferred, although / as shown in Figures 1 and 2

  
  <EMI ID = 99.1>

  
Note however that whatever the value of TR, the minimum thickness of each layer of metal must be approximately 0.00127 cm and the maximum weight of the laminate must be less than 9.76 kg / m <2> and in the case of retort polypropylene laminates with a thermoplastic core and aluminum as the metal layer on each side of the core, a maximum of 5.37 kg / m. In addition, from a practical point of view, TR must be greater than 0 (thermoplastic only) and less than absolute infinity (metal only) in that the laminates, metal-thermoplastic material-metal in the

  
  <EMI ID = 100.1>

  
As soon as TR is determined, if a thickness is chosen

  
  <EMI ID = 101.1>

  
thermoplastic core, the thickness for the layer of the compound &#65533; remaining health is easily determined. Note that in the specific case where the metal layers have

  
  <EMI ID = 102.1>

  
defined below, are not identical), the relative thicknesses of the metal layers must be specified in order to determine the value of YSm which

  
turn is necessary in order to calculate TR from TR (YS / TS) as shown below. Of course,

  
  <EMI ID = 103.1>

  
respective metal arbitrarily designated "i" and "ii") is known, the thickness required for the core layer

  
  <EMI ID = 104.1>

  
The way in which Figures 1 and 2 (and 3

  
  <EMI ID = 105.1>

  
described below are used to establish the values of TR (YSm / TSc) and therefore of TR alone is to choose values

  
  <EMI ID = 106.1>

  
proportionate depending on the intended use. For example, if the intended end application requires a

  
  <EMI ID = 107.1>

  
between 0.15 to about infinity (or just a value

  
at least 0.15) would be shown in Figure 1. If the appli-

  
  <EMI ID = 108.1>

  
then a TR (YSm / TSc) located between 0.065 and approximately infinity
(or simply at least equal to 0.11) would be indicated

  
  <EMI ID = 109.1>

  
for the final application envisaged, by choosing polypropylene (HDT = 60 [deg.] C, Tmc = 170 [deg.] C) as the partially crystallized thermoplastic core layer, the

  
  <EMI ID = 110.1> <EMI ID = 111.1>

  
to get a value of 0.89. This normalized HDT variable would require according to Figure 3 a value between 0.033 and about infinity (or again simply <EMI ID = 112.1> <EMI ID = 113.1>

  
The optimum values for TR (YS / TS) for a laminate

  
c -1

  
  <EMI ID = 114.1>

  
of 158 [deg.] C and a layer of polypropylene thermoplastic core would be the overlap region, namely between 0.15 and about infinity (or simply a value of at least

  
  <EMI ID = 115.1>

  
  <EMI ID = 116.1>

  
determined as soon as the metal layers - for example,

  
the

  
aluminum and more specifically / specific composition (type) and thickness of aluminum - are specified.

  
Since: TR (YS / TS) = 0.15

  
  <EMI ID = 117.1>

  
If, for example, for aluminum 1100-0

  
  <EMI ID = 118.1>

  

  <EMI ID = 119.1>


  
So TR must have a minimum value of at least

  
  <EMI ID = 120.1>

  
  <EMI ID = 121.1>

  
tick. An experimental laminate having the above specified combinations of properties with TR having a value of 0.162 is described in Example 2.

  
  <EMI ID = 122.1>

  
would remain unchanged since in this case the overlap region for TR (YSm / TSc) is identified only by the values shown in Figure 1.

  
On the other hand if the overlapping region

  
  <EMI ID = 123.1>

  
part by the value domain shown in Figure 3, not considering HDT in such cases would have

  
  <EMI ID = 124.1>

  
N / m <2>) as layers of metal and a block copolymer (HYTREL
4056, 11.7%) -poly (ethylene terephthalate) modified (HDTc =

  
  <EMI ID = 125.1>

  
Figures 1, 2 and 3 would indicate an optimum range between 0.015 and 0.107, and therefore a range of TR between 0.0149 and 0.106. An experimental sample of such laminates.

  
with a TR value of 0.047 is described in Example 96,

  
  <EMI ID = 126.1>

  
of the overlap for TR (YSm / TSc) determined from Figures 1 and 2 for the laminate described above would indicate a larger optimum range - i.e. consistent with minimum rigidity and thickness requirements metal noted above, a lower limit approaching 0 and an upper limit of approximately 0.114 - for TR (YSm / TSc). These values in turn would impose an extended TR range corresponding to a lower limit approaching 0 and an upper limit of approximately 0.113.

  
It should be noted that since the laminates according to the invention comprise two layers of metal, one on each side of the core layer of thermoplastic material, the layers of metal can have either the same or different compositions as long as the combination of the critical and important usage properties is obtained. Metallic layers with different thicknesses can also be used as long as such thicknesses come within the established limits

  
  <EMI ID = 127.1>

  
metal and the maximum weight requirement of laminates obtained and that the combination of critical properties is obtained. When metal layers having different compositions and / or different thicknesses are used, it is preferred that some of the important properties be substantially balanced in order to avoid, - problems &#65533; my such as curl, etc. when such

  
are exposed to temperature variations. As far as possible, the important properties of the metal layers must be balanced in such a way that:
(a) CLTEi = CLTEii
(b) tiEi = tiiEii 'and <EMI ID = 128.1>

  
respectively the coefficients of linear thermal expansion, the thicknesses, the elastic moduli, and the creep resistances of the respective metal layers arbitrarily designated by "i" and "ii". However, in a practical manner, it is generally preferred that the two layers of metal have the same composition and the same thickness.

  
In an example where the metal layers having different compositions (and different thicknesses) are

  
low in

  
employed - a layer of C 1010 carbon / steel of 0.00508 cm thickness annealed and a layer of aluminum 6061-0 of

  
  <EMI ID = 129.1> <EMI ID = 130.1>

  
between 0.0010 and 0.31 would be shown in Figure 1. If the intended end application also requires a CLTE &#65533;

  
  <EMI ID = 131.1>

  
shown in Figure 2.

  
The optimum values for TR (YS / TS) for a stratum.

  
  <EMI ID = 132.1>

  
would be between 0.043 and 0.31, the numerical overlap region for Figures 1 and 2.

  
The optimum values for TR alone can easily be determined given, as noted above,

  
be low in

  
  <EMI ID = 133.1>

  
106 N / m <2> with a maximum elongation percentage of 5%) are used as metallic layers. Given that :

  

  <EMI ID = 134.1>


  
  <EMI ID = 135.1>

  

  <EMI ID = 136.1>


  
Therefore,

  

  <EMI ID = 137.1>


  
and

  

  <EMI ID = 138.1>


  
Therefore, TR must be between 0.0185 and 0.133 for the above specified balance of IR, &#65533; and CLTE &#65533; for a laminate comprising a sheet thickness of 0.005GB cm

  
low in

  
  <EMI ID = 139.1>

  
is described in Example 156.

  
  <EMI ID = 140.1>

  
in turn measured from the aluminum side for the laminate

  
  <EMI ID = 141.1> <EMI ID = 142.1>

  
would require a range of values of TR (YS / TS) between 0.020 and 0.33, and about 0.023 and infinity as shown in Figures 1 and 2, respectively, the range 0.023 to 0.33 defining the region digital overlap. The values for TR alone would therefore be between 0.00989 and approximately 0.142, which range adapts perfectly to the TR value of 0.0654 for the laminate described in Example 156.

  
3. Other important properties

  
In addition to the above Critical Properties for

  
most

  
construction, / laminates within the limits of the present invention must also have excellent deformability at high temperatures, very good ductility

  
and a high energy absorption capacity.

  
Excellent deformability is a necessary property for laminates that need to be processed

  
  <EMI ID = 143.1>

  
that is, subject to subsequent shaping operations. Excellent deformability and very good ductility

  
metal-thermoplastic laminates - metal prepared from layers of ductile metal and a core layer of ductile thermoplastic so that such laminates can be made into a large number of shapes - from shapes slightly curved to deep-drawn forms - without breaking.

The terms "ductile" and "ductility" used

  
  <EMI ID = 144.1>

  
of metal and a core of thermoplastic material and the laminates, within the limits of the present invention, refer to these materials having an elongation in tension until rupture of at least 10% measured according to the method ASTM D638-72 for piastres.

  
The shaping (or, more precisely the subsequent shaping) of the laminate can easily be obtained according to the methods of these specialists in the field,

  
One of these methods which can be used here consists in subjecting the laminate to pressures at high temperature, that is to say a temperature which is high enough to soften the core layer of thermoplastic material and allow the implementation of a shaping operation without simultaneous delamination, weakening of the metal layers and / or the core layer of thermoplastic material, etc. For most of the laminates of the present invention, the setting operation

  
  <EMI ID = 145.1>

  
avoided since most of the laminates in

  
the limits of the present invention are not cold deformable for such temperatures, According to the present invention the laminates are not intended to be

  
  <EMI ID = 146.1>

  
te, the yield in a stamping test is

  
low and / or the degree of flexion is low and / or the yield in the Olsen test is poor, these tests being described below. In addition, an additional advantage for the implementation of the irise-shaped operation

  
high temperatures is that such temperatures will usually destroy the memory of the laminate at

  
  <EMI ID = 147.1>

  
recover its straight and / or flattened shape after release

  
shaping pressure. This loss of memory is maintained up to approximately the original shaping temperatures and for some laminates at even higher temperatures. Therefore, at elevated temperatures the laminates of the present invention prepared for example from the layers

  
  <EMI ID = 148.1>

  
ductile are deformable in structure retaining their shape permanently.

  
Significant wear in the deformability of the laminates of the present invention can be obtained by means of a stamping test, the typical conditions of which are given in the table below. In this test, a flat, circular sheet of laminate is forced into a female die by means of a male stamp to form

  
a cut A successful stamping with a high stamping ratio, (ratio of the diameter of the blank

  
the diameter of the print) is desirable. Stamping ratios comparable to those obtained for stamping

  
quality steel with equivalent stiffness is preferred Values that are 50% lower than this steel are acceptable for many applications

  
but values much lower than these would be considered insufficient. For example, as shown in the following table, a very good drawing ratio between 2.0 and 2.31 is obtained with aluminum / nylon 6,6 / aluminum or aluminum / polyester / polyester modified polyether block copolymer PET laminates. / aluminum when the tests are carried out at temperatures between 80 [deg.] C and 200 [deg.] C. This ratio is comparable to the values of 2.4 for stamping quality steel and, in some cases, better than the value of 2.1 for stamping quality aluminum. Laminates that include

  
a 6.6 nylon core and layers of steel metal

  
Low carbon ductile carbon was found to behave appropriately in the environmental drawing test.

  
It should however be noted that the drawing ratios indicated in the table below have no limit values, and therefore even higher drawing ratios for such laminates are envisaged.

  

  <EMI ID = 149.1>


  
a Polished print

  
b Smooth print

  
Another important measure of deformability

  
of laminates is their degree of flexure without breaking.

  
The degree of flexion that can be achieved by most

  
laminates according to the invention without breakage is extremely poor at ambient temperatures and in many

  
case would not be appropriate for all the applications requiring a simple bending around a radius even quite large. Bending is generally considered to be

  
weak if the laminate does not resist bending
90 [deg.] Around a radius of 2 times the thickness of the laminate.

  
  <EMI ID = 150.1>

  
easily be folded, without breaking around a radius small enough for many applications.

  
It should be noted, however, that some laminates within the limits of the present invention exhibit good bending capacity at room temperature, for example, laminates which had a 6.6 nylon core and low-strength steel metal layers ductile carbon content. It should however be understood that other laminates within the limits of the present invention also behave

  
good at bending tests at ambient conditions. A

  
another test for measuring deformability is the deviation test with a spherical stamp such as the Olsen test

  
which only involves drawing (no drawing) and where a sheet or sample of laminates is firmly fixed in an annular matrix and deformed by stretching until rupture (first appearance of crack) by means of a hemispherical stamp under conditions typically shown in the table below. A measure of performance is the deformation ratio (ratio of the depth of penetration of the stamp to the diameter of the stamp), a high ratio being desirable. Using

  
this test with low strain rates and ambient temperatures, excellent strain ratios between 0.300 and 0.400 were obtained for the laminates of the present invention for example, laminates! which included a 6.6 nylon core and layers

  
low ductile carbon steel metal and other laminates as shown in the table below. These values are comparable to (and in many cases better than) the values obtained for aluminum and steel. Even weaker ratios

  
that 0.300, for example as low as 0.150, are acceptable for certain applications but values much lower than these would be considered poor in this test.

  

  <EMI ID = 151.1>
 

  
Since stamping and bending

  
successfully most of the laminates of the present invention seem to require the use of high temperatures, it is ultimately advantageous for most laminates to carry out the deformation operation.

  
tion at elevated temperatures, particularly for most laminates which must be subjected to the subsequent elevated temperature conditions to be deformed and obtain their desired shape. And, as noted above, laminate temperatures between 80 [deg.] C and 200 [deg.] C are generally suitable for carrying out shaping operations.

  
It will be obvious of course that the laminates

  
of the present invention, when considered in relation to the combination of the critical properties they possess as well as the excellent deformability indicated in most cases by the high drawing ratio, the flexural and d The drawing obtained during the stamping, bending and drawing tests are obvious advantages over known laminates and other building boards used as building boards. By comparing

  
with the metals themselves, the combination of critical and important usage properties - low

  
coefficient of linear thermal expansion, low

  
inelastic ratio, excellent flexural rigidity low weight and excellent deformability in most

  
cases make the sheets even more desirable for use as building panels.

  
Very good ductilities at ambient temperatures are obtained for the laminates of the invention, when both the metal layers and the core of thermoplastic material are in a ductile state. He will be ; admitted that although it is possible to use non-formal forms

  
  <EMI ID = 152.1>

  
higher flexural strength and higher flexural modulus are obtained, the deformability discussed above is significantly reduced. However, when shaped structures are not required

  
are

  
or desired, and that substantially planar structures / necessary :) non-ductile forms of suitable metals can be used. The ductility measurement of the sheets can be obtained by Olsen b-test. Other measures of ductility are the tensile elongation which is measured according to the ASTM D682-72 test for plastics, and the

  
  <EMI ID = 153.1>

  
Gardner's shock resistance test.

  
In Gardner's test, a sample sheet

  
at least 5.08 cm times 5.08 cm of surface is arranged

  
on a flat horizontal surface with a heavy anvil

  
in steel. The sample is centered on a vertical cylindrical cavity (3.18 cm inside diameter). A print

  
made of light polished steel 1.59 cm in diameter with a hemispherical apex is placed on the upper center of the sample. A 1.82 kg hammer is dropped from a selected height onto the print, thereby subjecting the sample

  
at a determined impact energy in N-m. by the product of the weight of the hammer and its initial height in cm, Each laminate sample was struck only one ibis

  
and the formation of a crack on one side or the other of the sample is considered as a rupture for this particular shock. The test usually requires a relatively large number of samples (usually at least 10 to 16 for each test), and the maximum height at which more

  
half of the sample withstands without failure is used to calculate Gardner impact resistance (GIS)

  
+ 0.226 N-m. For these measurements, it was determined that the ductile sheets of the. present invention having

  
  <EMI ID = 154.1>

  
at impact energies up to at least 18.08 N-m and have noticeably smaller bumps for these impacts than 0.0813 cm thick steel panels. Similar results are also obtained with aluminum panels. Therefore, metal-thermoplastic-metal laminates also have good energy absorption capacity in that they are capable of absorbing high impact forces with few, if any, bumps. and, as an additional feature, when there are bumps, they can easily be treated with a hammer without any damage.

  
The capacity of the laminates according to the invention

  
withstand exposure to the weather without deterioration of the metal-thermoplastic adhesion

  
  <EMI ID = 155.1>

  
Another valuable property is critical properties.

  
It will be obvious of course that layers of metal,

  
unprotected steel etc, will corrode after long continuous exposure to the weather. However, the adhesion between the layers of metal and the layer of

  
core of thermoplastic material resists such weathering, in particular in those cases where the initial adhesion of the metal-thermoplastic material is very good.

  
Little or no loss of adhesion occurs with

  
aluminum-nylon-aluminum laminates after one month in boiling water. In addition, aluminum-nylon-aluminum laminates show no loss of adhesion after 13 months in water, or after 11 months in saturated aqueous solutions of calcium chloride and chloride.

  
sodium at room temperature.

  
  <EMI ID = 156.1>

  
laminates having a relatively low initial metal to thermoplastic adhesion (although having an air resistance greater than 1.75 x 10 <3> N / m) as noted below are more likely to experience partial deterioration in grip as it is

  
highlighted by a drop in adhesion strength. For example, aluminum - HDPE-aluminum laminates having a relatively low initial adhesion strength shows an approximately 50% drop in this resistance after more than 12 months in water at ambient temperatures. The metal-thermoplastic adhesion, however, remains sufficient to satisfy the combination of critical properties necessary and discussed above.

  
The adhesion strength of the laminate layers according to the invention is not as critical and can vary in wide areas. There are no particular upper limits of this resistance since for the envisaged construction applications, the stronger the adhesion and the more the laminate is generally suitable,

  
in particular for subsequent formatting operations. A lower limit of the adhesion strength for metal-core components of thermoplastic material is however much greater and it must be

  
  <EMI ID = 157.1>

  
49.

  
It will be evident that, in addition to each of the properties listed and discussed above, metal-thermoplastic-metal laminates have smooth metal surfaces. However, among the metals indicated above as suitable, some of the surfaces - for example steel, iron etc. get strung after continuous exposure to the weather, and it is very advantageous that a protective surface layer can be easily applied to these metal surfaces which tend to

  
corrode and cook these protective layers so

  
to increase the resistance and hardness of the coating and then its adhesion to the surface of the metal.

  
Therefore, shaped laminates as well as substantially flat, are easily protected by applying usual metal protective layers to at least one of the metal surfaces and by curing this layer at high temperatures. For example, since

  
the most common protective coating is paint, metal surfaces can easily receive a primer and then a coat of paint. The paint can be baked at high temperatures,

  
without the laminates being distorted,

  
especially when the core of thermoplastic material

  
  <EMI ID = 158.1>

  
as amorphous) as discussed above; are used. For example, with regard to automobiles. , baking paint is often done at temperatures as high as 325 [deg.] C. The painted laminate is then cooled to ambient temperatures.

  
It will however be admitted that the actual temperature used

  
  <EMI ID = 159.1>

  
  <EMI ID = 160.1>

  
actual employed, whether low or high, it is envisaged that the protective coating will be cured at. an appropriate temperature easily determined by these specialists in the field.

  
The laminates according to the invention, when used under conditions where temperatures are high

  
  <EMI ID = 161.1>

  
critical and important properties as well as other desirable properties described above, having a high distortion temperature in order to survive these conditions without warping or flattening (if these are

  
  <EMI ID = 162.1>

  
laminates are used as construction panels for applications for self-propelled vehicles,

  
  <EMI ID = 163.1>

  
existing in paint baking ovens - at least

  
case
135 [deg.] C, In such /, a high distortion temperature;
(HDT &#65533;) of at least 1350C is required, 163 [deg.] C being preferred:

  
  <EMI ID = 164.1>

  
even at the high temperatures existing in many paint baking ovens,

  
In those cases where a distortion temperature

  
East

  
  <EMI ID = 165.1>

  
of thermoplastic material core must have either a point:

  
  <EMI ID = 166.1>

  
the desired thermal distortion temperature.

  
For example, for automotive applications when a thermal distortion temperature

  
  <EMI ID = 167.1>

  
be at least 135 [deg.] C. It will be noted that although only those polymers which are partially crystalline

  
  <EMI ID = 168.1>

  
present invention (discussed below) have a sufficiently high glass transition temperature to allow laminates having very high distortion temperatures, it is preferable in such cases to employ! partially crystalline thermoplastics having sufficiently high melting points.

  
The melting point of thermoplastics

  
  <EMI ID = 169.1>

  
are subjected either to the temperature at which the apparent fusion is maximum or to the temperature at which at least traces of fusion are detected, the latter being preferred in the case where the difference between the two is appreciable, for example greater than 10 [ deg.] C.

  
The expression "partially crystalline" is used

  
  <EMI ID = 170.1>

  
of which at least 40% by weight are organic thermoplastic polymers, with at least 50% by weight of polymers, organic thermoplastics being chains of polymers or chain segments having a degree of crystallinity

  
(DC) greater than 15%. The degree of crystallinity is specified by the following formula:

  

  <EMI ID = 171.1>


  
or:

  
d is the density of the polymer chains or of chain segments of the partially crystallized polymers in the organic polymers part of the composition;

  
  <EMI ID = 172.1>

  
except for substantial volume fractions of other

  
of

  
non-crystallizable organic modifiers / polymers

  
or phases of inorganic fillers that the compositions of the thermoplastic core could contain.

  
  <EMI ID = 173.1>

  
polymer chains or segments of polymer chains

  
  <EMI ID = 174.1>

  
organic re of the thermoplastic composition partially crystallized at 23 [deg.] C, and

  
  <EMI ID = 175.1>

  
partially polymer chains or chain segments

  
\ crystallized from the organic polymer part of the compound

  
  <EMI ID = 176.1>

  
parameters of the crystal lattice obtained by wide angle X-ray diffraction measurements. The value

  
  <EMI ID = 177.1>

  
hardened furrows showing no apparent degree

  
crystallinity by X-ray diffraction or differential scanning calorimetric measurement. According to another

  
  <EMI ID = 178.1>

  
extrapolate from the density dependence of partially crystallized samples of the organic polymer with finite known values of apparent degree of crystallinity

  
  <EMI ID = 179.1>

  
  <EMI ID = 180.1>

  
diffracted and dispersed at large angles at once

  
by polymer crystallites and amorphous polymer parts or by differential scanning calorimetric measurements of the latent heat of fusion, so that,

  
  <EMI ID = 181.1>

  
the heat of fusion measured is a fixed estimated value for the perfect polymer crystal.

  
Similarly and for reasons noted above, for a core layer material of thermoplastic material, when a distortion temperature

  
  <EMI ID = 182.1>

  
metal layers (discussed below) should have a melting point above the most

  
  <EMI ID = 183.1>

  
we base ourselves on obtaining the desired thermal distortion temperature. That is, when the thermoplastic core layer is partially crystalline and has a temperature

  
  <EMI ID = 184.1>

  
then the metal layers must have melting points higher than Tm of the core layer of thermoplastic material. Similarly, when the thermoplastic material of the core layer is amorphous but has a temperature Tgc high enough to obtain HDT &#65533; metal layers must be painted

  
  <EMI ID = 185.1>

  
thermoplastic.

  
It was surprising and unexpected to find that the thermal distortion temperature of the laminates

  
  <EMI ID = 186.1>

  
expensive that of the melting point of partially crystalline materials from the thermoplastic core. Therefore, the distortion temperatures. The thermal performance of the laminates can exceed that of the core material of thermoplastic material by several hundred degrees when partially crystalline thermoplastic materials are used as the thermoplastic core layer.

  
For example, a laminate (example 24) comprising two layers of aluminum 1100-0 of 0.0127 cm and a layer of nylon core 6.6 of 0.295 cm thick interposed between the layers of metal and adhering thereto ci, had a thermal distortion temperature of 228 [deg.] C by comparison

  
  <EMI ID = 187.1>

  
dimensional stability under stresses at elevated temperatures is therefore a highly desirable characteristic for the laminate, particularly when core layers of thermoplastic material having either a

  
  <EMI ID = 188.1>

  
Note, however, that the remarkable increase

  
the thermal distortion temperature shown by laminates comprising partially crystalline thermoplastic core layers with respect to

  
to the core layers of thermoplastic material alone is not shown by similar laminates comprising a core layer of amorphous thermoplastic material. For example, a laminate (example 92) comprising two layers of aluminum 1100-0 with a thickness of 0.0127 cm and

  
a core layer of PET (polyethylene terephthalate) of

  
  <EMI ID = 189.1>

  
38% (i.e. partially crystalline) disposed between <EMI ID = 190.1>

  
thermal distortion temperature of 240 [deg.] C compared to only 89 [deg.] C for PET alone, an increase of

  
  <EMI ID = 191.1>

  
comprising two layers of aluminum 1100-0 0.0127 cm thick and a layer of amorphous PET 0.168 cm thick! its thermoplastic core had a thermal distortion temperature of only 79 [deg.] C compared to

  
68 [deg.] C for amorphous PET alone, an increase of only 11 [deg.] C.

  
The temperature of thermal distortion, also known as the temperature of deformation under a bending load, is measured according to a specific modification of test ASTM D 648-72 for plastics. In this modification, the width of the sheet sample b b ’is 2.22 cm, the length 7.62 cm,

  
  <EMI ID = 192.1>

  
4. Materials constituting the laminates.

  
Materials useful as a thermoplastic core layer for the present invention are not critical. However, such thermoplastics must necessarily have properties and characteristics which will give laminates having an improved combination; properties of use considered important and critical for the requested construction applications. Such an important and critical combination of properties:
as noted above has, among others, a lower coefficient of linear thermal expansion

  
  <EMI ID = 193.1>

  
and a flexural rigidity of at least 52.53 x 10 <3> N / m.

  
Examples of classes of thermoplastics suitable for the present invention are the thermoplastic polymers based on acetal-, acrylic, amide, arylene sulfide, arylene sulfone, arylene carbonate, cellulosic:
ester, imide, olefin, styrenic, and vinyl.

  
Examples of acetate-based thermoplastics are polyvinyl butyral, polyformaldehyde, polyacetaldehyde, copolymers and terpolymers thereof, block copolymers and grafted rubber modifications.

  
  <EMI ID = 194.1>

  
various nylons, nylon 6 or poly (&#65533; -caprolactam) or poly (imino &#65533; 1-oxohexamethylene), nylon 12 or poly (lauryl lactam) or poly

  
  <EMI ID = 195.1>

  
ne), nylon 6,6 or poly (hexamethylene adipamide) or poly
(imino-adipoylimino-hexamethylene), nylon 6.10 or poly (hexa-

  
  <EMI ID = 196.1>

  
poly (hexamethylenedodecanoamide) or poly (iminohexamethyleniminododecanedioyl), copolymers, terpolymer &#65533; block copolymers and graft copolymers thereof and many partially aromatic nylons (PARNs).

  
PARNs are obtained when an aromatic residue or aromatic unit is replaced in whole or in part

  
by an aliphatic residue or unit in an aliphatic nylon polymer. For example, substituting the whole

  
  <EMI ID = 197.1>

  
isophthalic acid (IA, or m -HOOC -C6-H5-COOH)

  
give suitable PARNs which are nylons 6, TA-co6, IA or poly (hexamethylene tere-co-isophthalamides) or
(poly-iminohexamethyleneiminoterephthaloyl-co-isophthaloyls). Other suitable PARNs are nylons 6,6 -co-6, TA, nylons 6,6 -co-6, IA, nylons 6,6-co-6, TA-co-6, IA, and d other similar PARNs, including PARNs or some or all of the diamine groups have a character!

  
i aromatic and those containing lactic acid groups such as 6-co-6,6-co -6-TA nylons.

  
Other thermoplastic materials based on suitable amide are crystalline and amorphous nylons with aliphatic or cycloaliphatic diamine groups with chain

  
  <EMI ID = 198.1>

  
amide-based plastics are blends of polyamides
(nylons) and grafted block and copolymers. Examples

  
of these mixtures of nylon 6 with nylon 6-block polymer
(of tetramethylene oxide) (nylon 6-block polymer (butylene oxide)), nylon 6,6 with nylon 6 block polymer (oxide of <EMI ID = 199.1> <EMI ID = 200.1>

  
nylon 6,6 with block polymer nylon 6 (propylene oxide), nylon 6,6 with butyl acrylate polymer - filled with nylon 6,6 and many other blends. Such materials can exhibit low notch sensitivity and high strength and good impact resistance even

  
at low temperatures.

  
Examples of suitable thermoplastics based on esters are poly (alkylene terephthalates) having

  
alkylene groups with up to two to ten atoms

  
  <EMI ID = 201.1>

  
poly (butylene terephthalate), or poly (tetramethylene terephthalate), poly (decamethylene terephthalate), poly
(1,4-cyclohexyl-dimethylol terephtahalate), and many similar poly (alkylene terephthalates) and poly (alkylene isophthalates) copolymers and terpolymers and block copolymers and grafted modifications of rubber.

  
Examples of arylene ether-based thermoplastics are oxidized poly (2,6-dimethylphenylene),

  
  <EMI ID = 202.1>

  
(SAN), acrylonitrile butadiene-styrene copolymers (ABS)

  
or resins, and block copolymers and rubber graft modifications.

  
The thermoplastic materials based on arylene sulfide are for example poly (phenyl sulfide).

  
Examples of thermoplastic materials based

  
  <EMI ID = 203.1> phenylene sulfonyl -1.4 phenylene) or simply polyether sulfone, and block copolymers and grafted rubber modifications.

  
Cellulosic thermoplastics are

  
for example cellulose acetate, cellulose propionate, cellulose butyrate, and cellulose acetate butyrate.

  
Examples of imide-based thermoplastics are poly (N-methylmaleimide), other poly (N-alkylene 'maleimides), copolymers and terpolymers thereof, and block copolymers and graft modifications of rubber, and polyimides and copoly (imide / amides) of pyromelletic dianhydride and m-phenylene diamine and other similar polyarylene imides and copoly (arylene imide / amides).

  
Examples of olei-based thermoplastics

  
  <EMI ID = 204.1>

  
greater than 0.944 g / cm <3>, low density polyethylenes
(LDPE), maximum density 0.944g / cm <3>, polypropylenes, poyl (1-butene), poly (3-methyl-butene), poly- (4-methyl-pentene), multipolymers derived from these corresponding monomers, copolymer &#65533; rubber blocks and modifications. Although the present invention excludes laminates which have a core of

  
  <EMI ID = 205.1>

  
high and aluminum applied to both sides of this core, it should be understood that such exclusions apply. only homopolymers and not multipolymers derived from the corresponding monomer or block copolymer or other modifications, for example, rubber modifications and load modifications which are described below. Similarly, in the claims the specific weight limitation of the laminates comprising

  
a polypropylene core and aluminum metal layers on both sides of the core apply only to homopolymers.

  
Vinyl-based thermoplastics are, for example, polyvinyl chloride (PVC), copolymers and terpolymers, block copolymers, reinforced modifications of grafted rubber, and modifications of ABS resin thereof.

  
Suitable styrene-based thermoplastics are, for example, copolymers containing polar functional groups such as poly (styreneco-acrylonitrile) (SAN) and grafted modifications of

  
  <EMI ID = 206.1>

  
cations are ABS resins.

  
Thermoplastics can be modified with fillers, reinforcing agents, plasticizers, stabilizers, flame retardants, and other polymer modifiers well known in the art,

  
aim to change their properties and thus broaden the scope

  
their applicability. One of these changes is

  
reinforcing thermoplastic materials with mineral and / or organic fillers and fibers which may have been treated with adhesion promoting agents or

  
coupling agents capable of increasing adhesion

  
fillers and fibers to the molecules of the matrix of thermoplastic material. A large number of compounds

  
  <EMI ID = 207.1>

  
particularly capable of carrying out the work of improving the adhesion between the thermoplastic materials and the mineral fillers and the glass fibers, thereby creating a synergistic effect in comparison with the untreated fillers and fibers.

  
Preferred mineral fillers are quartz,

  
with grain of small dimensions. wollastonite, feldspar,

  
  <EMI ID = 208.1>

  
these mineral fillers when used, can vary from very small quantities from 1 to 2% by weight up to 50% by weight or even more, with concentrations between 20 and 45% by weight being preferred.

  
  <EMI ID = 209.1>

  
are glass fibers and other high performance fibers

  
  <EMI ID = 210.1>

  
'of "

  
aromatic fibers% polyamides of potassium titanate fibers etc. It will be noted that, although such high performance and high modulus fibers - glass fiber for example - improve the strength and the modulus of bending; thermoplastic materials used, dis also produce a decrease in multiaxial impact resistance. Despite this apparent disadvantage, however, concentrations!

  
  <EMI ID = 211.1>

  
that 33% by weight) can be advantageously used

  
if we want to improve certain properties.

  
The metals which are useful for the present invention lie in a relatively broad field. Each layer of metal must, however, have a minimum thickness of at least 0.0127 cm. In addition, for certain specific applications of such metals, preferably / must have certain other properties. These properties are: a) metals, when a high thermal distortion temperature is desired for the laminate, must have a melting point higher than the melting point where at the highest glass transition temperature of the material core layer thermoplastic, depending on which one is used to designate the desired thermal distortion temperature. b) metals must have creep resistance <EMI ID = 212.1>

  
N / m <2> at temperatures above the temperature

  
  <EMI ID = 213.1>

  
substantially according to the ASTM D 638-72 test previously discussed, c) the metals must have a modulus of elasticity <EMI ID = 214.1>

  
ambient also determined according to the test previously; mentioned from ASTM D 638-72 and d) the metals must be ductile, particularly when it is desired that the resulting laminates must be subjected to subsequent shaping operations.

  
  <EMI ID = 215.1>

  
those allowing to obtain laminates having a critical and important combination of properties such

  
that coefficient of linear expansion less than 63 x 10

  
  <EMI ID = 216.1>

  
at flexion of at least 52.53 x 10 <3> N / m and a weight less than 9.76 kg / m <2> can be either ferrous or non-ferrous. Examples of ferrous metals are

  
steels, especially low carbon steels, stainless steels, galvanized iron, etc. Non-ferrous metals are for example aluminum, magnesium,

  
zinc, tin, nickel, titanium, copper, cobalt, beryllium, and alloys of each of these metals such as different brass; and bronzes.

  
The thermoplastic layer and the layers

  
of metal are evenly and firmly bonded together to. ' form the laminates. If desired, an adhering agent

  
1 suitable of those listed below can be used to facilitate the formation of laminates having the critical properties discussed in detail above.

  
Note that although the use of bonding agent for laminates is not essential,

  
in general it is preferred to use such an agent to guarantee good metal-thermoplastic adhesion. For example an adhesion strength of at least 1.75 x 10 <3> N / m is generally suitable. It will be obvious however

  
  <EMI ID = 217.1>

  
stique are preferred.

  
Adhesion agents when used, which are suitable for fixing the metal layers to the core of thermoplastic material to obtain suitable adhesion of the metal layers to this core, are not critical.

  
Such agents are for example organosilanes or coupling agents.

  
Examples of suitable classes of organosilanes,

  
  <EMI ID = 218.1>

  
silanes, glycidoxy-alkylthrialkoxysilanes, methacrylo & alkyltrialkoxysilanes and mixtures thereof. Among these

  
  <EMI ID = 219.1>

  
trimethoxysilane, gamma-glycidoxypropyltrimethoxysilane,

  
and gamma-methacryloxypropyltrimethoxysilane. These compounds are commercially available from Union Carbide Corporation New York, New York 10017 under the designations A-1100 silane ,! A-1120 silane, A-186 silane, A-187 silane, and A-174 silane respectively. Gamma-glycidoxypropyl-

  
  <EMI ID = 220.1>

  
trimethoxysilane are also commercially available

  
  <EMI ID = 221.1>

  
designations Z6040 silane, Z6020 silane, respectively.

  
Such silane coupling agents can be used in the form of alcoholic solutions, aqueous alcoholic solutions, or simply aqueous solutions. The concentration of these silane solutions typically located between 0.01% and 1.0% by weight.

  
Other adhesion promoting agents can also be used. Examples of such adhesion promoting agents are adhesives such as nitrile rubber.

  
  <EMI ID = 222.1>

  
  <EMI ID = 223.1>

  
amides, high melting point polyesters, polyesters

  
with high melting point crosslinked with polyisocyanates, modified polyisobutylene-butadiene styrene rubber, urethanes, ethylene-acrylic acid copolymers, copolymers

  
  <EMI ID = 224.1>

  
Among the adhesion promoting agents indicated above, organosilanes are preferred in that the metal-thermoplastic adhesion is generally stronger,

  
and better withstands deterioration or breakage.

  
Many techniques using these adhesion promoting agents to provide the necessary adhesion for the metal layer - core layer of thermoplastic material are suitable. Such a technique gives exceptional results when the metal layers are aluminum and the core layer of thermoplastic material is nylon, a nylon copolymer,

  
a nylon terpolymer, poly (ethylene terephthalate) or a modification. A process used for example to manufacture the laminates so as to guarantee a good metal-thermoplastic adhesion can be described as follows

  
with aluminum and nylon 6.6 used as the metal layer and the thermoplastic layer respectively. The aluminum layers are first subjected to a degreasing operation to remove all grease and dust

  
of their surface (although such degreasing may not

  
be necessary, and therefore can be omitted when the metal is already free from contamination). For example,

  
washing the surface or completely immersing it

  
  <EMI ID = 225.1>

  
If desired, the cleaned aluminum layers can be dipped in a solution of sulfuric acid - hot dichromate (chromic acid) or a dilute solution of an alkali metal hydroxide in aqueous solution - for example hydroxide, sodium or potassium hydroxide - to strip the surface

  
  <EMI ID = 226.1> although this pickling may not be absolutely necessary, Excess pickling agent, whether hot chromic acid or alkali metal hydroxide in dilute aqueous solution, is removed from the surface stripped by vigorous rinsing of such a surface in water,

  
After this pretreatment C if necessary), the surfaces of the aluminum layers are treated with an agent promoting the adhesion of organosilane,

  
The nylon 6.6 layer similarly can be

  
treated with an organosilane adhesion agent, but in all cases, the organosilane agent (or generally any agent promoting adhesion) is interposed in the surfaces in opposition to the aluminum layers

  
and of the nylon 6,6 layer whether it is placed on the surfaces of the aluminum layers or on the surfaces of the nylon 6,6 layer,

  
As noted above, the application of an agent promoting 1 adhesion of organosilane between the contact surfaces of the metal layers and the thermoplastic layer although practical is not absolutely necessary. Other adhesion promoting agents can be used although organosilane agents are preferred.

  
For example, laminates consisting of layers of aluminum as the metal applied to a core layer

  
high density polyethylene thermoplastic containing 10% by weight of glass fibers (HDPE / 10% of glass fibers), aluminum applied to low density polyethylene (LDPE), aluminum applied to nylon 6-co-6,6 reinforced with mineral matter (VYDYNE R-240), and aluminum applied to a block copolymer (HYTREL

  
  <EMI ID = 227.1>

  
without using any adhesion promoting agent. Such laminates have all of the important critical properties necessary for use. as panels-

  
of construction, even if the long-term stability: term of the adhesion metal-thermoplastic material can undergo

  
damage.

  
It will be understood, however, that, if used, the particular pretreatment and adhesion agent, and the miss process used to apply this agent to the laminate will vary both depending on the particular metal layers and the core layer. of thermoplastic material used and their condition.

  
The high temperatures and pressures used

  
  <EMI ID = 228.1>

  
Such temperatures necessary for the formation of a

  
  <EMI ID = 229.1>

  
wind vary for example between 100 [deg.] C and 350 [deg.] C. Similarly, suitable pressures are those which are sufficient to maintain contact between the contact surfaces.

  
of the two layers of metal and of the core layer of thermoplastic material in order to allow the formation of a metal-thermoplastic adhesion having an adhesion strength of at least 1.75 x 10 <3> N / m.

  
It will of course be understood that the conditions particu &#65533; temperature and pressure etc. will vary depending on the particular materials used to make the laminates.

  
A large number of sheet manufacturing processes; tees of the present invention can be implemented,

  
including compression molding, extrusion lamination, etc. A preferred method of manufacturing laminates is to extrude a sheet of thermoplastic material and laminate the layer of molten thermoplastic material between the two layers! of metal, so as to obtain an excellent adhesion as noted above. It is also possible to sink

  
  <EMI ID = 230.1>

  
tyl caprolactam, adipoyl-bis-caprolactam, terephthaloyibis-caprolactam &#65533; isophthaloyl-bis-caprolactameetc as initiators. It is also envisaged that the metal layers can be preformed to the desired shapes

  
by the usual shaping techniques and maintained in a mold while the core layer of ther-i moplastic material is injection molded, compression molded or polymerized between these metal layers.

  
5. Experimental examples:

  
The following examples illustrate the present invention! They should not be used for limiting purposes only illustrative. It should be understood that Examples 3 to 7 are not within the limits of the present invention.

Example 1:

  
A general description of the processes used to prepare metal-thermoplastic-metal laminates according to the invention is. given below. The process can be described as a batch process consisting of the following operations in the order indicated:
a) pre-treatment of the metal:

  
  <EMI ID = 231.1>

  
(2) cleaning / pickling of the metal b) pretreatment of the thermoplastic material c) application of the adhesive agent (if used) d) manufacture of the laminate. It will be noted however that steps (a) and / or (b) may not be necessary and therefore may be omitted when the metal layers and / or the core layer of thermoplastic material do not include contaminants such as grease, dust etc. for example, materials that have just been extruded.
(a) Pretreatment of the metal <EMI ID = 232.1>

  
  <EMI ID = 233.1>

  
trichlorethylene. According to another possibility, the surface; is cleaned ..with a cloth (Webril Litho Pad is suitable!

  
  <EMI ID = 234.1>

  
ethane, toluene, acetone, etc. The metal surface is then rinsed with a fresh solvent, either the same or another, for example an acetone rinse following the first cleaning with toluene, without wiping and it is allowed

  
  <EMI ID = 235.1> in excess solvent to evaporate. ''

  
(2) Cleaning / pickling of metal: After degreasing (step (a) (1)) (when it is used) the metal is preferably cleaned / pickled before applying the adhesive agent (when it is used) in order to obtain the best possible resistance to the adhesion of metal to the thermoplastic material, although in many cases this cleaning / stripping step is not necessary.

  
The metal surface can be etched by chemical or non-chemical means. Non-chemical pickling (mechanical abrasion) consists of brushing with a wire brush, sandblasting with alumina or steel, wet sanding, etc. Any of these pickling treatments is followed by degreasing like step (a) (1).

  
The chemical pickling medium can be either alkaline or acid or a combination of these. The suitable alkaline pickling medium consists of aqueous solutions of sodium hydroxide, sodium metasilicate, commercially available metal cleaners such as Apex 764 M (available from Apex Alkali Products Company, Philadelphia, Pennsylvania), etc. . Suitable acid pickling media are dichromic sulfuric acid solutions (chromic acid), aqueous hydrochloric acid solution, phosphoric acid solution, etc.

  
The particular environment used may vary depending on; metal used in that different metals sometimes

  
require different treatments. In some cases the

  
metals are cleaned properly by various treatments. Examples of treatment for specific metals are as follows:

  
(1) Aluminum
(a) sodium hydroxide solution, 2-5% at 25 [deg.] C.
(b) sodium metasilicate solution, 50.0 g per liter at 70 [deg.] C. <EMI ID = 236.1> and
(d) sodium dichromate solution, 30.0 g of bi- <EMI ID = 237.1>

  
  <EMI ID = 238.1>

  
and 1 liter of water at 60 [deg.] C.

  
(2) Low carbon steel
(a) phosphoric acid, 2% at 25 [deg.] C.

  
(3) Stainless steel
(a) Apex 764 M, 50.0 g / liter at 70 [deg.] C.
(b) wiped with a 1: 1 hydrochloric acid water solution, lightly abraded with a wire brush, then Apex 764 M, 50, Og <EMI ID = 239.1>
(c) lightly abraded using a wire brush, then Apex 764 M, 50.0 per liter to
70 [deg.] C. The metal surface is pickled by immersing the metal in a pickling medium for a suitable period of time. The durations of the treatments are typically :, sodium hydroxide solution 2-5 minutes, Apex 764 M and sodium metasilicate solution, 2 minutes.

  
dichromate and sulfuric acid solution (chromic acid &#65533; i =.

  
  <EMI ID = 240.1>

  
After the cleaning / pickling treatment, the metal is thoroughly rinsed with water. When an alkaline treatment is used, the metal is generally washed with hot running water while wiping with a clean cloth (a Webril Litho Pad is perfectly suitable), followed by rinsing with water hot without wiping. The metal is then blown dry using a jet

  
air or nitrogen.

  
When a treatment is carried out in an acid medium, in general the metal is washed successively with tap water and demineralized water. If we apply

  
an agent promoting adhesion based on silane during step (c), it is usually applied directly; wet metal although it can also be applied to dry metal if desired. If silane is not used, the metal is first blown dry as described above and then dried in the oven at a suitable temperature; nable. !
(b) Pretreatment of the thermoplastic material:

  
In order to obtain good metal-to-thermoplastic adhesion during step (d) above, any agent promoting treatment, for example a mold release agent as in the case of a sheet of poured thermoplastic material must be removed. If the thermoplastic material is not to be used at a temperature above its melting point in subsequent operations (step (d)), its surface is prepared by vigorously wiping with a clean cloth moistened with a solvent. abrades slightly, wipe the surface again, and finally dry. Of another

  
side, if step (d) involves the melting of the thermoplastic, the blowing and abrading steps do not

  
are not necessary unless they involve eliminating

  
  <EMI ID = 241.1>

  
plastic.

  
(c) Application of an agent promoting adhesion:

  
The application process for the adhesion promoter (when used) depends on the particular system used. When adhesion promoting agents, for example, organosilane coupling agents

  
are used, they are applied as dilute solutions (usually 0.01% to 1.0% by weight) to the surface in question. The amount of such an agent applied to the surface in question is generally very small and only

  
a small fraction is retained on the surface - a monomolecular layer being ideal for obtaining good mechanical adhesion - thermoplastic material. Adhesion promoting agents can be applied to the surface:
this metal and / or the surface of thermoplastic material

  
by immersing the surface in question in the solution or by spraying the solution on the surface. In any of these cases, the material is allowed to drain briefly and then dry either in air or in forced air by drying with a jet of air or nitrogen without touching the surface treated with the silane. . Another method involves the incorporation of the adhesion promoting agent

  
to thermoplastic material. However, application to the surface of the metal is the preferred method in that after this application the metal can easily be fired

  
at high temperatures usually 130 [deg.] C between

  
5 to 30 minutes, to guarantee a dryness of the metal surface before the implementation of step (d).

  
  <EMI ID = 242.1>

  
epoxy and nitrile-rubber / phenolic systems are used, they are usually applied by

  
usual coating techniques, for example with a roller. Such adhesion promoting agents are applied in an amount such that the thickness is

  
  <EMI ID = 243.1>

  
applied to the metal and / or to the surface of the thermoplastic material.

  
  <EMI ID = 244.1>

  
Method (1): laminate comprising an adhesion promoting agent - laminates containing adhesion promoting agents of the organosilane type are produced; qués by arranging a layer or sheet of metal of each:
side of a layer of thermoplastic material, the side

  
  <EMI ID = 245.1>

  
with the core layer of thermoplastic material.

  
For reasons of convenience and to avoid polymer splashes on the hot plates of the press during the rolling phase, a disposable reinforcing sheet is placed between the layers of treated metal and the plates of the press. Thin aluminum foil is useful for this purpose. Other additional reinforcing sheets for example, sheets of polished metal to ensure a polished surface on the

  
  <EMI ID = 246.1>

  
blage is placed in a press and heated to a temperature above the melting point (in the case of a partially crystalline thermoplastic core) or above the transition temperature of the

  
(in the case of an amorphous thermoplastic core)

  
polymer under sufficient pressure to maintain

  
contact between metal and thermoplastic material

  
and causing a flow of the thermoplastic material to obtain the desired thickness. Total thickness

  
r laminate; , in addition to the total thickness of the layers

  
of metal, is adjusted using suitable spacers between the plates or preferably a mold

  
metal coated with TEFLON (commercial designation) of specific thickness around the perimeter of the laminate assembly. Contact at the desired temperature is maintained for a period of time sufficient to guarantee good adhesion to metal and thermoplastic material, usually some seconds up to 30 minutes. The laminate, metal-thermoplastic-metal is then cooled

  
under pressure to a temperature below the melting point of the thermoplastic. We then release

  
the pressure and the laminate is removed from the press.

  
  <EMI ID = 247.1>

  
Alternatively, although not recommended, the laminate can be removed from the press while it is still hot and quenched at low temperatures, for example by placing the laminate between thick plates of cold metal.

  
  <EMI ID = 248.1>

  
this adhesive - laminates containing adhesion promoting agents are manufactured by disposing

  
a layer of metal on each of a core layer of thermoplastic material so that the adhesive promoting agent is disposed between the surfaces

  
facing the layers of metal and the core of thermoplastic material. The assembly is placed in a press and heated under pressure to cure the adhesive and obtain a metal-thermoplastic adhesion. Generally, the assembly is not heated to a temperature above the melting point of the thermoplastic. Therefore, the total thickness of the laminate: manufactured

  
is determined by the sum of the total thickness of the metal layers and the thickness of the core layer of thermoplastic used to prepare it.

  
Method (3): laminate, comprising no adhesion promoting agent - laminates containing neither adhesion promoting agents nor adhesive agents

  
are made by placing a layer of metal on each <EMI ID = 249.1> side of a core layer of thermoplastic material in a suitable mold. The assembly is placed in a press and laminated as described in method (1) above.

  
Process (4): Continuous extrusion process - The thermoplastic is subjected to extrusion in the molten mass between two layers of metal. Pressure contact is maintained in a compression device

  
such as rollers spread, heated and / or cooled and / or! plates.

  
Alternatively, one can allow the

  
  <EMI ID = 250.1>

  
sion to solidify before coming into contact with the layers of metal and subject the assembly to rolling as it is

  
  <EMI ID = 251.1>

  
depending on whether an agent promoting adhesion is used or not. Again, a compression device such as spaced, heated and / or cooled rollers and / or trays are used to make the necessary contact between the metal:
and the thermoplastic material.

Example 2:

  
A metal-thermoplastic-metal laminate

  
is made using 0.0127 cm 1100-0 aluminum as the metal layers and partially crystalline polypropylene as the core layer of thermoplastic material. The aluminum surface is degreased by immersion in

  
toluene followed by rinsing with acetone as described

  
  <EMI ID = 252.1>

  
by immersion in a 50 g / l aqueous solution of Apex 764

  
  <EMI ID = 253.1>

  
delphia, Pennsylvania) at 70 [deg.] C for a period of 2 minutes. Remove the aluminum from the pickling solution and rinse with warm running water while wiping

  
using a clean cloth (a cloth of the Webril Litho Pad type (commercial designation)) followed by rinsing with hot water without wiping and then blowing dry using a jet of nitrogen. A solution containing 2.5 mm of solution

  
  <EMI ID = 254.1>

  
  <EMI ID = 255.1>

  
drops of glacial acetic acid, at room temperature to form a clear solution in a single phase) in 1000 ml of ethanol is applied to the cleaned and pickled aluminum surface and the leaves hang vertically and drainage and drying are allowed to the air. The leaves were then heated in an oven at 130 [deg.] C for 5 minutes.

  
  <EMI ID = 256.1>

  
brushed with dicumyl peroxide solution

  
at 1% in toluene and dried vigorously in dry air.

  
The treated aluminum layers and the treated polypropylene layer are then assembled in a mold.

  
made of stainless steel coated with a layer of TEFLON (trade designation) 0.157 cm thick, the treated surfaces of the aluminum layers facing the treated surfaces of polypropylene. The assembly is placed in a, plate press, heated to 200 [deg.] C. Pressure is applied and held for 30 minutes after the polypropylene has flowed lightly to fill the mold cavity.

  
The laminate is then cooled under pressure to a temperature below 70 [deg.] C and then the pressure is released and the laminate is removed from the press. The properties of the laminate-: are shown in Table 1.

Example 3:

  
A laminate of metal-thermoplastic-metal

  
was prepared using 1100-0 aluminum as the metal layers and high density polyethylene (HDPE,

  
  <EMI ID = 257.1>

  
Missouri 63166 as MPE-210) as a layer

  
of thermoplastic material core. The aluminum surface is degreased by immersion in acetone as described in Example 1 above, and it is cleaned, etched

  
by immersion in a 5% aqueous solution in sodium hydroxide = oxide for a period of 5 minutes. Remove the aluminum from the alkaline solution and rinse with warm running water while wiping with a clean cloth
(Webril Litho Pad) followed by rinsing with hot water without wiping and then blowing with a jet of nitrogen.

  
  <EMI ID = 258.1>

  
  <EMI ID = 259.1>

  
ethanol is sprayed onto the cleaned aluminum surface / <EMI ID = 260.1> pickled and the leaves hang vertically to be drained and air dried. They are then heated in an oven at 130 [deg.] C for 5 minutes.

  
  <EMI ID = 261.1>

  
are then connected in a stainless steel mold coated with TEFLON, the treated surfaces of the aluminum layers facing the HDPE sheet. The assembly

  
  <EMI ID = 262.1>

  
  <EMI ID = 263.1>

  
(about 3 minutes). The laminate is then cooled under pressure to a temperature below 100 [deg.] C, and then the pressure is released and the composa is removed from

  
  <EMI ID = 264.1>

  
thicknesses of the components of the layers are indicated in table 1.

Example 4:

  
0.190cm metal-thermoplastic-metal laminate was prepared using aluminum
1100-0 of 0.0127 cm thick as layers of metal and HDPE as core layer of thermoplastic material according to the method described in Example 3 above except that one side of the HDPE sheet was brushed with a 0.1% solution of benzoy peroxide in ethanol

  
and she was allowed to air dry and the plate press was heated to 175 [deg.] C. The properties of the laminate are shown in Table 1.

Example 5:

  
a metal-thermoplastic-metal laminate having a thickness of 0.198 cm is prepared using aluminum 5052-0, 0.0127 cm as the metal layers and HDPE as the core layer of the thermoplastic material

  
  <EMI ID = 265.1>

  
tion that the aluminum layers were degreased in

  
acetone and cleaned / etched by immersion in 5% aqueous sodium hydroxide solution at room temperature for 5 minutes, treatment with ducumyl peroxide was omitted and the laminate produced was cooled to 100 o C before be removed from the press. The properties of the laminate are shown in Table 1.

Example 6:

  
The process described in example 2 above

  
is repeated except that the aluminum surface

  
is degreased in acetone and cleaned / pickled

  
by immersion in an aqueous solution of Apex 764 M for a period of only 1 minute, the treatment with dicumyl peroxide is omitted, and the laminate is omitted. manufactured was cooled to 100 [deg.] C before being removed

  
  <EMI ID = 266.1>

  
shown in Table 1.

Example 7:

  
This example illustrates the preparation of a denetal-thermoplastic-metal laminate without subjecting the metal layers either to degreasing or to cleaning / pickling.

  
A laminate is prepared using 0.0140 cm thick aluminum Lithoplate as the metal layers and HDPE as the core layer of thermoplastic material. The aluminum sheets were immersed in a solution;

  
  <EMI ID = 267.1>

  
(prepared as described in Example 2 above) in 1000 ml of ethanol. and the leaves hang vertically to be drained and air dried. They were then heated in an oven at 1300C for 30 minutes.

  
HDPE surfaces were brushed using

  
  <EMI ID = 268.1>

  
benzene and they are allowed to dry vigorously in dry air.

  
The aluminum layers treated with silane and the treated HDPE layer are assembled in a stainless steel mold coated with 0.27 cm TEFLON, the surfaces

  
  <EMI ID = 269.1>

  
treated with HDPE. The assembly is arranged in a press

  
with trays heated to 175 [deg.] C. Pressure is applied and maintained for 30 minutes after HDPE has flowed to fill the mold cavity. The laminate was then cooled under pressure to 100 [deg.] C and then the pressure

  
  <EMI ID = 270.1> laminate tees are shown in Table 1.

Example 8:

  
This example shows the preparation of a metal-thermoplastic-metal laminate without the use of an adhesion promoting agent.

  
Laminate - 0.175 cm thick is prepared using 1100-0 aluminum 0.0127 cm thick as metal layers and high density polyethylene

  
  <EMI ID = 271.1>

  
10% glass fibers) as a core layer of thermoplastic material. The aluminum surface is degreased by immersion in 1,1,1-trichloro-ethane as described in exe # ple 5 above and cleaned / pickled by immersion in a solution of sodium dichromate (acid chromic container
30.0 g of sodium dichromate dihydrate, 150 ml of concentrated sulfuric acid (specific weight 1.84), and 1 liter

  
  <EMI ID = 272.1>

  
cleaning / stripping solution, rinsed thoroughly

  
under running water followed by rinsing with demineralized water, dry sulfurization using a jet of nitrogen and heated to
1300C for 2 minutes.

  
Aluminum cleaned / pickled and HDPE / 10% fiber

  
  <EMI ID = 273.1>

  
  <EMI ID = 274.1>

  
for 3 minutes and then the pressure is increased to 13605 kg during the minute. The laminate is then cooled under pressure to 38 [deg.] C and then the pressure is released and the laminate removed from the press. The properties of the laminate are shown in Table 1.

  
Examples 9-10

  
These examples show the separation of metal-thermoplastic-metal laminates without the use of adhesion-promoting agents.

  
The laminates were prepared using 1145-0 aluminum as the metal layers and low density polyethylene (LDPE) as the core layer of thermoplastic material. The aluminum surface is degreased by immersion in 1,1,1-trichloroethane as described

  
) in Example 1 above and then cleaned ^ pickled by immersion in a solution of sodium dichromate (chromic acid) containing 30 g of sodium dichromate dihydrate,
150 ml of concentrated sulfuric acid (specific weight 1.84),

  
  <EMI ID = 275.1>

  
removed from the chromic acid solution, rinsed vigorously under running water followed by rinsing with demineralized water and dry blowing using a jet of nitrogen. The aluminum is then heated in an oven at 130 [deg.] C for 2 minutes.!

  
The aluminum and LDPE layers are then assembled in a closed mold. The assembly is placed in a plate press, heating at 204 [deg.] C. A pressure of 1814 kg or moire is applied for 3 minutes and then increased until
22675 kg for 1 minute. The laminate is cooled under

  
  <EMI ID = 276.1>

  
laminate is removed from the press. The properties of the laminates, including the thicknesses of the layers of the components, are shown in Table 1.

  
Examples 11-14:

  
The process described in Examples 9-10 is repeated except that aluminum 1100-0 is used as the metal coating. The properties of the laminates, including the thicknesses of the components of the layers are indicated in

  
table 1.

  
Examples 15-17:

  
The process described in Examples 9-10 is repeated

  
except that aluminum 5052-0 is used as the layer ^; of metal. The properties of the laminates, including the thicknesses of the component layers are indicated in

  
table 1.

  
Examples 18:

  
A laminate of metal-thermoplastic material-metal using aluminum 6061-0 of 0.052 cm thickness as layers of metal and a mold in TEFLON coated stainless steel having a thickness of 0.102 cm is prepared according to the process described in examples 9-10. The properties of the laminate are shown in Table 1.

  
Examples 19-21:

  
These examples show the preparation of metal-thermoplastic-metal laminates without subjecting the metal layers to either degreasing or pickling cleaning.

  
The laminates are prepared using aluminum Lithoplate as the metal layer and LDPE as the core layer of thermoplastic material. The core is immersed in a solution comprising 4 ml of a hydrololized silane A-174 solution (prepared as described in Example 2 above) in 1000 ml of ethanol and

  
leaves are hung vertically to drain

  
and air dry. They are then heated in a

  
oven at 130 [deg.] C for 30 minutes.

  
The surfaces of LDPE were brushed using a 5% solution of cumene hydroperoxide in benzene

  
and they are allowed to air dry.

  
The treated aluminum layers and the treated LDPE were assembled in a closed mold, the treated surfaces of the aluminum layers facing the treated surfaces of LDPE. The assembly is arranged in a press

  
  <EMI ID = 277.1>

  
maintains it for 15 minutes after the LDPE has

  
poured to fill the cavity. The laminate is then cooled under pressure to 38 [deg.] C and then the pressure is released and the laminate removed from the press. Laminate properties including layer thicknesses

  
components are shown in Table 1.

Example 22:

  
A 0.155 cm thick metal-thermoplastic-metal laminate is prepared using 6061-T6 aluminum 0.0152 cm thick as the metal coating and LDPE as the core layer of the thermoplastic material process described in the examples

  
9-10 except that after degreasing with trichloro1,1,1 ethane, the aluminum surface is sanded with sandpaper and degreased again, and the press

  
was heated to 221 [deg.] C. The properties of the laminate are shown in Table 1.

Example 23:

  
A metal-thermoplastic-metal laminate,

  
\ is prepared using aluminum 1100-0 &#65533; 0.00.508 cm thick as layers of metal and nylon 6.6 having

  
a degree of crystallinity of 33% as a core layer

  
of thermoplastic material. The aluminum surface is degreased by immersion in trichlorethylene, as

  
it is described in Example 1 above, and then cleaned / pickled by immersion in a 5% aqueous solution of sodium hydroxide at room temperature for

  
5 minutes. The aluminum is removed from the alkaline solution and rinsed with warm running water while wiping with a clean cloth (Webril Litho Pad) followed by uri

  
  <EMI ID = 278.1>

  
dry using a nitrogen spray. An aqueous solution

  
with 0.4% silane A-1100 is applied to the aluminum surface

  
  <EMI ID = 279.1>

  
to drain and air dry. They are then heated in an oven at 130 [deg.] C for 30 minutes.

  
The treated aluminum layers and the nylon 6,6 are !, assembled in a stainless steel mold coated with TEFLON having a thickness of 0.178 cm, the treated surfaces of the aluminum layers facing the nylon.

  
6.6. The assembly is arranged in a plate press; heated to 285 [deg.] C. Pressure is applied and maintained

  
  <EMI ID = 280.1>

  
fill the mold cavity. The laminate was then cooled under pressure to 2000C and then the pressure was released and the laminate removed from the press. The properties of the laminate are shown in Table 1.

  
Examples 24-30:

  
  <EMI ID = 281.1>

  
using aluminum 1100-0 as the metal layers and nylon 6.6 as the core layer of thermoplastic material were prepared according to the method described in the example;
23 above. The properties of the laminates including the thicknesses of the layers of the components are indicated in

  
table 1.

Example 31:

  
A metal-thermoplastic-metal laminate

  
0.185 cm thick e &#65533; prepared using aluminum foil 5052-0 of 0.00254 cm as metal layers and nylon 6.6 having a degree of crystallinity of

  
33% as a core layer of thermoplastic material. The aluminum surface is degreased by immersion in toluene followed by rinsing with acetone as described in example 1 and then cleaned / de-

  
  <EMI ID = 282.1>

  
  <EMI ID = 283.1>

  
2 minutes. The aluminum is removed from the solution and rinsed with hot running water while wiping with a clean cloth (Webril Litho Pad) followed by rinsing

  
in hot water without wiping and then blow dry

  
by means of a nitrogen jet. A solution containing 2.5 ml of silane A-1100 in 1000 ml of distilled water is applied to the cleaned / pickled aluminum surface and the leaves hang vertically and are allowed to drain and air dry.

  
  <EMI ID = 284.1>

  
were assembled in a stainless steel mold coated with TEFLON 0.180 cm thick and rolled as described in Example 23 above. The properties of the laminate are shown in Table 1.

  
Examples 32-35:

  
Laminates of metal-thermoplastic material -mé

  
  <EMI ID = 285.1>

  
metal and nylon 6.6 having a degree of crystallinity

  
33% as a core layer of thermoplastic material were produced according to the process described in Example

  
  <EMI ID = 286.1>

  
shown in Table 1.

Example 36:

  
A metal-thermoplastic material laminate
- metal is made using aluminum 5052-0 0.00762 cm thick as layers of metal and nylon 6.6 having a degree of crystallinity of 33% as layer

  
of thermoplastic material core. The aluminum surface is degreased by immersion in 1,1,1 trichloro. ethane as described in Example 1 above and then cleaned / pickled by immersion in a solution of sodium dichromate (chromic acid) containing 30, Og of sodium dichromate dihydrate sulfuric acid concen - &#65533;

  
  <EMI ID = 287.1>

  
5 minutes. The aluminum is removed from the chromic acid solution and rinsed thoroughly with running water followed

  
  <EMI ID = 288.1>

  
0.4% silane A-1100 in distilled water (pH adjusted

  
to 4.0 with formic acid) is applied to the cleaned / pickled surface of wet aluminum. The aluminum sheets are blown dry using a jet of nitrogen and heated in an oven at 130 C for 2 minutes.

  
The treated aluminum and nylon 6,6 layers

  
are assembled in the coated stainless steel mold

  
of TEFLON having a thickness of 0.133 cm, the treated surfaces of the aluminum layers facing the surfaces of nylon 6,6. The assembly is arranged in a press

  
with tray * heated to 285 [deg.] C. A pressure of 453.5 kg or less is applied for 3 minutes and then the pressure is increased :, 13605 kg for 1 minute. The laminate is cooled under pressure to 138 [deg.] C, and then the pressure is released and the laminate is removed from the press. The owners

  
  <EMI ID = 289.1>

  
Examples 37-45: Laminates of metal -thermoplastic -metal using aluminum 5052-0 as the metal layers and nylon 6,6 having a degree of crystallinity of 33% as the core layer of the thermoplastic material - Qués according to the method described in Example 36 above. Laminate properties are shown in the table
1.

Example 46:

  
A 0.187 cm thick metal-thermoplastic-metal laminate is prepared using 304 (annealed) stainless steel sheets 0.00254 cm thick as layers of metal and nylon 6.6 having

  
a degree of crystallinity of 33% as a material layer

  
  <EMI ID = 290.1>

  
by immersion in toluene as described in Example 1 above and then cleaned / pickled by immersion!

  
i sion in a 50.0 g / liter solution of Apex 764 M

  
(a product of Apex Alkali Products Company, Philadelphia,

  
  <EMI ID = 291.1>

  
stainless steel cleaning / pickling solution and rinse with warm running water while wiping

  
using a clean cloth (Webril Litho Pad) followed by rinsing with hot water without wiping and then blowing dry with a jet of nitrogen. A solution containing 2.5 ml of silane A-1100 from 1000 ml of distilled water is applied to the cleaned / pickled stainless steel surface and the leaves are hung vertically to drain and air dry. The leaves are then heated in an oven at 90 [deg.] C for
10 minutes.

  
The treated stainless steel layers and

  
nylon 6,6 are assembled in a mold chassis

  
in stainless steel coated with TEFLON, 0.182 cm thick

  
  <EMI ID = 292.1>

  
  <EMI ID = 293.1>

  
placed in a plate press ;, will heat. 285 [deg.] C,

  
Pressure is applied and maintained for 10 minutes after nylon 6,6 has flowed to fill the mold cavity. The laminate is then cooled

  
under pressure up to 175 [deg.] C and then the pressure is released and the laminate removed from the press. The properties of the laminate are shown in Table 1,

  
Examples 47-58:

  
Laminates of metal-thermoplastic material
-metal are prepared using stainless steel
304 (annealed) as layers of metal and nylon 6,6 having a degree of crystallinity of 33% as a core layer of thermoplastic material according to the method described in Example 46 above. The properties of the laminates are shown in Table 1.

Example 59:

  
A metal laminate - thermoplastic material-

  
  <EMI ID = 294.1>

  
0.0152 cm thick as layers of metal and nylon 6.6 having a degree of crystallinity of 33% as a layer of thermoplastic material according to the process described in Example 23 above, except that after the stage

  
  <EMI ID = 295.1>

  
glass and cleaned / pickled in 2.5% aqueous sodium hydroxide solution. A 0.122 cm thick TEFLON coated stainless steel mold was also used. Laminate properties are shown in the table
1.

  
Examples 60-62

  
Metal-thermoplastic-metal laminates were prepared using aluminum 6061-T6 as the metal layers and nylon 6.6 having a degree of crystallinity of 33% as the core layer of the thermoplastic material. than. The aluminum surface is degreased by immersion

  
  <EMI ID = 296.1>

  
  <EMI ID = 297.1>

  
1 tion of 10% aqueous hydrochloric acid at room temperature for 10 minutes. The aluminum is removed from the cleaning / pickling solution and rinsed vigorously with running water followed by rinsing with demineralized water, dabbed with iron wool and air-dried. The aluminum sheets are immersed in an aqueous solution of about 0.4% of silane A-1100 in distilled water and they hang vertically for drainage

  
and air drying. They are then heated in an oven

  
at 130 [deg.] C for 30 minutes.

  
The laminates are assembled and fabricated as described in Example 23 above. The properties of the laminates, including the thicknesses of the component layers, are shown in Table 1.

  
Examples 63 -65

  
Metal-thermoplastic-metal laminates using aluminum 6061-0 as the metal layers and:
nylon 6,6 having a degree of crystallinity of 33% as the core layer of thermoplastic material was prepared according to the method described in Example 59 described above. Laminate properties, including thicknesses

  
  <EMI ID = 298.1>

  
Examples 66 - 69! These examples show the preparation of metal-thermoplastic-metal laminates without subjecting the layers

  
metal either for degreasing or cleaning / pickling.

  
Laminates were prepared using Lithoplate aluminum as the metal and nylon 6,6 layers having a degree of crystallinity of 33% as the core layer of thermoplastic material. The aluminum sheets were immersed in a solution containing 4 ml of silane A-1100 in 1000 ml of 95% ethanol and they hang vertically to drain and air dry. They are then heated in an oven at 130 [deg.] C for 30 minutes. The laminates are assembled and manufactured as described in the example

  
23. Properties of laminates, including thicknesses

  
  <EMI ID = 299.1>

  
Examples 70-75:

  
Metal-thermoplastic-metal laminates are prepared using low-grade steel

  
made of C 1010 carbon - annealed as layers of metal and nyloni 6.6 having a degree of crystallinity of 33% as a core layer of thermoplastic material according to the method described in Example 23 above except that cleaning and pickling is carried out by immersion in a 2% aqueous solution of phosphoric acid at room temperature for a period of 0.25 minutes (15 seconds). Laminate properties, including thicknesses of

  
  <EMI ID = 300.1>

  
Examples 76-77,

  
These examples show the preparation of metal-thermoplastic-metal laminates comprising metal layers of different compositions and of different thickness on each side of the core layer of thermo-plastic material.

Example 76:

  
A laminate having a thickness of 0.284 cm was prepared using 304 (annealed) stainless steel of

  
  <EMI ID = 301.1>

  
  <EMI ID = 302.1>

  
33% degree of crystallinity as a core layer of! thermoplastic material. The layers were degreased bet

  
  <EMI ID = 303.1> immersion in 1,1,1-trichloroethane as described in example 1 above and then cleaned / decapa by immersion in an aqueous solution at 50.0 g per liter

  
  <EMI ID = 304.1>

  
The metal layers are removed from the cleaning / pickling solution and rinsed thoroughly with running water followed by rinsing with demineralized water. A 0.3% aqueous solution of silane A-1100 in distilled water

  
(pH adjusted to 4.0 with formic acid) is applied

  
to cleaned / pickled surfaces of wet metals.

  
The metal sheets are blown

  
dry with a jet of nitrogen and heated in an oven

  
at 130 [deg.] C for 2 minutes.

  
The treated metal layers and the nylon 6,6 are assembled in a stainless steel mold coated with

  
  <EMI ID = 305.1>

  
is of metal facing nylon 6,6. The assembly Arranged in a plate press heated to 285 [deg.] C. A pressure of 907 kg is applied for 3 minutes and then the pressure is increased to 13605 kg for 1 minute. The laminate is then cooled under pressure to 38 [deg.] C then the pressure!

  
  <EMI ID = 306.1>

  
The properties of the laminates are indicated in the table.
1.

Example 77:

  
A laminate of metal - thermoplastic-metal of 0.279 cm is prepared using stainless steel
304 (annealed) 0.0058 cm thick and aluminum
3003-H25 0.0127 cm thick as a metal layer

  
and nylon 6,6 having a degree of crystallinity of 33% as a core layer of thermoplastic material according to the method described in Example 76. The properties of the laminate are shown in Table 1.

Example 78:

  
A metal-thermoplastic-metal laminate

  
is prepared using aluminum 1100-0 having a thickness of 0.0127 cm as the metal layers and ZYTEL ST-801 (trade designation) (a nylon 6.6 with high impact resistance) as the core layer of material

  
(thermoplastic according to the process described in Example 31

  
except that the aluminum is cleaned / pickled in an aqueous solution of 50.0 g / liter of Apex 764 M and

  
we use a stainless steel mold coated with TEFLON

  
  <EMI ID = 307.1>

  
are shown in Table 1.

Example 79:

  
This example shows the preparation of a laminate

  
  <EMI ID = 308.1>

  
an agent promoting adhesion.

  
A laminate 0.190 cm thick is prepared

  
using 0.0127 cm thick 1100-0 aluminum as layers of metal and VYDYNE R-240 (trade designation) (6-co-6.6 nylon reinforced with Monsanto's mineral material) as a layer of core of thermoplastic material. The aluminum surface is degreased by immersion

  
  <EMI ID = 309.1>

  
by immersion in a sodium dichromate solution
(chromic acid) containing 30.0 g of sodium dichromate dihydrate, 150 ml of concentrated sulfuric acid (specific gravity 1.84) and 1 liter of water at 60 [deg.] C for a period of

  
5 minutes. We remove the aluminum from the cleaning / pickling solution, rinse vigorously with running water followed

  
by rinsing with demineralized water, dry blowing using a jet of nitrogen and heating in an oven at 130 [deg.] C for 2 minutes.

  
Aluminum layers cleaned / pickled dry

  
  <EMI ID = 310.1>

  
stainless steel coated with 0.165 cm TEFLON, the cleaned / pickled surfaces of the aluminum layers facing the VYDYNE R-240. The assembly is placed in a plate press heated to 285 [deg.] C. Pressure of 1814 kg or less is applied for 3 minutes and then increased to 22675 kg for 1 minute. The laminate is then cooled under pressure to 138 [deg.] C, and then press it

  
is is sion / released and laminate / removed from the press. The properties of the laminate are shown in Table 1.

Example 80:

  
The process of Example 79 is repeated except that aluminum 6061-0 of 0.0152 cm is used as the metal layers and a coated stainless steel mold

  
  <EMI ID = 311.1>

  
are shown in Table 1,

Example 81:

  
We. repeat the process of example 79 with the exception that aluminum 6061-T6 of 0.0152 cm is used as the metal layers and a stainless steel mold coated with TEFLON of 0.0152 cm of thickness, properties

  
  <EMI ID = 312.1>

Example 82:

  
The process of Example 79 above is repeated, except that 5052-0 aluminum having a thickness of 0.165 cm is used as the metal layers and a TEFLON coated stainless steel mold having a thick-:
0.165 cm. The properties of the laminate are shown in Table 1.

Example 83:

  
The process of Example 82 above is repeated except that a stainless steel mold coated with TEFLON of 0.152 cm is used. The properties of the laminate are indicated in Table 1,

Example 84:

  
A laminate of metal-thermoplastic material-metal is prepared using aluminum 5052-0 of

  
  <EMI ID = 313.1>

  
co-6.6 reinforced with mineral material (commercially available from Monsanto Company, St. Louis, Missouri 63166 USA under the trade designation VYDYNE R-220) as a core layer of thermoplastic material. We degrease

  
the aluminum surface by immersion in trichlorethylene as described in example 1 above and cleaning / pickling is carried out by immersion in an aqueous solution

  
at 5% sodium hydroxide at room temperature for

  
5 minutes. We remove the aluminum from the alkaline solution

  
and rinsing thoroughly with running water followed by rinsing with demineralized water. We apply a solution

  
  <EMI ID = 314.1>

  
> cleaned / pickled surface of wet aluminum, The aluminum sheets are blown dry using a

  
jet of nitrogen and heat in an oven at 130 [deg.] C for 15 minutes.

  
The treated aluminum layers and VYDYNE R-220 are assembled in a coated stainless steel mold.

  
0.168 cm thick TEFLON, the treated aluminum surfaces facing the VYDYNE R-220. The assembly is placed in a plate press heated to 285 [deg.] C.

  
A minimum pressure is applied for 3 minutes and then the pressure is increased up to 22675 kg during

  
1 minute. The laminate is then cooled under pressure to
200 [deg.] C and then release the pressure and remove the laminate from the press. Laminate properties

  
are shown in Table 1.

Example 85:

  
A laminate of metal-thermoplastic material-metal is prepared using a low carbon steel C 1010 (annealed) 0.00508 cm thick as layers of metal and VYDYNE (trade designation) R-240 as a layer of thermoplastic material core. The steel surface is degreased by immersion in 1,1,1 trichloro

  
  <EMI ID = 315.1>

  
then cleaned / pickled by immersion in a 2% aqueous solution of phosphoric acid at room temperature for 5 minutes. The steel is removed from its phospho- solution; risk and rinse vigorously under running water followed

  
by rinsing with demineralized water. An aqueous solution of 0.2% silane A-1100 in distilled water (pH adjusted to 4.0 with formic acid) is applied to the cleaned / pickled surface of the wet steel. The steel sheets are blown dry by a jet of nitrogen and heated in an oven

  
at 130 [deg.] C for 2 minutes.

  
  <EMI ID = 316.1>

  
assembled in a 0.124 cm thick TEFLON coated stainless steel mold, the treated surfaces

  
steel facing VYDYNE R-240. The assembly is

  
  <EMI ID = 317.1>

  
pressure of 907 kg or less is applied for 3 minutes and then increased to 13605 kg for 1 minute. The laminate is then cooled under pressure to 66 [deg.] C, and then the pressure is released and the laminate is removed

  
of the press. The properties of the laminate are shown in Table 1.

Example 86:

  
A 0.127 cm thick metal-thermoplastic-metal laminate is prepared using 304 (annealed) stainless steel 0.00762 cm thick as the metal layer and VYDYNE (trade designation) R-240 as core layer of thermoplastic material

  
according to the method described in Example 85 above. With the exception that cleaning / pickling is carried out by immersion in an aqueous solution of 50.0 g / liter of Apex 764 M

  
at 70 [deg.] C for 2 minutes, a stainless steel mold coated with TEFLON 0.112 cm thick is used and

  
the manufactured laminate is cooled to 38 [deg.] C before releasing the pressure. The properties of the laminate are shown in Table 1.

Example 87:

  
A metal-thermoplastic-metal laminate 0.185 cm thick is prepared using 1100-0 aluminum 0.027 cm thick as layers

  
of metal and nylon 6.6 containing 10% by weight of

  
glass fibers as the core layer of thermoplastic material according to the process described in Example 46 above, except that degreasing in toluene is followed by rinsing with acetone, the aluminum sheets treated with silane A -1100 dry are heated

  
in an oven at 130 [deg.] C for 5 minutes, and a stainless steel mold coated with 0.160 cm TEFLON is used. The properties of the laminate are shown in the table!
1.

  
Example 88:

  
A metal-thermoplastic-metal laminate 0.193 cm thick was prepared using 1100-0 aluminum 0.0127 cm thick as layers of

  
  <EMI ID = 318.1>

  
  <EMI ID = 319.1>

  
1 except that a stainless steel mold coated with 0.168 cm TEFLON is used. The properties of the laminate are shown in Table 1.

Example 89:

  
The process of Example 88 is repeated except that nylon 6 containing 10% by weight of glass fibers is used as the core layer of thermoplastic material and a 0.157 cm TEFLON coated stainless steel mold. thickness is used. The properties of the laminate are shown in Table 1.

Example 90:

  
A metal-thermoplastic-metal laminate 0.234 cm thick is prepared using 1100-0 aluminum having a thickness of 0.0127 cm as layers

  
  <EMI ID = 320.1>

  
having a degree of crystallinity of 35% as a core layer of thermoplastic material according to the method described in Example 36 with the exception of the following:

  
The treated aluminum layers and the PARN 56/44 are assembled in a stainless steel mold coated with TEFLON of 0.208 cm, the treated surfaces of the aluminum layers facing the PARN 56/44. The assembly is placed in a plate press heated to 299 [deg.] C. A pressure of 1814 kg or less is applied for 3 minutes and then the pressure is increased by 13605 kg during

  
1 minute. The laminate is then cooled under pressure

  
  <EMI ID = 321.1>

  
is removed from the press and annealed at 170 [deg.] C for 1 hour! The properties of the laminate are shown in tablej
1.

Example 91:

  
This example shows the use of amorphous thermoplastic material as a layer of thermoplastic material.

  
  <EMI ID = 322.1>

  
what follows:

  
The treated aluminum layers and the PARN 56/44 are assembled in a stainless steel mold coated with 0.178 cm TEFLON, the treated surfaces of the aluminum layers facing the PARN 56/44. The assembly is placed in a plate press heated to 310 [deg.] C. Pressure of 1814 kg or less is applied for 3 minutes and then increased to 13605 kg for 1

  
  <EMI ID = 323.1>

  
in an ice-water mixture. The properties of the laminate are shown in Table 1.

Example 92:

  
A 0.179 cm thick metal-thermoplastic-metal laminate is prepared using 1100-0 aluminum 0.0127 cm thick as layers of metal and poly (ethylene terephthalate) (PET) )

  
having a degree of crystallinity of 38% as a core layer of thermoplastic material according to the method described in Example 36 above with the exception of the following:

  
The treated aluminum layers and the PET are assembled in a coated stainless steel mold

  
of 0.154 cm thick TEFLON, the treated surfaces of the aluminum layers facing the PET. The assembly

  
  <EMI ID = 324.1>

  
A pressure of 1814 kg or less is applied for 3 minutes and then the pressure is increased to 13605 kg for 1 minute. The laminate is then cooled under pressure to 55 [deg.] C and then the pressure is released. The laminate is removed from the press and annealed at 150 [deg.] C for 1 hour. The properties of laminate. are shown in Table 1.:

Example 93:

  
The process of Example 92 is repeated except that a stainless steel mold coated with TEFLON with a thickness of 0.254 cm is used. The properties of laminate; are shown in Table 1.

Example 94:

  
A laminate of metal-thermoplastic material-metal is prepared using aluminum Lithoplate of

  
  <EMI ID = 325.1>

  
(ethylene terephthalate) (PET) having a degree of crystallinity of 38% as a core layer of thermo material

  
  <EMI ID = 326.1>

  
methylene chloride as described in Example 1 above and allowed to air dry.

  
A solution of Z6020 silane is prepared by stirring

  
a mixture of 11.1 g of Z6020 silane in a solution

  
3 drops of glacial acetic acid in 3.6 g of room temperature water to form a clear solution

  
to a phase which is diluted with 2254.0 g of ethanol.

  
We wet the degreased aluminum energetically by

  
the Z6020 silane solution prepared above, is blown dry using a nitrogen jet and heated in an oven at 100 [deg.] C for 10 minutes.

  
The treated aluminum and PET layers are assembled,

  
  <EMI ID = 327.1>

  
0.279 cm, the treated surfaces of aluminum facing PET. The assembly is arranged in a press

  
tray heated to 282 [deg.] C. A minimum pressure is applied for 3 minutes and then it is increased to 22675 kg during <1> minute. The laminate is

  
then cooled under pressure to 66 [deg.] C and then the pressure is released and the laminate is removed from the press. Laminate properties are shown in the table
1.

Example 95:

  
This example shows the use of amorphous thermoplastic material as a core layer of thermoplastic material. The process of example 92 is repeated above with the exception of the following,

  
  <EMI ID = 328.1>

  
  <EMI ID = 329.1>

  
aluminum 1100-0 as the metal layer and PET as the core layer of thermoplastic material according to

  
the methods described in Example 91 above except that the temperature of the plate press ^ was

  
of 285 [deg.] C. The properties of the laminate are shown in Table 1.

  
Examples 96-103:

  
The examples show the preparation of laminates

  
metal-thermoplastic-metal without pickling

  
metallic layers or using a favoring agent

  
  <EMI ID = 330.1> The laminates are prepared using aluminum
1100-0 as layers of metal and a molten mixture of

  
PET having a degree of crystallinity of 38% and 11.7% of poly (butylene tere-co-isophthalate) -poly (butylene glycol)
-block (HYTREL (commercial designation) 4056, commercially available from E.I. du Pont de Nemours & Co, Wilmington, Delaware 19898USA), as a layer, of thermoplastic core. The aluminum surface is degreased by immersion in trichlorethylene as described in Example 1 above, the sheets are hung vertically- <EMI ID = 331.1>

  
The scrub is repeated with methanol.

  
Degreased aluminum layers and PET / mixture
11.7% HYTREL 4056 are assembled in a stainless steel mold coated with TEFLON, the degreased surfaces
(any of the surfaces of the metal layer)

  
aluminum layers facing the PET / 11.7% HYTREL 4056 mixture. The assembly is arranged in a press

  
  <EMI ID = 332.1>

  
for 3 minutes and then increase the pressure to!
22675 kg for 1 minute. The laminate is then cooled under pressure to 100 [deg.] C and then the pressure is released and the laminate is removed from the press. Properties

  
of the laminate, including the thicknesses of the component layers are shown in Table 1.

  
  <EMI ID = 333.1>

  
A laminate of metal-thermoplastic material -metal

  
is prepared using as layers of metal aluminum 1100-0 0.0127 cm thick and PET / 11.7% HYTREL 4056 as the core layer of thermoplastic material. The aluminum is degreased in trichloro-1,1,1 ethane as described in Example 1 above, and is then cleaned / pickled by immersion in an aqueous solution of

  
5% sodium hydroxide at room temperature for 5 minutes. Aluminum is removed from the alkaline solution

  
and rinsed. ' vigorously with running water followed by rinsing with demineralized water. A solution of 0.9985 g of silane A 1100 in 3.126 g of water and 243 g of ethanol (pH adjusted to 4.0 with formic acid) is sprayed onto the cleaned / pickled surface of the wet aluminum. The aluminum sheets are blown dry using a

  
jet of nitrogen and then heated in an oven at 130 [deg.] C for 15 minutes.

  
The layers of treated aluminum and PET / 11.7 # HYTREL 4056 are assembled in a stainless steel mold coated with TEFLON, 0.150 cm thick,

  
the treated surfaces of the aluminum layers making

  
against PET / 11.7% of HYTREL 4056. The assembly is placed in a plate press and heated to 279 [deg.] C.

  
A pressure of 2721 kg is applied for 3 minutes and then the pressure is increased to 22675 kg during

  
1 minute. The laminate is then cooled under pressure to 52 [deg.] C and then the pressure is released. The laminate is removed from the press and annealed by heating to
150 [deg.] C for 20 minutes. The properties of the laminate are shown in Table 1.

Example 105:

  
  <EMI ID = 334.1>

  
the exception is that a stainless steel mold coated with 0.165 cm TEFLON is used. The properties of the laminate are shown in Table 1.

Example 106: i

  
A laminate of metal-thermoplastic material-metal is produced using aluminum 5052-0 of 0.0127 cm thickness as layers of metal and PET / 11.7% HYTREL
4056 as a core layer of thermoplastic material.

  
  <EMI ID = 335.1>

  
1,1,1 ethane as described in Example 1 above and then cleaned / pickled by immersion in a sodium dichromate solution (chromic acid) containing 30 mg of sodium dichromate dihydrate, 150 ml of sulfuric acid

  
  <EMI ID = 336.1>

  
for 5 minutes. The aluminum is removed from the chromic acid solution and rinsed vigorously with running water followed by rinsing with demineralized water. A 4% aqueous solution of silane Z 6040 in distilled water

  
  <EMI ID = 337.1>

  
the cleaned / pickled surface of wet aluminum. The aluminum sheets are blown dry using a

  
  <EMI ID = 338.1>

  
your.

  
  <EMI ID = 339.1>

  
  <EMI ID = 340.1>

  
in a stainless steel mold / TEFLON

  
0.203 cm thick, the treated surfaces of the aluminum layer facing the core layer of thermoplastic material. The assembly is arranged in a press

  
with trays heated to 279 [deg.] C. Pressure of 1814 kg or less was applied for 3 minutes and then increased: up to 22,675 kg for 1 minute. The laminate is then i refrddi under pressure up to 138 [deg.] C and then we release

  
the pressure and the laminate is removed from the press. The properties of the laminate are shown in Table 1.

  
Examples 107-109

  
Laminates from metal-thermoplastic-metal are prepared using aluminum 5052-0 as the metal layers and PET / 11.7% HYTREL 4056 as the metal layer.

  
core of thermoplastic material according to the method described in Example 106 above. The properties of the laminates including the thicknesses of the component layers are shown in Table 1.

  
Examples 110-113:

  
Laminates of metal-thermoplastic-metal are prepared using aluminum 6061-0 as the metal layers and a molten mixture of PET / 11.7% of HYTREL 4056 as the layer of thermoplastic material. The aluminum surface is lowered by immersion in trichlorethylene followed by rinsing with acetone as described in example 1 above and is then cleaned / pickled by immersion in an aqueous solution at 2 , 5% sodium hydroxide at room temperature for 5 minutes. The aluminum is removed from the aqueous solution and rinsed vigorously with running water followed by rinsing with demineralized water. The wet aluminum is immersed in a mixture of 40 ml of a silane solution A-1100 (prepared by mixing 0.83 g

  
of silane A-1100 with 208.0 g of water) and 50 ml of a solution of silane A-174 (prepared by stirring a mixture of <EMI ID = 341.1>

  
glacial acetic acid at room temperature to form a clear, single-phase solution, and diluting with 2449.0 g of water and 10 ml of ethanol), blow with a jet of nitrogen and heated in an oven at 130 [deg. ] C for 2 minutes.

  
The layers of treated aluminum and PET (11.7% HYTREL 4056 are assembled in a stainless steel mold coated with TEFLON, the treated surfaces of aluminum

  
  <EMI ID = 342.1>

  
dried in a plate press heated to 279 [deg.] C. A pressure

  
  <EMI ID = 343.1>

  
increases to 22675 kg for an additional 3 minutes. The laminate is then cooled under pressure to 66 C j and then the pressure is released and the laminate is

  
removed from the press. The properties of the laminate, including the thicknesses of the component layers are shown in Table 1.

Example 114-116

  
The process described in Examples 110-113 is repeated except that aluminum 6061-T6 is used as the metal layers and the ethanol is omitted from the silane solution A-174. The properties of the laminates, including the thicknesses of the component layers, are shown in Table 1.

Example 117:

  
The process described in Example 94 is repeated except that a molten mixture of PET / 11.7% HYTREL 4056 is used as the core layer of thermoplastic material. The properties of the laminate are shown in Table 1.

Example 118

  
  <EMI ID = 344.1>

  
0.127 cm thick metal using low carbon steel (0.00508 cm thick annealed as metal layers and PET / 11.7% HYTREL 4056 as the core layer of thermoplastic material depending on the process described in Example 85 above except that the steel layers are immersed in a phosphoric acid solution for 2 minutes, a coated steel mold is used

  
  <EMI ID = 345.1>

  
says the laminate manufactured at 38 [deg.] C before removing it from the press. The properties of the laminate are shown in Table 1.

Example 119:

  
The process described in example 118 is repeated

  
except that a coated stainless steel mold

  
0.208 cm thick TEFLON is used. The properties of the laminate are shown in Table 1.

Example 120:

  
  <EMI ID = 346.1>

  
  <EMI ID = 347.1>

  
thick as a metal coating and a molten mixture of PET having a degree of crystallinity of 38% and 11.1% of poly (ethylene terephthalate) -45% poly (butylene oxide) block (PETBCP), with the polymer block poly (butylene oxide) having a molecular weight of 1000, as a core layer of thermoplastic material. The aluminum is degreased by immersion in methylene chloride as described in Example 1 above and is allowed to dry.

   The aluminum was immersed in an equivolume solution (50 ml of each kind) of a solution of silane A-1100 (preparations mixed 10.6 ml of silane A-1100 and 31.3 ml of water with 3095 ml ethanol) and a solution of silane A-174 (prepared by stirring a mixture of 9.6 ml of silane A-174, 2.5 ml of water, and 2 drops of glacial acetic acid at room temperature for 30 minutes to form the clear solution to a

  
  <EMI ID = 348.1>

  
it is blown dry using a jet of nitrogen and heated in an oven at 130 [deg.] C for 2 minutes.

  
The treated aluminum layers and the PET / 11.1% PETBCP are assembled in a stainless steel mold coated with 0.282 cm TEFLON and laminated as described in Examples 110-113 above. The properties of the laminate are shown in Table 1,

  
Examples 121-124:

  
Laminates from metal-thermoplastic metal are prepared using aluminum 6061-0

V

  
as layers of metal and a molten mixture of PET / 11.1% PETBCP as core layer of thermoplastic material according to the method described in Examples 110-113 except that rinsing with acetone is omitted during the degreasing step. The properties of laminates,

  
including the thicknesses of the component layers are indicated in Table 1,

Example 125:

  
A laminate of metal-thermoplastic-metal is prepared using aluminum 6061-T6 0.0152 cm thick as the metal layers and a molten mixture of PET / 11.1% PETBCP as the core layer of material. - re thermoplastic as described in the examples'
121-124 except that after degreasing, we submit; aluminum to wet sandblasting with sandpaper before pickling in a 2.5% aqueous solution of sodium hydroxide. Laminate properties

  
are shown in Table 1.

Example 126:

  
A laminate. of metal - thermoplastic material - metal is prepared using aluminum of 0.0127 cm

  
  <EMI ID = 349.1>

  
terephthalate) -5% poly (butylene oxide) -block (PET-b-5% PBO), partially crystalline, the PBO block having a molecular weight of 1000 as a core layer of thermoplastic material according to the method described in the example

  
36 above. The properties of the laminate are indicated in the table.

Example 127:

  
This example shows the preparation of a laminate

  
metal-thermoplastic-metal without pickling

  
metal or using an adhesion promoting agent,

  
Laminate is prepared using aluminum
1100-0 0.0127 cm thick as layers of metal

  
  <EMI ID = 350.1>
- block (PET-b-24% PBO), partially crystalline, PBO blocks having a molecular weight of 1000 as a core layer of thermoplastic material, Aluminum is degreased by immersion in methylene chloride as described in l Example 1 above and allowed to air dry. Degreased aluminum layers and PET-b-24% PBO are assembled in the mold

  
made of 0.292 cm thick TEFLON coated steel, the degreased surfaces (any surface) facing the PET-b-24% PBO. The assembly

  
  <EMI ID = 351.1>

  
Minimum pressure is applied for 3 minutes and then increased to 22675 kg for an additional 3 minutes. The laminates are then cooled under

  
  <EMI ID = 352.1>

  
and the laminate is removed from the press. Properties

  
of the laminate are shown in Table 1.

  
Examples 128-131: Laminates are produced from thermo-metallic material! plastic-metal using aluminum 1100-0

  
as metal layers and a molten mixture of poly (ethylene terephthalate) (PET) having a degree of crystallinity &#65533; 38% and 23.5% of HYTREL 4056 (commercial designation

  
  <EMI ID = 353.1>

  
according to the method described in examples 110-113 with the exception that methylene chloride is used as degreasing solvent and that cleaning / pickling

  
of the aluminum surface is produced by immersion in a 5% aqueous solution of sodium hydroxide at room temperature for 10 minutes. The properties of the laminates are shown in Table 1.

Example 132:

  
The process described in Example 94 above is repeated except that the molten mixture of PET having a degree of crystallinity of 38% and 23.5% HYTREL 4056 is used as the core layer of thermoplastic material. than. The properties of the laminates are shown in Table 1.

Example 133;

  
The process described in Example 91 above is repeated, with the exception that a molten mixture of PET having a degree of crystallinity of 38% and 10% is used.

  
  <EMI ID = 354.1> <EMI ID = 355.1>

  
lene) propane carbonate) or simply polycarbonate or

  
PC commercially available under the trade designation MERLON M100 from Mobay Chemical Corporation, Pittsburgh, Pennsylvania, 15205, USA) is used as a thermoplastic layer and a 0.183 cm thick TEFLON coated stainless steel mold is used. The properties of the laminates are shown in Table 1.

Example 134:

  
  <EMI ID = 356.1>

  
0.190 cm thick using aluminum 1100-0 0.0127 cm as metal layers and poly (ethylene 80% terephthalate -co-20% isophthalate) (PET / I 80/20) having

  
a degree of crystallinity of 32% as a core layer of thermoplastic material and an aqueous solution of 0.4%

  
silane A-1100 in distilled water (pH adjusted

  
4.0 with formic acid) as a promoting agent

  
  <EMI ID = 357.1>

  
ple 106 above with the exception of the following:

  
The treated aluminum layers, and PET / I 80/20 are assembled in a stainless steel mold coated with 0.165 cm TEFLON, the treated surfaces of the aluminum layers facing PET / 1 80/20 .

  
The assembly is placed in a plate press heated to 240 [deg.] C. Apply a pressure of 1814 kg or less for 3 minutes and then increase the pressure to 13605 kg for 1 minute. The pressure laminate is then slowly cooled to 54 [deg.] C and then the pressure is released and the laminate is removed from the

  
  <EMI ID = 358.1>

  
table 1.

Example 135:

  
The process of Example 91 is repeated except that amorphous PET / I 80/20 having a degree of crystallinity of only 5% is used as the core layer of thermoplastic material, and a stainless steel mold coated with 0.170 cm thick TEFLON, and the trays

  
of the press are heated to 285 [deg.] C. The properties of the laminates are shown in Table 1.

  
r

Example 136:

  
The process of Example 135 above is repeated

  
except that the amorphous PET / I 80/20 had a

  
degree of crystallinity of only 3.3% and we use

  
a stainless steel mold coated with 0.142 cm TEFLON. The properties of the laminate are shown in Table 1.

Example 137:

  
A metal-thermoplastic-metal laminate is prepared using 1100-0 aluminum 0.0127 cm thick as the metal layers and a partially crystalline melt mixture of poly (ethylene 80% terephthalate-co-20 % isophthalate) (PET / i 80/20) and

  
11.7% HYTREL 4056 as a core layer of thermoplastic material. The aluminum surface is degreased by immersion in methylene chloride as described in Example 1 above and it is allowed to air dry. The degreased aluminum is immersed in a 0.4% solution of Z6020 silane in ethanol. (prepared as described in Example 94 above), blow dry with a jet of nitrogen and heat in an oven at 100 [deg.] C for 10 minutes.

  
The treated aluminum layers and PET / I 80/20 /
11.7% HYTREL 4056 are assembled in m stainless steel mold coated with 0.282 cm TEFLON, the aluminum treated surfaces facing PET / I 80/20 / 11.7% HYTRE1 4056. The assembly is arranged in a plate pressXheated to 249 [deg.] C. A minimum pressure is applied for 3 minutes and then the pressure is increased to 22675 kg for an additional 3 minutes. The laminate is then cooled under pressure to
66 [deg.] C, the pressure is released and the certification removed from the press. The laminate is melt annealed to
150 [deg.] C for 20 minutes. Laminate properties

  
are shown in Table 1.

Example 138:

  
The process of Example 137 above is repeated

  
except that aluminum lithoplate 0.0140 cm thick is used as the metal layer and a stainless steel mold coated with TEFLON 0.279 cm thick. The properties of the laminate are shown in Table 1

Example 139

  
The process described in Example 134 is repeated except that poly (butylene terephthalate) (PBT) is used as the core layer of thermoplastic material and

  
a stainless steel mold coated with TEFLON is used

  
0.165 cm. Laminate properties are shown

  
in table 1.

Example 140:

  
The process described in Example 139 is carried out using a stainless steel mold coated with TEFLON

  
0.282 cm. The properties of the laminate are shown in Table 1.

Example 141:

  
The method described in example 94 above is put

  
implemented except that partially crystalline poly (butylene terephthalate) (PBT, available

  
commercially under the designation VALOX 310 from

  
General Electric Company, Pitssfield, Massachusetts 01201, USA) as a core layer of thermoplastic material and

  
press plates heated up to 252 [deg.] C. The properties of the laminate are shown in Table 1.

Example 142:

  
The process described in Example 137 is repeated except that a partially crystalline mixture of PBT and 11.7% HYTREL 4056 (PBT / 11.7%) is used.

  
HYTREL 4056) as a core layer of thermoplastic material. Laminate properties are shown in the table
1.

Example 143:

  
The process of Example 142 is repeated, except that aluminum lithoplate 0.0140 cm thick is used as the metal layers. The properties of the laminate are shown in Table 1.

Example 144:

  
The process of Example 141 is repeated except that aluminum 1100-0 0.0127 cm thick is used as the metal coating, a partially crystalline mixture of PBT and 23.5%. HYTREL- 4056) as the core layer of thermoplastic material and a stainless steel mold coated with TEFLON 0.247 cm thick is used. The properties of the laminate are shown in Table 1.

Example 145:

  
The method described in Example 144 is used for

  
  <EMI ID = 359.1>

  
0.0140 cm thick as layers of molten metal and a stainless steel mold coated with TEFLON 0.277 cm thick. The properties of the laminate are shown in Table 1.

Example 146:

  
A 0.211 cm thick laminate was prepared

  
  <EMI ID = 360.1>

  
as layers of metal and HYTREL 7246 as core layer of thermoplastic material according to the method described in Example 36 above except that the initial pressure applied was 1814 kg or less and that! The laminate produced is cooled to 54 [deg.] C before being removed from the press. The properties of the laminate are shown in Table 1.

Example 147:

  
The process described in Examples 128-131 is repeated except that a poly (.butylene terephthalate-

  
  <EMI ID = 361.1>

  
coated with 0.282 cm thick TEFLON. The properties of the laminate are shown in Table 1.

Example 148:

  
  <EMI ID = 362.1>

  
  <EMI ID = 363.1>

  
except that HYTREL 7246 (trade designation) is used as the core layer of thermoplastic material. The properties of the laminate are shown in Table 1.

Example 149:

  
A laminate of metal - thermoplastic material - metal is prepared according to the process described in Example 94 above.

  
  <EMI ID = 364.1>

  
partially crystalline (HYTREL 6346) as a core layer of thermoplastic material, The properties of the laminate are shown in Table 1,

Example 150:

  
A metal-thermoplastic-metal laminate is prepared according to the method described in Example 141

  
  <EMI ID = 365.1>
-co-isophthalate) -poly (butylene oxide) -block partially crystalline (HYTREL 5555) (trade designation) as a layer of thermoplastic material 'and a stainless steel mold coated with TEFLON 0.226 cm thick is used. The properties of the laminate are shown in Table 1.

Example 151;

  
The method of Example 14 is implemented except

  
  <EMI ID = 366.1>

  
crystalline (HYTREL 4055) as a core layer of thermoplastic material. The properties of the laminate are shown in Table 1.

Example 152:

  
A metal-thermoplastic material laminate is prepared
-metal using aluminum 1100-0 0.0127 cm <EMI ID = 367.1>

  
or simply polycarbonate available under the designation

  
  <EMI ID = 368.1>

  
field, Massachusetts 01201, USA) as the core layer of

  
  <EMI ID = 369.1>

  
seated by immersion in toluene followed by rinsing in acetone as described in Example 1 above and cleaned / pickled by immersion in a 5% aqueous solution of sodium hydroxide at ambient temperatures for

  
2 minutes. The aluminum is removed from the cleaning / stripping solution, rinsed in hot running water while wiping:

  
using a clean cloth (Webril Litho Pad) followed by rinsing with hot water without wiping and then blowing dry using a jet of nitrogen. A solution of 2.5 ml of silane A-1100 in 1000 ml of water is sprayed onto the cleaned / pickled surface and the leaves hang vertically for drainage and air drying.

  
We wash the polycarbonate with acetone, we proceed

  
sandblasting with sandpaper, wash again

  
with acetone and dried overnight (about 16 hours)

  
at 60 [deg.] C in a vacuum oven purged with nitrogen.

  
The treated aluminum layers and the treated polycarbonate are assembled in a stainless steel mold coated with 0.12 cm TEFLON, the treated surfaces

  
aluminum layers facing the polycarbonate treated surface. The assembly is placed in a plate press heated to 230 [deg.] C. The press is applied and maintained for 20 minutes after the polycarbonate

  
flowed to fill the mold cavity. The laminate is then cooled to a lower temperature

  
at 70 [deg.] C and then the pressure is released and the laminate is removed from the press. Laminate properties

  
are shown in Table 1.

Example 153:

  
A laminate of metal-thermoplastic material-metal is made using aluminum 1100-0

  
0.0127 cm as layers of metal and an acrylonitrile-butadiene-styrene (ABS) copolymer as a core layer of thermoplastic material according to the method described in Example 152 above, except that a 2.5 ml solution of hydrolyzed silane A-187 (prepared by stirring 10 g of silane A-187, 2.3 g of water and 2 drops of galcial acetic acid at room temperature for 30 minutes to form a clear solution

  
  <EMI ID = 370.1>

  
as an agent promoting adhesion, a mold is used

  
in stainless steel coated with TEFLON of 0.190 cm to adapt the thickness of the core layer of thermoplastic material and the plate press: is heated to
200 [deg.] C. The properties of the laminate are indicated in the

  
r table 1.

Example 154:

  
The process of Example 153 above is repeated at

  
  <EMI ID = 371.1>

  
core layer of thermoplastic material and a mold

  
in stainless steel coated with TEFLON 0.147 cm thick to adjust the thickness of the core layer! thermoplastic material. The properties of the laminate are shown in Table 1.

Example 155:

  
A laminate of metal-thermoplastic material-metal is prepared using 304 stainless steel 0.00254 cm thick, annealed as layers of metal and

  
  <EMI ID = 372.1>

  
commercially available from Union Carbide Corporation, New York, New York 10017) as a core layer of thermoplastic material. The aluminum surface is degreased

  
by immersion in 1,1,1 ethane trichloco as described in example 1 above and then cleaned / pickled by immersion in an aqueous solution of 50 g / liter of Apex 764 M at 70 [deg.] C for a period of 2 minutes. Steel is removed from cleaning / pickling solution

  
and rinsed vigorously under running water under vacuum by rinsing with demineralized water. An aqueous solution to

  
0.3% silane A-1100 in distilled water (pH adjusted

  
at 4.0 with formic acid) is sprayed onto the cleaned / pickled surface of the wet steel. The sheets

  
  <EMI ID = 373.1>

  
The layers of treated steel and polysulfone are assembled in a stainless steel mold coated with 0.0864 cm thick TEFLON, the treated surfaces of the steel facing the polysulfone. The assembly is arranged in a plate press; heated to 329 [deg.] C. A pressure of 907 kg or less is applied for 3 minutes and then the pressure is increased to 13605 kg for 1 minute. The laminate is then cooled under pressure to 66 [deg.] C and then the pressure is released and the laminate is removed from the press. The properties of the laminate are shown in Table 1.

  
Examples 156-157:

  
These examples show the preparation of metal-thermoplastic-metal laminates of compositions of different metal layers on each side of the core layer of thermoplastic material.

Example 156:

  
A laminate is made using steel

  
low carbon C 1010 0.00508 cm thick, annealed and alumina 6061-0 0.0152 cm thick as metal layers and polysulfone as core layer of thermoplastic material according to the process described in Example 155 above with the exception that a stainless steel mold coated with TEFLON 0.310 cm thick is used. The properties of the laminate are shown in Table 1.

Example 157:

  
We prepare a laminate using steel

  
low carbon C 1010 0.00508 cm thick, annealed and aluminum 3003-H25 0.0140 cm thick as metal layers and polysulfone as the core layer of thermoplastic material

  
the method described in Example 156 described above with the exception that a stainless steel mold coated with TEFLON of 0.311 cm is used. The properties of the laminate are shown in Table 1.

  
Examples 158-161:

  
These examples show the manufacture of metal-thermoplastic-metal laminates by polymerization of the monomers in situ between the metal layers.

  
Laminate properties are shown in the table
1.

  
The laminates are prepared using 0.0127 cm thick aluminum as the metal layers.

  
The aluminum surface is degreased by immersion in toluene followed by rinsing with acetone as

  
  <EMI ID = 374.1>

  
  <EMI ID = 375.1>

  
at 5% at room temperature for two minutes. The aluminum is removed from the alkaline solution and rinsed for 10 minutes under running water followed by rinsing

  
with demineralized water. 0.4% solution is sprayed

  
of silane A-1100 in ethanol on the cleaned surface /, pickled from wet aluminum. The aluminum sheets are blown dry using a jet of nitrogen and heated

  
in an oven at 130 [deg.] C for 30 minutes.

Example 158:

  
A laminate is prepared in situ by polymerization of a nylon 6 block copolymer between layers of aluminum from Lithoplate. A solution is prepared containing

  
6.0 g of VORANOL 2120 (commercial designation) (polyoxy-

  
  <EMI ID = 376.1>

  
commercial nation) (1,2-dihydro-2,2,4,4-quinoline

  
  <EMI ID = 377.1>

  
  <EMI ID = 378.1>

  
reduced pressure. A separate catalyst solution is prepared by stirring 7 ml of 3 molar ethylmagnesium bromide in diethyl ether at 175 g of [pound] -caprolactam at 100 ° C. dry melted. The solution is subjected to a vacuum to remove the ether and ethane and maintained at 100 [deg.] C

  
under nitrogen until used.

  
A mold is prepared by placing two aluminum sheets between heated plates of a closed press

  
in such a way that the treated surfaces will face the polymerized thermoplastic material. The aluminum sheets are separated by 0.318 cm thick TEFLON spacers. With the mold and the reaction solutions at 130 [deg.] C, these solutions are pumped into the mold using pumps of the Zenith type. The volume ratio of a stream of monomer solution to a catalyst solution is 1.12: 1. The streams are mixed using static mixers of the Kenics type. After 5 minutes in the mold, the laminate is removed and allowed to

  
to cool. The nylon 6 block copolymer contained

  
20% by weight of polyoxypropylene: block.

Example 159:

  
A laminate was produced similar to the example
158 except that aluminum 1100-0 is used as the metal layers.

Example 160:

  
A nylon 6 laminate is prepared by polymerization

  
  <EMI ID = 379.1>

  
The mold is prepared as described in the example

  
158 above. A solution is prepared containing 350 g of [pound] -caprolactane in fusion, 1.5 g of FLECTOL H (commercial designation) and 3.4 g of PEI-1000 (polyethyleneimine, 30% aqueous solution). The solution is dried by distillation.

  
  <EMI ID = 380.1>

  
in diethyl ether followed by vigorous gas evolution under vacuum. The temperature of the solution is adjusted to 130 [deg.] C and

  
  <EMI ID = 381.1>

  
to serve as the initiator. The solution is then poured into the mold heated to 180 [deg.]. The casting is allowed to harden for 10 minutes before being removed from the mold.

Example 161:

  
A nylon laminate reinforced with calcined clay of the 40% kaolinite type is prepared by reacting caprolactane between aluminum sheets 1100-0. The mold is prepared as described in Example 158 above. A mixture of 230 g of [pound] -caprolactam, 1.5 g of FLECTOL H, and 2.0 g of PEI-1000 is heated under a nitrogen atmosphere at 130 [deg.] C. To this stirred solution is added 120 g

  
  <EMI ID = 382.1>

  
dough at a temperature above 100 [deg.] C. To the

  
resulting paste 1.2 ml of silane A-1100 are added. Vacuum is created and dried by distillation of 50 ml of caprolactam. The vacuum is replaced by nitrogen and the dough is cooled to 100 [deg.] C. To this mixture is added 3.2 ml of 3 molar ethyl magnesium bromide in diethyl ether followed by vigorous gas evolution under vacuum. We replace the vacuum with

  
  <EMI ID = 383.1>

  
catalyze the dough followed by stirring for 30 seconds. We pour the dough into the mold heated to 180 [deg.] C and allow to harden for 10 minutes before removal

  
of the mold.

  
Examples 162 - 163:

  
These examples show the manufacturing of laminate

  
of metal-thermoplastic material - metal using

  
adhesive adhesion agents.

  
The laminates are prepared using 1100-0 aluminum 0.0127 cm thick as the metal coating.

  
  <EMI ID = 384.1>

  
in toluene followed by rinsing with acetone as described in Example 1 above and cleaning / stripping by immersion in 50 g / 1 of aqueous Apex 764 solution

  
M to 70 [deg.] C for a period of 2 minutes. The aluminum is removed from the cleaning / pickling solution and rinsed with hot running water while wiping with a clean cloth (Webril Litho Pad) followed by rinsing with hot water without wiping and then blowing dry using a nitrogen spray. The aluminum is then heated in an oven at 110 [deg.] C for 5 minutes and 130 [deg.] C for 10 minutes, respectively for Examples 162 and 163.

Example 162:

  
  <EMI ID = 385.1>

  
hexylacrylate -co-methyl-acrylate-co-acrylic acid- co-glycidylmethacrylate) or simply acrylate copolymer) adhesive with 25% solid is applied to the cleaned / pickled surface of aluminum and allowed to air dry for
15 minutes and then at 90 [deg.] C for 2 minutes.

  
A sheet of polyvinyl chloride (PVC) is wiped off with a clean cloth moistened with acetone, sandblasting is carried out with emery paper, it is wiped again using a clean cloth dampened with acetone and dried in a vacuum oven purged with nitrogen at 60 [deg.] C.

  
The treated aluminum and PVC layers are assembled, the surfaces treated with adhesive facing the PVC, and are laminated under a pressure of 200 [deg.] C during
20 minutes. The laminate is cooled under pressure to a temperature below 70 [deg.] C and removed from the press.

  
  <EMI ID = 386.1>

  
  <EMI ID = 387.1> An epoxy adhesive consisting of a mixture by weight of 67:33 EPON 871 (commercial designation) is applied:

  
EPON 871 (trade designation) (aliphatic epoxy resin, epoxy weight, 390-470 and bisphenol epoxy resin

  
A unmodified, weight by epoxy, 185-192 respectively commercially available from Shell Chemical Company, Houston, Texas 77002) with curing agent EPON V-25 (a polyamide, equivalent weight (quantity reacting with a molar 'epoxy) on the cleaned / pickled surface of aluminum in the form of a thick film of 0.00508!

  
  <EMI ID = 388.1>

  
the aluminum surfaces treated with the adhesive facing the nylon 6,6 are assembled and are laminated under pressure at 285 [deg.] C for 10 minutes, cooled under

  
  <EMI ID = 389.1>

  
of the laminates are shown in Table 1.

Example 168:

  
The properties of the metal-thermoplastic-metal laminates prepared according to Examples 2 to 163 and of the layers of metal and thermoplastic material are given in Tables 1, 2 and 3 respectively. Samples for all parts were preconditioned at 23 [deg.] C for at least 18 hours. With the exception of the coefficient of linear thermal expansion and measurements of the thermal distortion temperature, all

  
tests were done at 23 [deg.] C with relative humidity

  
50%. All unlaminated polyamide samples are kept dry, as molded in airtight containers, with anhydrous magnesium perchlorate or anhydrous calcium sulfate used as a desiccant during the preconditioning period at 23 [deg.] C. All other samples are preconditioned with a relative humidity of 50%.

  
It should be clearly understood that the values for the thickness of the layer of thermoplastic material indicated in table 1 represent an average value for the various samples of laminates used in the physical tests carried out on the laminates and it should be understood that variations minimal of the thickness may exist__ among these samples obtained from samples

  
of prepared experimental laminates.

  
Unless otherwise stated, the properties of the stated voltage

  
for metals refer to metals before they are subjected to thermal rolling conditions and it is recognized that these values do not change significantly after being subjected to thermal rolling conditions in the corresponding examples.

  

  <EMI ID = 390.1>


  

  <EMI ID = 391.1>
 

  

  <EMI ID = 392.1>


  

  <EMI ID = 393.1>
 

  

  <EMI ID = 394.1>


  

  <EMI ID = 395.1>
 

  

  <EMI ID = 396.1>


  

  <EMI ID = 397.1>
 

  

  <EMI ID = 398.1>


  

  <EMI ID = 399.1>
 

  

  <EMI ID = 400.1>


  

  <EMI ID = 401.1>
 

  

  <EMI ID = 402.1>


  

  <EMI ID = 403.1>
 

  

  <EMI ID = 404.1>


  

  <EMI ID = 405.1>
 

  

  <EMI ID = 406.1>


  

  <EMI ID = 407.1>
 

  

  <EMI ID = 408.1>


  

  <EMI ID = 409.1>
 

  

  <EMI ID = 410.1>


  

  <EMI ID = 411.1>
 

  

  <EMI ID = 412.1>


  

  <EMI ID = 413.1>
 

  

  <EMI ID = 414.1>


  

  <EMI ID = 415.1>
 

  

  <EMI ID = 416.1>


  

  <EMI ID = 417.1>
 

  

  <EMI ID = 418.1>


  

  <EMI ID = 419.1>
 

  

  <EMI ID = 420.1>


  

  <EMI ID = 421.1>
 

  

  <EMI ID = 422.1>


  

  <EMI ID = 423.1>
 

  

  <EMI ID = 424.1>


  

  <EMI ID = 425.1>
 

  

  <EMI ID = 426.1>


  

  <EMI ID = 427.1>
 

  

  <EMI ID = 428.1>


  

  <EMI ID = 429.1>
 

  

  <EMI ID = 430.1>


  

  <EMI ID = 431.1>


  

  <EMI ID = 432.1>
 

  

  <EMI ID = 433.1>


  

  <EMI ID = 454.1>


  

  <EMI ID = 434.1>


  

  <EMI ID = 435.1>
 

  

  <EMI ID = 436.1>


  

  <EMI ID = 437.1>
 

  

  <EMI ID = 438.1>


  

  <EMI ID = 439.1>
 

  

  <EMI ID = 440.1>


  

  <EMI ID = 441.1>
 

  

  <EMI ID = 442.1>


  

  <EMI ID = 443.1>
 

  

  <EMI ID = 444.1>


  

  <EMI ID = 445.1>
 

  

  <EMI ID = 446.1>


  

  <EMI ID = 447.1>


  

  <EMI ID = 448.1>
 

  

  <EMI ID = 449.1>
 

  

  <EMI ID = 450.1>


  

  <EMI ID = 451.1>
 

  

  <EMI ID = 452.1>


  

  <EMI ID = 453.1>
 

  

  <EMI ID = 455.1>
 

  

  <EMI ID = 456.1>


  

  <EMI ID = 457.1>
 

  

  <EMI ID = 458.1>


  

  <EMI ID = 459.1>


  

  <EMI ID = 460.1>
 

  

  <EMI ID = 461.1>


  

  <EMI ID = 462.1>
 

  
Of course, various modifications can be made by those skilled in the art to the laminates and methods which have just been described only by way of nonlimiting examples without departing from the scope of the invention.


    

Claims (1)

Claims: 1. Metal laminate of thermoplastic material - metal characterized in that it has in combination: an inelastic ratio of less than 93%, a coefficient <EMI ID = 463.1> bending density of at least 52.53 x 10 <3> N / m, and a weight maximum not exceeding 9.76 kg / m <2>, these laminates include providing a core layer of thermoplastic material, and a layer of laminated metal on each side of this layer of thermoplastic core, each layer of metal having a minimum thickness of about 0.00127 cm, provided that aluminum does not scalp the metal layer of two sides of the laminate when the thermoplastic layer is high density polyethylene and further provided that when polypropylene is the core; of thermoplastic material, aluminum is the layer of laminated metal on each side of the core, the laminate has 2 a maximum weight of 5.37 kg / m, where the thickness ratio from the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material is determined by the digital overlap region of the TR (YS / TS) parameter determined in the defined areas <EMI ID = 464.1> lower zones being defined by the equation of a straight line y = mx + b where y is the y axis parameter for IR and CLTE. , x is the x axis parameter for TR (YS / TS), m is the slope of the straight line and b is the intersection on the axis  <EMI ID = 465.1> b is zero for values of x from 0 to 0.65, and m is <EMI ID = 466.1>  <EMI ID = 467.1> for values of x from 0 to 0.1, and m is 0 and b is 9 x 10-6 for values of x greater than 0.1. and the upper limit of these areas is defined by the equation of a straight line as defined above with the condition that: when y is IR, m equals 280 and b equals 30 for values of x from 0 to 0.25, and m is 0 and b is equal to 100 for values of x greater at 0.25, and when y and CLTE. , m equals -2.88 x 10-3 and b equals 216 x] 0 for values of x from 0 to 0.05, <EMI ID = 468.1> values of x from 0.05 to 0.26, and m equals 0 and b equals  <EMI ID = 469.1> <EMI ID = 470.1> bending with 5% stress and the outer layers of metal at the point of maximum deflection CLTE &#65533; is the coefficient of linear thermal expansion of the laminate. <EMI ID = 471.1> from the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material. <EMI ID = 472.1> for a thickness and average weight of the two layers of metal with an elongation limit of 5%. and TSc is the tensile strength of the core layer of thermoplastic material. 2. Laminate according to claim 1, characterized in what the core layer of thermoplastic material is an olefin-based thermoplastic. 3. Laminate according to claim 2, characterized in that the olefin-based thermoplastic material is a polypropylene. 4. Laminate according to claim 2, characterized in that the olefin-based thermoplastic material is a high density polyethylene. 5. Laminate according to claim 2, characterized <EMI ID = 473.1> is a low density polyethylene. 6. Laminate according to claim 3, characterized in that the metal layers are not aluminum. 7. Laminate according to claim 4, characterized in that the metal layers are not aluminum. 8. Laminate according to claim 5, characterized in that the metal layers are not aluminum. 9. Laminate according to claim 3, characterized in that only one of the metal layers is aluminum. 10. Laminate according to claim 4, characterized in that only one of the metal layers is aluminum. 11. Laminate according to claim 5, characterized <EMI ID = 474.1> minimum. 12. Laminate according to claim 2, characterized in that the olefin-based thermoplastic material is a multipolymer originating from monomers chosen from the group comprising ethylene, propylene, butene-1, methyl-3 butene and methyl-4 pentene. 13. Laminate according to claim 1, characterized in that the core layer of thermoplastic material is an amide-based thermoplastic. 14. Laminate according to claim 13, characterized in that the amide-based thermoplastic material is nylon 6,6. 15. Laminate according to claim 13, characterized in that the amide-based thermoplastic is nylon 6. 16. Laminate according to claim 13, characterized in that the thermoplastic material based on amide is nylon 6-co 6,6. 17. Laminate according to claim 13, characterized in that the amide-based thermoplastic material is partially aromatic nylon. 18. A laminate according to claim 17, characterized in that the partially aromatic nylon is nylon 6, terephthalic acid-co-6, isophthalic acid. 19. A laminate according to claim 18, characterized in that the nylon 6, terephthalic acid -co-6, isophthalic acid is nylon n-70% 6, terephthalic acid-co- ' 100-30% 6, isophthalic acid. 20. Laminate according to claim 1, characterized in that the core layer of thermoplastic material is an ester-based thermoplastic. 21. Laminate according to claim 20, characterized in that the thermoplastic ester-based material is an <EMI ID = 475.1> 22. Laminate according to claim 21, characterized in that the polyalkylene terephthalate has an alkylene group comprising 2 to 10 carbon atoms. 23. Laminate according to claim 22, characterized in that the polyalkylene terephthalate is a polyethylene terephthalate. 24. Laminate according to claim 22, character- <EMI ID = 476.1> polybutylene terephthalate. 25. Laminate according to claim 22, characterized in that the polyalkylene terephthalate is a <EMI ID = 477.1> i 26. Laminate according to claim 25, characteristic  <EMI ID = 478.1> <EMI ID = 479.1> glycol. 27. The laminate according to claim 1 in that the core layer of thermoplastic material is a <EMI ID = 480.1> 28. A laminate according to claim 27, characterized in that the thermoplastic material based on arylene carbonate is a polycarbonate, 29. Laminate according to claim 1, characterized in that the core layer of thermoplastic material is a styrene-based thermoplastic material. <EMI ID = 481.1> laughed in that the styrene-based thermoplastic is ABS. 31. Laminate according to claim 1, characterized in that the core layer of thermoplastic material is a vinyl-based thermoplastic material. 32. Laminate according to claim 31 characterized in that the vinyl-based thermoplastic is polyvinyl chloride. <EMI ID = 482.1> risé in that the core layer of thermoplastic material is a thermoplastic material based on arylene sulfone. 34. Laminate according to claim 33, characterized in that the thermoplastic material based on arylene sulfone is a polysulfone. 35. Laminate according to any of i claim 1 to 34, characterized in that the material of the core layer of thermoplastic material contains a modifier. 36. Laminate according to claim 35, characterized in that this modifying agent consists by high modulus high performance fibers. 37. Laminate according to claim 36, characterized in that the high performance fibers high modulus are glass fibers. 38. Laminate according to claim 37, characterized in that the glass fibers are present. concentration between 1 and 33% by weight. 39. Laminate according to claim 35, characterized in that the modifying agent is a mineral filler. 40. Laminate according to claim 39, characterized in that the mineral filler is present in! a concentration between 1 to 50% by weight. 41. Laminate according to claim 40, characterized in that the mineral filler is a calcined kaolinite clay. 42. Laminate according to claim 41, charac- of terized in that the calcined clay / kaolinite is present in a concentration of 20 to 45% by weight. 43. Laminate according to claim 1, characterized in that the core layer of thermoplastic material is partially crystalline. 44. Laminate according to claim 43, characterized in that the layer of partially crystalline thermoplastic material comprises a degree of crystallinity of at least 15%. 45. A laminate according to claim 44, characterized in that each of the metal layers has a melting point above this melting point of the partially crystalline thermoplastic core layer and the thickness ratio; from the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material is further described by the parameter TR (YSm / TSc) determined by the defined area <EMI ID = 483.1> the lower limit of this area being defined by the equation of a straight line y = mx + b <EMI ID = 484.1> slope of the straight line and b is the intersection on the y axis with the condition that: m equals 1 and b equals 0 for values of x from 0 to 0.05, m equals 10 and b equals -0.45 for values of x from 0.05 to 0.12, and m equals 0 and b equals 0.75 for values of x greater than 0.12. and the upper limit of this area is defined by the equation of a straight line as defined above with the condition that m equals 112.5 and b equals 0 values of x from 0 to 0.004, m equals 15.3 and b equals 0.389 for values of x from 0.004 to 0.04, and m equals 0 and b <EMI ID = 485.1> <EMI ID = 486.1> of normalized thermal distortion where HDT is the thermal distortion temperature of the laminate. HDT is the thermal distortion temperature of the core layer of thermoplastic material. Tm is the crystalline melting point of the vs core layer of thermoplastic material. TR is the thickness ratio of the sum <EMI ID = 487.1> core layer of thermoplastic material. YSm is the creep resistance under tension for an average thickness and weight of two layers of metal! with an elongation limit of 5%. and! TS is the tensile strength of the core layer of thermoplastic material. 46. Laminate according to claim 1, characterized in that the metal layers laminated on each side of the thermoplastic core layer have the same composition. 47. Laminate according to claim 46, characterized in that the metal layers are aluminum. 48. Laminate according to claim 46, characterized in that the layers of the metal are made of low carbon steel. 49. A laminate according to claim 46, characterized in that the metal layers are stainless steel, 50. Laminate according to claim 1, characterized in that the metal layers have different compositions. 51. Laminate according to claim 50, characterized in that certain important properties of the metal are substantially balanced so that: (a) CLTEi = CLTEii <EMI ID = 488.1> are, respectively, the coefficients of linear thermal expansion, the thicknesses, the elastic moduli, and the resistances to creep under tension of the layers <EMI ID = 489.1> 52. Laminate according to claim 51 characterized in that the layer of metal laminated on one side on the core layer of thermoplastic material is aluminum and that that laminated on the other side is a layer of low-strength steel carbon content. 53. Laminate according to claim 51, characterized in that the metal layer laminated on one side of the layer! of thermoplastic material core is aluminum and that laminated on the other side is stainless steel. 54. Laminate according to claim 1, characterized in that the layers of laminated metal on each side of the layer this core of thermoplastic material are thick- <EMI ID = 490.1> 55. Laminate according to claim 1, characterized in that the metal layers laminated on each side of the core layer of thermoplastic material have different thicknesses. 56. Laminate according to claim 1, characterized in that the metal layers on both sides of the core layer of thermoplastic material are ductile. 57. Laminate according to claim 56, characterized; in that it is ductile, 58. Laminate according to claim 57, characterized! in that it is deformable at high temperatures into permanent structures of defined shape. 59. Laminate according to claim 1, characterized in that it is constituted by a substantially flat structure. 60. Laminate according to claim 1, characterized in that it has a structure of defined shape. 61. Laminate according to claim 1, characterized in that the core layer of thermoplastic material and the metal layers are uniformly laminated together by means of an adhesion-promoting agent disposed between the contact surfaces of these layers. 62. Laminate according to claim 61 characterized in that the adhesion promoting agent is a promoter <EMI ID = 491.1> 63. Laminate according to claim 62, characterized in that the organosilane is an amino alkyltrialkoxysilane. 64. The laminate according to claim 63, characterized in that the amino alkyltrialkoxysilane is a gamma-aminopropyltriethoxysilane, 65. Laminate according to claim 63, characterized <EMI ID = 492.1> ethyl) -gamma-aminopropyl-trimethoxysilane. 66. Laminate according to claim 62, characterized in that the organosilane is a glycidoxyalkyltrialkoxysilane. 67. Laminate according to claim 66, characterized in that the glycidoxy alkyltrialkoxysilane is a gamma glycidoxypropyltrimethoxysilane. 68. A laminate according to claim 62, characterized in that the adhesion promoting organosilane is a methacryloxy alkyltrialkoxysilane. 69. Laminate according to claim 68, characterized in that the methacryloxy alkyltrialkoxysilane is gamma-methacryloxypropyltrimethoxysilane. 70. A laminate according to claim 62, cauterized in that the adhesion-promoting organosilane is a metal. <EMI ID = 493.1> alkyltrialkoxysilane. 71. Laminate according to claim 70, characterized in that the amino-alkyltrialkoxysilane and the methacryloxy trialkoxysilane of the mixture are gamma-aminôpropyltrialkoxysilane and gamma-methacryloxypropyltrimethoxysilane! respectively. 72. Laminate according to claim 61, characterized in that the adhesion promoting agent is an adhesive. 73. Laminate according to claim 72, characterized in that the adhesive is an epoxy resin. 74. Laminate according to claim 1, suitable as an auto-panel panel characterized in that: (a) the thermal coefficient of linear expansion is <EMI ID = 494.1> (b) the inelastic ratio is less than 75%. (c) the flexural rigidity is at least equal to 262.65 x 10 <3> N / m. and (d) the maximum weight is less than 6.34 kg / m <2> this further laminated, having a thermal distortion temperature of at least 135 [deg.] C. 75. A method of preparing a metal-thermoplastic-metal laminate according to any one of claims 1 to 74 comprising in combination an inelastic ratio of less than 93%, a coefficient of expansion <EMI ID = 495.1> a bending stiffness of at least 52.53 x 10 <3> N / m and a maximum weight not exceeding 9.76 kg / m <2>. characterized in that this process consists in: have a layer of metal with a minimum thickness of 0.00127 cm on each side of a core layer of thermoplastic material, provided that aluminum is not the metal layer on both sides of this laminate when the layer of core of thermoplastic material is high density polyethylene and further provided that when polypropylene is the core of thermoplastic material and aluminum is the layer of laminated metal on each side of the core, this laminate has a maximum weight of 5.37 kg / m <2>. where the ratio of the thicknesses of the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material is defined by the <EMI ID = 496.1> determined by the zones defined by the ratio of TR (YSm / <EMI ID = 497.1> being defined by the equation of a straight line y = mx + b <EMI ID = 498.1> parameter of the y axis of TR (YS / TS), m is the slope of the straight line and b is the intersection with the y axis, with the condition that, <EMI ID = 499.1> the values of x from 0 to 0.65, and m equals 0 and b equals 70 for the values of x greater than 0.65 and <EMI ID = 500.1> <EMI ID = 501.1> m equals 0 and b equals 9 x 10-6 for values of x greater than 0.1. and the upper limit of these zones is defined by the equation of the straight line as defined above with the condition that: <EMI ID = 502.1> for values of x from 0 to 0.25, and m equals 0 and b equals 100 for values of x greater than 0.25 and <EMI ID = 503.1> b equals 216 x 10 -6 for the values of x from 0 to 0.05, <EMI ID = 504.1> <EMI ID = 505.1> values of x greater than 0.26. <EMI ID = 506.1> measured in bending with a stress of 5% in the outer layers of metal at the location of the maximum deflection. <EMI ID = 507.1> laminate; TR is the ratio of the thicknesses of the sum of the thicknesses of metal layers to the thickness of the core layer of thermoplastic material, YSm is the creep resistance under tension for a thickness and average weight of the two layers of the metal with <EMI ID = 508.1> the core layer of thermoplastic material, laminate the thermoplastic layer and the metal layers by subjecting the assembly to high temperatures and pressures sufficient to maintain contact. and cool to room temperature. 76. Method according to claim 75, characterized in that the core layer of thermoplastic material is partially crystalline, each layer of metal having a melting point higher than this melting point of the crystalline layer of thermoplastic material, and the ratio thicknesses of the sum of the thicknesses of the metal layers to the thickness of the layer of thermoplastic material is further defined by the parameter TR (YSm / TSc) determined in the zone defined by the ratio of TR (YSm / TSc) to <EMI ID = 509.1> being defined by the equation of a straight line y = mx + b <EMI ID = 510.1> x is the parameter of the x axis. of TR (YS / TS), m is the slope of the straight line and b is the intersection on the y axis, provided that m equals 1 and b equals 0 for the values of x from 0 to 0.5, m equals 10 and b equals -0.45 , for values of x from 0.05 to 0.12, and m equals 0 and b equals 0.75 for values of x greater than 0.12. and the upper limit of this area is defined by the equation of a straight line defined above with the condition that: m equals 112.5 and b equals 0 for values of x from 0 at 0.004, m equals 15.3 and b equals 0.389 for the values of x from 0.004 to 0.04 and m equals 0 and b equals 1 for values of x greater than 0.04. or <EMI ID = 511.1> normalized thermal distortion temperature <EMI ID = 512.1> <EMI ID = 513.1> thermal of the core layer of thermoplastic material ^. Tm is the melting point of the crystalline thermoplastic material of the core layer of thermoplastic material. TR is the ratio of the thicknesses of the sum of the thicknesses of the metal layers to the thickness of the core layer of thermoplastic material. YS is the creep resistance under tension for average values of thickness and weight of two layers of metal with an elongation limit of 5% and TS is the tensile strength of the vs core layer of thermoplastic material. 77. Method according to claim 75, characterized in that the high temperatures are between 100 0 and 350 C C. 78. Method according to claim 75, characterized; in that an adhesion promoting agent is interposed between the facing surfaces of the metal layers and the core layer of thermoplastic material. 79. The method of claim 75, characterized in that the adhesion promoting agent is an organosilane promoter. 80. The method of claim 79, characterized in that the adhesion promoting organosilane is an aminoalkyltrialkoxysilane. 81. Method according to claim 80, characterized <EMI ID = 514.1> aminopropyltriethoxysilane. 82. Method according to claim 80, characterized <EMI ID = 515.1> (aminoethyl) -gamma-aminopropyltrimethoxysilane. 83. Process according to claim 79, characterized in that the organosilane is a glycidoxy alkyltrialkoxy-silane. 84. Method according to claim 83, characterized in that the glycidoxy alkyltrialkoxysilane is gammaglycidoxypropyltrimethoxysilane. 85. Method according to claim 79, characterized in that the organosilane is a methacryloxy alkyltrialkoxysilane. 86. The method of claim 85, characterized in that the methacryloxy alkyltrialkoxysilane is gammamethacryloxypropyltrimethoxysilane. 87. Method according to claim 86, characterized in that the core layer of thermoplastic material is a polypropylene, the surfaces of which have been treated with dicumyl peroxide, the metal layers are 1100-0 aluminum, and the high temperature is 200 [deg.] C. 88. Method according to claim 79, characterized! in that the adhesion promoting organosilane is a mixture of amino-alkyltrialkoxysilane and methacryloxyalkyltrialkoxysilane. 89. Process according to claim 88, characterized in that the amino-alkyltrialkoxysilane and the methacryloxyalkyltriethoxysilane of the mixture are gamma-aminopropyltriethoxysilane and gamma-methacryloxypropyltrimethoxysilane respectively. 90. The method of claim 78, characterized in that the adhesion promoting agent is an adhesive. 91. Method according to claim 90, characterized in that the adhesive is an epoxy resin. 92. Method according to claim 75, characterized in that it also consists in: (a) applying a weather-resistant protective coating to at least one of the metal surfaces of the metal-thermoplastic-metal laminate. (b) bake the protective coating at high temperatures. and then (c) cool to ambient temperatures. 93. A method of preparing a laminate of metal-thermoplastic material-metal, characterized in that it consists in: (a) orienting the two layers of metal to obtain a spatial separation between them; and (b) casting a core layer of thermoplastic material between the two layers of metal by in situ polymerization between these layers of a monomer material under the polymerization conditions. 94. Method according to claim 93, characterized <EMI ID = 516.1> of thermoplastic material core is nylon 6. 95. Method according to claim 93, characterized <EMI ID = 517.1> acyl-bis-caprolacta &#65533; and a polyoxypropylene glycol and the core layer of thermoplastic material is a nylon 6 / block polymer copolymer of polyoxypropylene. 96. Method according to claim 95, characterized in that the acyl-bis-caprolactam is isophthaloyl-biscaprolactam. 97. Method according to claim 93, characterized in that the monomeric material is [pound] -caprolactam mixed with calcined kaolinite clay and the core layer of thermoplastic material is nylon 6 reinforced with calcined clay. 98. Method according to claim 97, characterized the nylon 6 reinforced with calcined kaolinite consists of nylon 6 reinforced with 20 to 45% of calcined kaolinite clay. Approved 37 added words.