FR2740385A1 - Thermoplastic lamination useful for washing machine ornamental finish - Google Patents

Abstract

Lamination, for decoration of a substrate, comprises at least three layers, C1 outside, C2 middle, and C3 inside. C1 comprises (co)polymer(s), is appreciably transparent, and has a thickness of at least 300, pref. 400, especially 500-2000 mu m; C2 comprises (co)polymer(s) of (co)polyolefins optionally modified or their mixtures; and C3 comprises non-woven fibrous material(s). Also claimed are: (i) processes for manufacture of lamination; (ii) manufacture of articles incorporating lamination; (iii) decoration of articles using the lamination; and (iv) several processes for incorporating the laminate into materials including extrusion, hot pressing, and injection.

Description

 The field of the present invention is that of multilayer structures, commonly called laminates, comprising in each layer one or more films or sheets of thermoplastic polymers. Laminates are, in fact, construction elements included or attached to the surface of various articles, in which they can perform the functions of mechanical reinforcement, protection against bumps and scratches or even decoration.

 The present invention is therefore particularly aimed at these multilayer or laminated structures, as well as their manufacturing processes.

 In addition, the present invention relates to finished articles coated and / or incorporating said laminates for ornamental and / or reinforcing and / or protective purposes.

 Without this being limiting; the present invention more particularly relates to the decoration of substrates of all kinds, using thermoplastic laminates referred to above. The most preferably used technique, in this context, is that of transfer of sublimable inks within thermoplastic laminates considered, without excluding the conventional techniques of screen printing or other.

 Thermoplastic laminates are therefore intended to be associated with multiple substrates, which presupposes, ultimately, outlets in many technical sectors where one seeks to protect, strengthen and decorate articles. We will mention, especially the automobile; Appliances; sanitary equipment; electrical engineering; furniture; sporting goods (such as fins, windsurf boards, boat hulls, water skis, skateboards, alpine or Nordic skis, monoskis, surfboards ...); or the shoe (plastic shell) among others.

 Thermoplastic decorative and / or protective and / or reinforcing laminates are conventionally incorporated and / or attached to the substrate by any known and appropriate means, of the extrusion, flat extrusion, extrusion inflating, hot pressing, hot-lamination, welding, bonding, thermo-adhesion, injection, injection-blow molding, compression, rotomolding, (on) molding. They must therefore be made from materials suitable for these incorporation and / or fixing operations.

In addition, to assume the functions of reinforcement and / or protection, it is appropriate that the structure and the nature of the materials constituting the laminates are such that the latter resist: - chemical attack (attacks of solvents - such as acetone - or acids), - light and heat attack (yellowing effects, aging and
UV-induced mechanical damage), - mechanical stresses, such as shocks and scratches, - or even thermal stresses (low and high temperatures).

 Such physico-chemical specifications are also expected with regard to another possible destination for these laminates, namely, decoration.

This destination itself imposes other constraints, among which we can mention the ability to lend themselves to traditional printing techniques, including silk screen printing and transfer of sublimable inks (sublimation). Moreover, it is important that the decorations or ornaments, which can be supported by said laminates, are chemically and thermally stable and resist mechanical stresses (shocks, scratches). In addition, the materials of the laminates must not absorb moisture, always in order to preserve the decorations that may be present. In addition, these laminated materials must be easily formable, weldable and heat-sealable for incorporation and / or attachment to the substrates.

 Since they are used as decorative media, laminates must meet specifications specific to this application.

 In this field of decorating laminates or finished articles, several printing techniques are known.

Screen printing is part of the printing techniques that have been used a lot in the past, to make decorations on different items. This technique has a certain number of disadvantages which are: - the numerous necessary manipulations, - the sophistication required for the equipment used, - the cost price and the limitations imposed on the choice of colors and colors.
shades, - and the use of solvents harmful to the environment.

As a result of all these flaws, screen printing has largely begun to be supplanted by the more modern methods of printing sublimated ink transfer (sublimation: see FR-A-2 387 793).

While in screen printing it is necessary to use protective lacquer to preserve surface-printed decoration patterns, sublimation, which underlies the penetration of inks within the support material, implicitly provides improved protection of the decor compared to scratches, shocks, wrenching or other.

Sublimation is not binding on the use of the widest range of colors, as long as the corresponding pigments are sublimable.

In practice and in the case of laminates, the decoration is printed by sublimation in a material or in a sheet of transparent thermoplastic material. Sublimable inks penetrate the thermoplastic receiver material. This sheet can be observed in contrast with an opaque background, consisting of a layer in the background.

The joining of these two layers with any substrate is generally ensured by a third layer formed by at least one adhesion film. The latter is obtained by the conventional methods of hot plaxing, heat sealing, hot pressing, thermoadhesion, heat sealing or injection of molten thermoplastic material on the adhesion layer (overmoulding).

Adhesion to the substrate aside, one of the other virtues desired for the laminate, whether decoration, reinforcement or protection, is its thermoformability, so as to lend itself to thermoforming techniques, all quite ordinary in the field of manufacturing parts made of thermoplastic materials.

 The prior art comprises various technical proposals, which aim, in vain, to offer a protective thermoplastic laminate and / or reinforcement and / or decoration of different substrates, such as skis.

Thus patent application FR 2 596 286 discloses a ski with a protected decoration, the upper face of which comprises a protective element formed by a two-layer decorative laminate, in which the transparent upper layer is made of polyamide 11 and is joined together , on its underside, a layer made of polyamide polyether block (PEBA). It is also intended, in accordance with the invention described in this patent application, a possible lower additional layer C3, formed by a woven material or not and aimed at improving the adhesion of the laminate on the substrate, namely the ski. Notwithstanding this provision, such a laminate has relatively poor substrate adhesion properties and, at the least, not satisfactory from an industrial point of view. Moreover, this multilayer structure is subject to a crippling phenomenon of hot creep. one or more of its constituent layers. This causes the appearance of side beads whose elimination costs time, resources and energy, so money, ultimately resulting in a passable quality.

Moreover, in order to have a maximum thickness of protection for the decoration pattern obtained by sublimation, the inventors of the decorated ski object of this patent application have imagined making laminates in which the sublimation is performed on the inner face a transparent upper layer. After sublimation, said inner face is attached to a lower layer forming an opaque white background of contrast. This variant is purely conceptual and academic and, as such, has never been put into practice. For if this had been the case, the inventors would have realized that, on large thicknesses, the PA 11 is no longer transparent, but milky and that additionally fixing an opaque layer of contrast under the transparent layer Sublimated is an extremely delicate operation, which it is doubtful that it could actually be done, already knowing that the patent application in question does not provide a satisfactory solution to the adhesion of the laminate on the substrate.

In addition, this laminate poses problems of random bonding of the different layers.

Finally, the cost price of these laminates is relatively high.

 Patent application FR 2 620 974, which also relates to a sublimation technique on the inner face of a thermoplastic decorative laminate, does not amend a satisfactory solution either. According to this application, the sublimation is performed on the inner face of the lower contrast layer, the sublimated inks being intended to pass through the latter to finally settle in the transparent layer. The practical results obtained are not convincing. The quality of the decor is average and the problems of the milky appearance of the transparent layer of polyamide and bonding of the laminate on the substrate are not solved.

The patent application FR 92-13 040 relates to a laminate for reinforcing, protecting and decorating a substrate comprising: at least one layer of a polyamidelpolyolefin alloy containing at least one agent
for compatibilizing, and at least one layer of a coextrusion binder, the layer of coextrusion binder
being in contact with said substrate.

In practice, the alloy is composed of PA 6 and polypropylene added with a compatibilizer formed by maleic acid grafted polypropylene, while the binder is preferably constituted by a low density polyethylene grafted maleic anhydride. On high thicknesses greater than 300 μm, the alloy described in this application has the same drawbacks as the PA 11, as regards transparency.

Moreover, they have proved unsatisfactory as regards their ability to bond to the substrates. Indeed, the binder or bonding film (LDPE grafted maleic anhydride) of the outer layer of alloy has the disadvantage of giving rise to random bonding phenomena related to a very narrow bonding temperature range and not compatible with a industrial process. In addition, this maleic LDPE film is particularly difficult to handle, especially because of its strong tendency to wrinkle.

In addition, the outer layer of alloy suffers from having a definitively non-glossy appearance and does not allow the elimination of certain appearance defects inherent in the manufacture (heat treatment). This layer has poor mechanical characteristics (cold shocks) as well as poor resistance to aging (yellowing). The decoration likely to be contained in this outer layer is also penalized by this lack of resistance to aging. Moreover, the adhesion between the outer layer
C1 alloy and PA contrast medium layer is bad.

And, in addition, the presence of polypropylene in the alloy contained in the outer layer C1 seems to hinder the penetration of the sublimation inks and causes a migration over time (fuzzy decoration).

 It is apparent from this review of the prior art that there is an unmet need for a laminate, in particular for decoration, having at least one opaque contrast layer and a transparent layer capable of receiving sublimation inks and intended to be sublimated. so that the resulting decoration is closer to the inner face of the transparent layer than its outer face, to mitigate, by the same, its vulnerability to external aggression.

 There is also no laminate whose transparent layer has a large thickness, to protect the maximum decoration obtained by sublimation. This large thickness may, for example, be between 700 and 800 clam. Such a thick layer must be perfectly transparent so as to protect the decoration from shocks, scratches or other damage, without altering the aesthetic quality and visual definition of said decoration.

 One of the essential objectives of the present invention is to provide a laminate meeting these specifications.

 Another essential objective of the invention is to provide a laminate, in particular for decorating substrates, with a low cost and having a transparent thick top layer, decorable by sublimation.

 Another essential objective of the invention is to provide a laminate, in particular for decorating substrates, comprising at least one thick transparent upper layer which can be decorated by sublimation and which can moreover be fixed efficiently and durably on a substrate.

 Another essential objective of the invention is to provide a laminate, in particular for decorating substrates, comprising a transparent, thick upper layer and in which sublimation decoration can be implanted, the latter being located closer to the inner surface of the substrate. transparent layer than its outer face.

 Another essential objective of the invention is to provide a method of manufacturing, simple industrial and economical laminate referred to supra.

 Another essential objective of the invention is to provide a process for obtaining articles coated or incorporating a laminate of the type referred to above.

 Another essential objective of the invention is to provide a method of decorating a substrate in which the aforementioned laminate is used.

At least some of these objectives, among others, are achieved by the present invention which relates, in the first place, to a laminate, in particular for decorating a substrate, characterized:
. in that it comprises at least three layers, respectively external
C intermediate C2 and internal C3, with reference to the substrate to which said
laminate is intended to be associated,
and in that::
* C, comprises at least one (co) polymer, is substantially
transparent and has a thickness greater than or equal to
300 clam, preferably 400, um and more preferably
between 500 and 2000 pm,
C2 comprises at least one (co) polymer chosen from
(co) modified or unmodified polyolefins and mixtures thereof;
and C3 comprises at least one fibrous nonwoven material.

 Such a laminate comprises a thick transparent layer C1 and which has, moreover, a high resistance to abrasion, chors and scratches, as well as excellent gloss and transparency. Furthermore, C1 is at least partly constituted by a sublimable ink receiving medium entirely appropriate, so as to ensure a high quality of printing, for the decoration that the layer is likely to accommodate.

This laminate also has the advantage of being thermally and chemically resistant. It has, more than a low sensitivity to the phenomenon of moisture recovery. Regarding the thermoformability, the laminate has the expected characteristics. Finally, the laminate according to the invention does not pose a problem of adhesion to the substrate. In addition, this laminate can be easily obtained economically.

The present invention will be better understood and its advantages will become apparent from the following detailed description, several of its embodiments and its preferred features, with reference to the accompanying drawings in which:
FIG. 1 represents a right cross section of a first
embodiment of the laminate according to the invention considered as
that such or already incorporated and / or fixed on a substrate not shown
in the Fig .;
FIG. 2 represents a right cross section of a second
embodiment of the laminate of FIG. 1;
FIG. 3 represents a right cross section of a third
embodiment of the laminate of FIG. 1;
FIG. 4 represents a right cross section of a fourth
embodiment of the laminate of FIG. 1; ;
Fig. 1 shows the laminate of the invention in its first embodiment. This laminate is obtained by superposition and assembly of three layers C1,
C2, C3 initials.

 Once secured to each other, these three layers and more precisely the C2 layer and the C3 layer, give rise to a hybrid and interstitial C23 layer. The latter is in fact a junction zone between C2 / C3 and results from the interpenetration of the fibrous network and the C3 matrix in the constituent (co) polymer material of C2, as will be detailed further below.

 The thick transparent layer C1 includes a decoration D made of inks having penetrated by sublimation and having gathered to form a layer proximal to the inner face of C1 or in other words distal to the outer face.

 As already indicated above, the inside and the outside are defined by reference to the substrate which can be coated and / or to incorporate the laminate, via the available face of C2.

According to a preferred arrangement of the invention, the transparent Cl layer is formed by at least one film made from a material M1 chosen from the following list:
(co) amorphous polyamides, (co) polyamides semi-aromatic, (co) polyamides 6/12 amorphous or non (co) polyamides PAl 1 and PA12,
polycarbonates,
polyolefins terephthalates, preferably polyethylene terephthalates, polyolefins terephthalates, preferably polyethyleneterephthalates, polyolefins, terephthalates, preferably polyethylene terephthalates,
alloys and / or mixtures of the above (co) polymers.

The amorphous (co) polyamides M1 that are preferred in the context of the invention are more precisely PA6 or PA6 / 12.

As examples of such amorphous (co) PAs, mention may be made of those sold under the trade names:
DURETHAN C38 from the BAYER Company
TROGAMID @ x 7323 of ELF ATOCHEM Company
GRILONX CR8-CR9 from EMS Company
The semi-crystalline, crystalline non-amorphous (co) polyamides which may be used are advantageously PAI 1; PA12; PA6; PA6.6; PA6,12, alone or in mixture.

By way of examples of commercial products, mention may be made of coPA 6,12 of VESTAMIDX brand D18 or D22 or ESTAMDX x 7376 of the company HULS.

In this class of (co) PA suitable for constituting at least one of the materials M1 of C1, it is possible to isolate, eg, at least one alloy:
an amorphous (co) PA or not selected from the following compounds
PA6; PA 11; PA 12; PA 4.6; PA 6.9; PA 6.10; PA 6.12; PA
10.12; PA 12.12; PAMXD, 6; PA 6 / PA12; PA 11 / NHAU, BACM6;
PA BACM, 10; PA BACM, 12; BMACM PA, 12; PA 6 / 6.6; and their
mixtures, PA 11 and / or 12 being preferred;
an aromatic and / or semi-aromatic PA is selected from
(co) PAs: PA 6 / 6T; PA 6.6 / 6, T; PA 6, T / 6, I; PA 6/6, T / 6, I
PA 11/6, T; PA 12/6, T; PASA and their mixtures, PASA being
prefer; said alloy optionally further comprising at least one bonding agent.

This particular polyamide alloy provides many advantages to the laminates according to the invention. More specifically, these polyamides are painted with commonly used techniques: light flame or primer, polyamide type for example, without excluding the proven painting techniques on polyolefin: flaming for example or plasma treatment. On the other hand, the high melting temperature of these polyamides leaves a relatively large margin of maneuver with respect to the sublimation temperature. The latter can thus be relatively high, so that all the peppers, including those having a low power of penetration, can penetrate into the receiving medium. This can only improve the quality of the decor obtained.

It is also conceivable to use mixtures of crystalline (or semi-crystalline) (co) polyamides and / or amorphous, semi-amorphous aromatic or semi-aromatic (co) PAs. For example, mixtures:
- (co) PAl l + PASA
- (co) PA12 + PASA
- (co) PA6,12 + PASA are particularly preferred.

 As regards M1 polycarbonates, it can be specified about them, that they are products obtained by condensation of bis-phenol A and phosgene. Amorphous polycarbonates will preferably be selected.

These polymers have the advantage of being endowed with a very high transparency and resistance to shocks and scratches.

MAJCROLON29 3103 from the BAYER Company is an example, among others, of polycarbonate.

The polyolefin terephthalate M1 concerned by the invention are preferably:
polyethylene terephthalate PETP.

 the amorphous polyethylenes terephthalates PETPTR.

 polyethylene terephthalate Glycol PETPG.

 polybutylenes terephthalates PBTP.

More generally, these products are defined as thermoplastic polyesters (linear) which result from the condensation of terephthalic acid with different diols, eg:
- terephthalic acid + ethylene glycol o PETP
terephthalic acid + butylene glycol PBTP.

As an example of commercial products, mention may be made of KODARs brands marketed by Eastman Kodak or ARNITEt) of DSM.

According to a remarkable feature of the invention, it is conceivable to use different additives in this layer.
It is possible, for example, to mix with the (co) polymers M1 described above, elastomer compositions whose role is known in any polymer matrix and whose object is to reduce the flexural modulus and to increase the resistance to shocks. These elastomers may be present in amounts of up to 50% by weight, preferably 5 to 25% by weight relative to M1.

Examples of such elastomers are given below: - ethylene and maleic polypropylene rubbers containing 0.1 to 2% by weight
maleic anhydride, the EPRm being more preferably used in the context of
of the invention; copolymers of ethylene, propylene and maleic diene (EPDMm); copolymers of ethylene, alkyl (meth) acrylate (such as methyl acrylate,
ethyl, n-butyl) and optionally maleic anhydride containing from 2 to 40% by weight
weight of alkyl (meth) acrylate and from 0.01 to 8% by weight of anhydride relative to
total weight of the copolymer.

 In practice, a concrete example of M1 material supplemented with softening elastomers, is given by an alloy: (co) PA + functional terpolymer + binding agent.

More specifically, it may be an alloy (co) PAll + terpolymer E / EA / AM + binder (co) PA6,12 hot melt, this alloy may be of the type marketed under the trademark RILSANS BESNO TL - MB 3800.

 The additives included in the M1 material of Cl can also be fillers, such as fibers or glass beads, carbon fibers, aramid fibers, talcs, silica, etc. Quantitatively, these fillers can reach 50 % by weight relative to the alloy and the compatibilizer, preferably 40% by weight at most.

As another additive, it is also possible to mention agents for protection against ultraviolet radiation, brighteners, release agents, antistatic agents or protection agents against thermal degradation.

 The M1 base material of Cl can be prepared at once, in particular by compounding. The constituents, usually in the form of granules with an average diameter of less than 5 mm, are mixed in the molten state, generally in a kneader, at a temperature between 230 and 300 ° C. After regrinding of the Once obtained, the granules with an average diameter of less than 5 mm are obtained again, and it is also possible to prepare the M1 material (s) in several times, for example by dilution, eg during the extrusion. additives mentioned above can be mixed in the melting state or dry.

 It has been seen above that C1, like the other layers C2 and C3, may comprise one or more transparent sublayers. In particular, C1 can be constituted, according to an advantageous variant of the invention, by a bilayer comprising two sub-layers C11 and C12 of material M1.

Preferably, C11 is a (co) polyamide (eg (co) PA1) and C12 is formed by a mixture and / or an alloy of at least one (co) polyamide aliphatic and at least one (co) polyamide semi-aromatic ((co) PA + PASA). C11 and C12 are advantageously and respectively external and internal, the opposite is not excluded. In the case where C11 is respectively (co) PA and is external, its thickness is, for example, between
150 and 250 m.

 The layer C2, which is preferably intended to form the contrast layer, also plays an essential role in the adhesion of the laminate to the substrate.

In a preferred manner, the layer C2 is formed by one or more sheets made from a material M2 chosen from the following list:
olefinic terpolymers, blocks or statistics, preferably
statistics, the constituent monomers of said terpolymers are
preferably chosen from mono- and / or diolefins; the esters
vinyl esters of saturated carboxylic acid, unsaturated mono- and dicarboxylic acids, their esters and their salts, anhydrides
saturated or unsaturated dicarboxylic acids and more preferably
still, among the following monomers: ethylene, propylene, butene,
pentene, hexene, heptene, octene, vinyl acetate, (meth) acrylate
alkyl, linear or branched C, -C6, (meth) acrylic acid, anhydride
maleic acid and mixtures thereof, said monomers being
possibly be modified, preferably by anhydride residues
maleic.

homo or olefinic copolymers whose monomers are
selected from the following list: ethylene, propylene, butene,
pentene, hexene, heptene, octene and mixtures thereof;
said homo or copolymers possibly being modified by
carboxylic groups preferably derived from anhydride
maleic;
homo or copolymers of modified ethylene and / or propylene
maleic anhydride being particularly preferred;
. monomers, preferably of the polyolefin type, advantageously
polyethylene grafted with inorganic salts;
. mixtures and / or alloys of the aforesaid (co) polymers.

 In the case where M2 corresponds to an olefinic terpolymer and according to a preferred characteristic of the invention, the olefinic monomer represents at least 50% and, preferably, at least 60% by weight of the total of the terpolymer. The terpolymers may have a linear or branched structure.

Among the preferred functional terpolymers are the random terpolymer of ethylene (E), acrylic ester (EA) and maleic anhydride (AM): EtEA / AM.

This corresponds, in particular, to the following commercial products: LOTADERX 3410 or 3210 by ELF ATOCHEM.

 M2 may also correspond to olefinic homo or copolymers optionally modified with an unsaturated carboxylic acid derivative.

The possible modification of this (co) polyolefin with an unsaturated carboxylic acid derivative may result from a copolymerization, a terpolymerization or even a grafting, for example. These (co) polyolefins can be used alone or mixed with other polyolefins.

These polyolefin compositions can be obtained as described in US Pat.
US Pat. No. 4,552,942, namely: 1 -filling an unsaturated carboxylic acid derivative (for example maleic anhydride) on
a polyolefin (eg linear polyethylene or polypropylene), 2 -mixing the resulting grafted (co) polymers with another polyolefin comprising:
a homopolymer of ethylene,
or an ethylene / α-olefin copolymer,
- or a copolymer of ethylene and unsaturated esters or their derivatives,
or a mixture of these polyolefins, all combinations being possible.

Another way of obtaining (co) polyolefins from C2 is to carry out the direct grafting of a mixture of polyolefins. According to another possibility, the binder used is a copolymer or terpolymer comprising an unsaturated carboxylic acid derivative resulting from a radical copolymerization.

As modified polyolefins used in C2, there may be mentioned, by way of examples, the following compositions obtained by polymerization of:
A - a monomer of ethylene or α-olefin or optionally
diolefin
B - at least one comonomer chosen from vinyl esters of acid
saturated carboxylic acid, unsaturated mono- and di-carboxylic acids,
their esters, salts, the anhydrides of saturated dicarboxylic acids or
no.

Olefin, i. e. the olefinic monomer represents at least 50% and preferably at least 60% of the total weight of the copolymer. The copolymers may be polymerized randomly or sequentially and have a linear or branched structure, for the copolyolefins according to the invention.

Examples of these methods of grafting or composition of (co) polyolefins modified are given, without limitation, in the following patents EP 0 210 307, EP 0 033 220, EP 0 266 994, FR 2 132 780, EP 0 171,777, US P4758477, USP 4,762,890, USP 4,966,840, USP 4452,942, USP 3,658,948.

Modified (co) polyolefinic panels, commonly used in many combinations, will preferably be chosen from the following chemical composition products: copolymers of ethylene copolymerized with butene, hexene, octene, mixed
optionally with ethylene-propylene copolymers, grafted with anhydride
maleic, said ethylene / olefin copolymers contain from 35 to 80% by weight
of ethylene, the amount of maleic anhydride grafted is between 0.01 and 1% by weight,
preferably between 0.05 and 0.5%, relative to the total weight of copolymer; copolymers of ethylene and vinyl acetate (EVA), whether or not maleicized (anhydride
maleic material that can be grafted or terpolymerized), particularly containing from 2 to
40% by weight of vinyl acetate, 0.01 to 0.5% by weight of maleic anhydride
graft or from 0 to 10% by weight of terpolymerized maleic anhydride relative to
total weight of copolymer; copolymers of ethylene, alkyl (meth) acrylate (such as methyl acrylate,
ethyl, t-butyl) and maleic anhydride containing from 2 to 40% by weight of
(meth) acrylate and from 0.01 to 8% by weight of anhydride by weight
total of the copolymer.

As examples of commercial products of polyolefins (alone or mixed with each other) modified with a carboxylic acid group by grafting maleic anhydride, mention may be made of those commercially available in the form of granules under the following ATOCHEMS brands: OREVACX 18302, OREVACX 18212, OREVACX PP-C, OREVACX PP-CHV, as well as under the following brands EXXONG): EXXELORX 1015 and 1015 F, EXXELORs PE 805 and 808, MELORs VA 1801, 1803, 1810 and 1820.

The layer C2. thus constituted by the modified (co) polyolefins M2 described above, does not flow, is perfectly compatible with C 1 and actively participates in the adhesion of the laminate to various substrates in combination with C 3.

In addition to or instead of terpolymers and / or homo or copolyolefins optionally modified with carboxylic derivatives, it is possible to use M2 ionomers of (co) polyolefin type, eg polyethylene, grafted with inorganic salts such as Zn or Na.

By way of examples of such products, mention may be made of the ionomers of the SIJRLYNX 8550 brand from the DUPONT DE NEMOURS Company or IOTEKS 3110 from the EXXON Company.
Chemical.

 It is conceivable to optimize the composition of the film or sheets C2, providing that it comprises at least one functional additive of polymeric nature, preferably selected from polyamides and mixtures thereof. In practice, this additive is advantageously of the same nature as the constituent (s) of C 1.

According to a preferred variant, it is possible to use a functional additive consisting of an alloy of at least one polyamide and at least one polyolefin.

Advantageously, this functional additive is present in an amount of less than 50% by weight, preferably of between 1 and 40% by weight and, more preferably still, of between 9 and 35% by weight, relative to the weight of the polyolefin mixture. modified + functional additive.

 According to a remarkable characteristic of the invention, the layer C2 may comprise one or more elastomers of the type of ethylene-maleic-propylene rubber (EPRm), of ethylene-propylene-maleene-diene copolymer (EPDMm) or of ethylene copolymers, alkyl (meth) acrylate (such as methyl, ethyl, N-butyl acrylate) and, optionally, maleic anhydride.

Such elastomers are already described supra since they can also be added to C1, as previously indicated. The amounts of elastomers added are e.g. between 5 and 25%, preferably between 5 and 15% by weight.

 Like the other layers, the layer C2 may be composed of one or more sheets or one or more sheets, made from the constituent materials described in this presentation.

 As regards C3, it should be specified that it is highly preferable that it be formed by at least one layer of nonwoven composite fibrous material M3 comprising fibers included in a polymer matrix, said fibers preferably being in polymer and, more preferably still, in modified cellulose or not, and the polymer of the matrix is preferably selected from synthetic (co) polymers and, more preferably still, from (co) polyesters and / or co) polyolefins.

 More specifically, the above nonwoven composite fibrous material may be constituted by a cellulosic matrix (modified cellulose or not) and polyester fibers and / or polyolefin, e.g. polypropylene. By way of example of such a composite nonwoven material, mention may be made of the product marketed by DEXTER under the name AOD68.

According to an alternative, the nonwoven composite fibrous material is characterized by a matrix and polyester and / or polyolefin fibers (eg polypropylene). As an example of this type of material, mention will be made of the one sold by the company
NORDLYS under the name REEMAY HL 150 W and HL 150 B.

The weight proportions matrix / fiber can vary from 30/70 to 70/30 parts by weight.

According to an original and preferred feature of the invention, the layers C2 and
C3 interpenetrate over a given thickness representing more than 50%, preferably more than 60% and more preferably still between 70 and 80% of the total thickness of
C3. The emergent portion of C3 has a thickness of at least 30 μm, preferably between 40 and 70 μm.

In fact, on this thickness the layers C2 and C3 are intimately mixed with each other and form what may be called a junction zone (layer C23 of Figures 1 to 4).

This intimate connection is made during the manufacture of the laminate thermally (hot pressing: plaxing, calendering, heat sealing, heat sealing). In this junction zone, the matrix, including the C3 fibers, comprises both polymeric material C2 and polymeric material C3. There is thus in C23 an intimate mixture of M2 and M3, a mixture which is able to play an active role in bonding the laminate to a substrate. In reality, there is a synergy between C2 and C3 with regard to membership.

Advantageously, the film, from which C3 is obtained, has a fiber-rich face and a matrix-rich face, the latter being that brought into contact with
C2 before the interpenetration between C2 and C3.

By "rich side" is meant in the sense of the present invention, a face consisting essentially of the matrix products or the fibrous product, as the case may be.

 According to another advantageous arrangement of the invention, the constituent material of C3 (it being specified that C3 may be formed from one or more sheets) has an elongation sufficient to be deformable and to be suitable for the thermoforming operations to which the laminate according to the invention. invention can be submitted. Preferably, the C3-forming foil (s) have a lateral elongation and a longitudinal elongation greater than or equal to 30%, preferably 50% and, more preferably, 100%.

In order to benefit at best from the entire thickness of protection conferred by the transparent layer, it is important that, in the case where the decoration is provided by sublimation, and in accordance with an advantageous characteristic of the invention, said layer C1 comprises within it a decoration made of inks and that, moreover,
The essential of these decorative inks is closer to the inner face of C1 than its outer face.

In the case where the nature of the material M1 allows it to receive sublimable inks, it is advantageous that the decoration is carried out from below the or of one of the sheets of C1, that is to say through its inner face.

In this respect, it is interesting to note that the fact of using sublimation printing on this inner face of Cl does not in any way detract from the possibilities of bonding this layer C1 with the layer C2, for example by thermoforming. adhesion, by hot pressing, (eg by hot plaxing), by welding, and while preserving the integrity of the decoration achieved.

 Advantageously, the laminate according to the invention may comprise at least one contrast film belonging to one of the layers C1 to C3, preferably C2, and comprising at least one contrast pigment.

This contrast film, which may be the layer C1, C2 or C3 as a whole, is particularly useful in the context of the decoration, particularly by sublimation, of the laminate according to the invention. In this case, the opaque background pigmented white or any other solid color or not, brings out the decoration pattern by transparency.

The contrast pigment is, in fact, a color additive which may be, for example, titanium dioxide.

According to the first preferred embodiment of the invention shown in
Fig. 1, the laminate comprises three layers C1, C2, C3, each formed by a film of their constituent material, these films being interpenetrated one into the other, as far as
C2 and C3, and related to each other, as regards C1 and C2.

As an example of this preferred embodiment of FIG. 1, mention will be made of the one in which:
. C1 comprises at least one amorphous (co) PA film, and / or alloy
(mixture or copolymer) of PA 11 or PA 12 and PASA,
(optionally with a binding agent) and / or in (co) PA 6, 12, and / or
amorphous (co) PA6, 12 + (co) PA and / or amorphous (co) PA6,12, and
optionally at least one polycarbonate film and / or
polyethylene terephthalate amorphous or not and optionally glycolized.

. C2 comprises at least one film of statistical terpolymer
ethylene / vinyl acrylate / maleic anhydride and / or polyethylene
low density and / or polypropylene grafted maleic anhydride and / or
ethylene monomer;
C3 comprises at least one nonwoven film made from
cellulose and / or polyolefin (eg polyethylene) included in a matrix
polyester and / or polyolefin (eg polyethylene).

The laminate according to the second embodiment shown in FIG. 2, consists of three layers C1, C2, C3 and a hybrid layer C23, as the embodiment shown in FIG. 1. In these two embodiments of Figs. 1 and 2, only the structure of C1 differs. The layer C1 of FIG. 2 comprises at least one transparent film 120 made of material M1, preferably made of polycarbonate, coated with at least one transparent protective coating that forms:
at least one lower film 110 intended to be in contact with the upper face of the polycarbonate film 120 and chosen from the same materials M2 as those constituting C2,
and at least one upper film 100 made of (co) polyamide (s), advantageously selected from the materials M1 to PA as described above in the description and / or the following aliphatic M1 (co) polyamide (s):
PA6, PA 11; PA 12; PA 4.6; PA 6.9; PA 6.10; PA 6.12; PA
10.12; PA 12.12; PA MXD, 6; PA 6 / PA12; PA 11 / NHAU, BACM6;
PA BACM, 10; PA BACM, 12; BMACM PA, 12; PA 6 / 6.6; and their
mixtures, PA 11 and / or 12 being preferred;
In the embodiment of the C1 / C2 / C3 laminate, the transparent and thick layer C1 is more specifically characterized in that it comprises three sub-layers 100, 110, 120, transparent assembled to one another for form C1. The innermost underlayer is constituted by the polycarbonate film 120, which is capable of including a layer D of sublimable inks forming the decoration. The latter is obtained by using the sublimation technique performed on the face. interior of the underlayer 120 before assembly with C2. The polycarbonate of the underlayer 120 has the advantage of being very transparent and resistant to shocks, scratches and abrasions.
UV. The thickness of this sub-layer 120 may for example be between 300 and 2000 clam, preferably of the order of 500 m + 100clam.

 The upper and lower films 100 and 110, respectively, form a protective coating of the underlayer 12, so that its resistance to solvents (acetone) is improved.

The lower film 110 is, for example, made of ethylene / acrylic ester / maleic anhydride (E / EA / AM) terpolymer and / or maleic anhydride grafted low density polyethylene (PEB, DC) and / or modified maleic anhydride polypropylene ( PP
AM). In this case, it is eg terpolymer E / EA / AM.

 The upper film 100 of C1 is formed by a (co) polyamide or a mixture of (co) polyamide, such as: PAl 1; PAl 2; PA6; PA6.66; PA6, 12.

 The total thickness of the sublayers 100 and 110 is advantageously greater than 50, preferably 100, and more preferably of the order of 150 Cim.

 The layers C2 and C3, whose joining at the interface gives rise to the hybrid layer C23, are of the same type as those described in the first embodiment of the laminate mentioned above. The total thickness of C2 / C3 is e.g. between 100 and 500 μm.

According to the third embodiment of the invention, the laminate comprises at least one film (200) of material M2, preferably polyolefin terephthalate, said film being assembled by its lower face to the layers C2, C23, C3, by means of a bond laminate comprising
at least one upper adhesive transparent film (210) made from a material M3 as defined above,
oet at least one lower film (220) transparent made from a material M1 as defined above, and M1 as defined above.

Fig. 3 attached is an illustration of this second embodiment. It appears that the laminate shown in this figure is also of the three-layer type
C1 / C2 / C3, like those described above (Fig. 1 and 2). The singularity of the laminate of the
Figure 3 is the structure of its layer C1 composed of three sublayers 200, 2i0 and 220.

 The outer sub-layer 200 is formed by the transparent film polyolefin terephthalate (preferably polyethylene terephthalate amorphous or not, glycolized or not).

 This undercoat material M2 = PET, has a thickness greater than or equal to 300 μm and preferably twist 450 μm + 50 μm.

 The bonding laminate of the sub-layer 200 of C1 to the layer C2 is constituted by the sub-layers 210 and 220 which respectively correspond to the transparent upper adhesion film and to the lower transparent film assembled to C2.

 The adhesion film 210 is, for example, made of E / EA / AM terpolymer.

Its optimum thickness is greater than or equal to 50 clam, preferably of the order of 100 μm.
As regards the lower transparent film 220, it is likely to contain the decoration D materialized by a stratum of sublimable inks, located near the upper face of the film 220. In fact, in this case, this decoration by sublimation was performed through the upper face of the underlayer 220, before assembly to the underlayer 200 using the adhesion film 210. But it is perfectly conceivable to achieve sublimable ink transfer via the lower face of the film 220, before its assembly with the layer C2.

 The film 220 is, for example, constituted by a (co) polyamide or a mixture of (co) polyamide, of the PAl 1 type; PA12; PA6; PA6.6; PA6.66 and PA6.12.

 The thickness of the film 220 is greater than or equal to 300 μm, preferably of the order of 400 μm + 50 μm.

 The total thickness of C2 / C3 is e.g. between 100 and 500 μm.

According to the fourth embodiment of the invention, the laminate is characterized in that C2 is formed:
by at least one film 300 made of M2 material as defined above
and by at least one barrier film C2b preferably made of material M2b corresponding to the same definition as that given above for M1 or for M1,
M2b may also be chosen especially from the ethylene / vinyl alcohol ethylene (co) polymers EVOH, polycarbonates.

 Figure 4 illustrates this fourth embodiment. In the trilayer laminate C 1 / C2 / C 3 it represents, only the layer C2 is different from that described for the other embodiments of the laminate of the invention. In particular, C1 may be a C1 analogue of FIG. 1, of FIG. 2 or Fig.3.

This layer C2 thus comprises a sub-layer C2b having a function of barrier to the migration of the inks of the decoration D under the action of temperature, in the case where the decoration D is carried out by transfer of sublimable inks. This barrier
C2b is interpenetrated with the C3 layer of the type described above, to form a hybrid C23 layer. The material M2b constituting this barrier C2b is, for example, a copolyamide or a mixture of copolyamide of the Peace type; PA12; PA6; PA66; PA6.66; PA6, 12.

According to an advantageous characteristic of the invention; of this material M2b is colored, so as to improve the useful contrast for the visualization of the decoration
D included in the C1 layer. This coloration can be obtained by adding any suitable pigment or dye.

 The underlayer or film 300 is made from a material M2, which may be, for example, an E / EA / AM terpolymer, a PEBDC or a PP-AM. This underlayer 300 may also be colored by any suitable pigment or dye.

The preferred thicknesses for the different layers and sub-layers of the laminate of FIG. 4 are as follows:
- thickness of C1 = 300 to 2000 clam.

 C2 / C3 thickness = 100 to 500 μm.

 - thickness of C23 = 0.15 to 0.20 clam.

 emergent C3 thickness = 0.030 to 0.070 clam.

 It goes without saying that the invention is not limited to these four embodiments but that it encompasses all variants and in particular those consisting of combining the structural and constitutional characteristics of the laminates of FIGS. 1 to 4.

With regard to the thicknesses of the various layers C1, C2, C3 of the laminate according to the invention, the embodiments in which: the translucent layer C1 has a thickness of between approximately 0.1 and approximately 1 mm, will be retained more preferably; the contrast layer C2 has a thickness of between 0.1 and 1 mm,
preferably between 0.15 and 0.5 mm, and the optional layer C3 a thickness of between 10 × 10 -3 mm and 300 × 10 -3 mm,
preferably between 10.10-3 mm and 100.10-3 mm.

 The thickness given for C2 takes into account the possibility that C2 comprises a bonding zone in which C2 and C3 interpenetrate and form a hybrid layer C23 in the materials M2 and M3 are intimately maleic.

Thanks to these judiciously selected structural and functional characteristics, the laminate according to the invention offers numerous advantages, including in particular those listed below: their mechanical properties (in particular impact resistance, thermal resistance,
resistance to abrasion and resistance to cuts and tears); - their great chemical inertness; - their dimensional stability between - 40 and + 150 C; - their good aging behavior, - their great ability to glue and decorate (thermal resistance, resistance to
creep) ;; - the exceptional brilliance and transparency of their outer layer, - the very great thickness of this external transparent layer which has the value of
protection for a sublimated decor included in said layer or das one of its sub
layers, and finally their great aptitude for thermoforming (molded or extruded parts, films and
extruded sheets, overmolding, hot gluing, hot-setting, hot-pressing or
thermoforming on complex parts or on films or sheets).

 The sublimation decoration does not alter the brilliance of the outer layer.

But, in addition, this brightness can be further increased by a non-oxidizing flame, which causes a surface recrystallization of the polymer. This provides a protective film and / or reinforcement and / or decoration that can be easily restored and can find a high gloss.

 According to another of its aspects, the present invention also relates to the embodiment of the laminate described supra, as well as a finished article, for example molded or extruded, incorporating the aforesaid laminate.

Thus, the present invention aims, firstly, a method of manufacturing a laminate, as described above, characterized in that it consists essentially:
to produce and / or to implement the layers C, to C3 alone,
. to assemble C2 and C3 by hot pressing, ensuring that they
interpenetrate as prescribed above,
then to join the subassembly C2 / C3 to C1 by hot pressing,
thermo-adhesion, gluing or welding.

 At the base, the films or sheets, constituting each of the layers C 1 and C 2, can be obtained according to known extrusion techniques, such as flat extrusioncalandrage, extrusion-plaxing, extrusion-blowing, etc.

 For C1 and C2 extrusion bonding, temperatures of 20 to 60 OC are generally used above the melting points of M1 and M2.

 With respect to C3, the nonwoven composite fibrous M3 material is obtained by traditional nonwoven manufacturing technologies such as Spunbond.

 It goes without saying that many variants are possible for the realization of the laminate. It is thus possible to modify the assembly order of the different layers, as well as the assembly techniques used, e. g .: pressing, plating or hot calendering at the extruder outlet.

 Instead of being an insert, the laminate according to the invention and / or the layers that constitute it, can be likened to building elements of a more complex article and thus be completely integrated in the manufacture of said article.

This is why the present invention also relates to a method of manufacturing articles incorporating the laminate described above, which process is characterized in that it consists essentially of:
. to be implemented as building blocks to be
assembled together and with the substrate, the different layers
constituting the laminate, singly or pre-assembled,
. and to have recourse for the assembly of the aforesaid elements to at least
one of the following techniques: extrusion, flat extrusion, extrusion
inflating, hot pressing, hot plaxing, welding, gluing,
thermo-adhesion, injection, injection-blow molding, compression,
rotomoulding, (on) molding.

 This refers to manufacturing techniques in which the laminate is made in situ, its constituent layers being assembled to the rest of the article either separately from each other, or after being formed into pre-assembled multilayer subassemblies.

It goes without saying that if one does not aim exclusively the reinforcement and the protection of the substrate, but also its decoration, the inner layer C is subjected to printing, preferably by sublimation, so that sublimable inks having penetrated C1 are as far as possible from the outer face of C1, so as to take advantage of the protection that can offer a thick outer layer C. In the case where C1 has only one film, it amounts to sublimation on the inner side of
C1. On the other hand, if C1 is made of several sub-layers, it is possible to carry out the transfer of inks, in particular, on the outer face of one of the internal sub-layers.

 As we have just seen, the present invention can therefore also be understood as a process for decorating a substrate.

 According to a first implementation, this decoration process may consist essentially of adorning the laminate as described above, a decoration and fix the laminate thus adorned on a substrate.

 According to a second implementation, the decoration process essentially consists of omitting at least one insulated layer and / or a sub-assembly of a layer intended to enter into the constitution of the laminate as described above, of a decoration and to form the laminate concomitantly or not with the article to which the laminate is intended to be associated and, where appropriate, to fix the laminate thus adorned on the substrate to produce the finished article.

 Preferably, the decoration is carried out by sublimable ink transfer printing technique -Cf. Patent FR No. 2,387,793 (sublimation). But it can also be carried out according to other techniques, such as screen printing, painting or varnishing, heat transfer, pad printing, inkjet, laser marking, it being understood that all these techniques of decoration may be applied to all films of the present invention and all articles by deriving in all their forms.

 The present invention also relates to any substrate or article formed by a substrate comprising, and preferably, at least partly coated with a laminate, decorated or not, as described supra.

 Finally, the invention also aims at the use of a laminate, as described above, in particular for the decoration and / or the reinforcement and / or the protection of substrates, preferably by using the technique of sublimation printing.

The list of substrates on which or in which the laminate according to the invention can be applied or incorporated is not limiting. All polyamides, copolyamides, mixtures and alloys based on polyamides, polypropylene as well as all its homopolymers, random copolymers or block copolymers, epoxy resins, polyester resins, metals (steel, aluminum, ...), wood and wood agglomerates, ethylene and vinyl alcohol copolymers, polyurethane foams, high and low density polyethylenes, as well as their polyester base alloys, styrenic polymers (and in particular ABS and PS), PVC and PVC compounds, or even thermoplastic elastomers.

The substrates, and the articles concerned by the present invention, relate to various fields of application, among which we may mention: the field of the automobile, with for example the production of internal parts of
vehicles, such as all or part of the dashboard, the armrests, the cons
doors, etc ...., the realization of external parts of vehicles such as, for example,
wings, doors, hubcaps, bumpers, etc.

- household appliances with, for example, the realization of scales,
washing machines or other household appliances; - the sanitary sector with the production of toilet lids, dispensers
cotton, tablets and towel rails; - the field of electrical engineering and, in particular, the front façades of
command, control keys, synoptic tables, etc .; - the area of furniture which includes, inter alia, cupboard doors,
windows, kitchen fronts, wall coverings, billboards, etc .; - the field of sport, which includes, in particular, the creation of sets or
protection on items as different as fins, windsurfers,
pumps or hulls of boats, water skis, skateboards,
alpine or Nordic skis, mono skis, surfboards, as well as any other spare parts
forming part of the structure of said articles (ie for skis, spatulas or
heels, as well as attachment platforms or others).

When referring to the incorporation of the laminate according to the invention in shaped parts, the targeted applications are, in particular: - the field of footwear with the manufacture of buttresses or patches
on shoe shells or soles, etc.

- the field of the automobile with the manufacture of objects, articles of various sizes, by
example monograms, control keys, bumper elements, etc .; - the field of household appliances with the manufacture of control keys,
decorating elements in superstructures, etc .; - the field of furniture with, for example, the gluing of elements of
handling or decor, etc .;
The present invention will be better understood in light of the following examples of manufacture of the laminates, (with or without decoration corresponding to the embodiments of Figures 1 to 4). These examples will also illustrate the fixing of these laminates on items to be decorated.

EXAMPLES
EXAMPLE 1: (FIGURE 1)
1 - 1. Production of transparent monolayer sheet
In a flat-die extrusion machine (250 mm), a C1 monolayer sheet is produced by mixing a polyamide PAl 1 of the RILSAN BESNOTL type marketed by ELF ATOCHEM and a semi-aromatic polyamide (PASA) of the following type:
GRILAMIDE TR55 marketed by the company EMS in the proportion of 70 parts of PAl 1 and 30 parts of PASA whose characteristics are as follows:
PA11 - density .... . 1.03 - notched Charpy impact strength
(ISO 179) .... . 50 Kjouleslm2 - flexural modulus at 23 C
50% RH (ISO 178 standard) .. .. 000 MPa - equilibrium moisture content 50% RH, 23 C ... 0.9% - melting point (ASTM D789) 183-187 ° C
PASA - density. . . 1.04 - notched Charpy impact strength ..> 7 Kjoules / m2 - equilibrium flexural modulus at 23 C .. 1900 MPa - melting point .. 178C C
The gap of the die is set at 3 mm and the die temperature is 200 to 230 C.

The temperatures of the calendering rollers are: - upper roller .. 45 C - middle roller .... 400 C - lower roller. . . . 35 C
At the end of the die is obtained a monolayer sheet (C1) transparent 0.600 mm thick with a print speed of om / minute.

1 - 2. Manufacture of opaque plastering layer
In a manchine identical to that used in 1-1, the extrusion of a two-layer sheet comprising a layer C2 based on:
- 100 parts by weight of polypropylene grafted maleic anhydride of
ELP ATOCHEM OREVAC PPC type having the characteristics
following: - density (ISO 1183) .. 0.89 - melting temperature (by DSC according to ISO R1218) .. 1510 C - flexural modulus at equilibrium at 23 C
50% RH (ISO 178 standard) ... 580 MPa - Shore A hardness (ISO R868) .. 48 - VICAT point (ASTM D1525) 1220 C and added with EPRm.

- 12 parts by weight of a white NEOSAR dye masterbatch of
CLARIANT society.

The extrusion conditions are identical to those given in 1 - 1.

On leaving the extruder, the DEXTER AOD68 cellulose (fiber) polyester (matrix) cellulose (fiber) composite layer C3 is hot-lined.

A two-layer sheet is obtained comprising 0.25 mm of white OREVAC PPC, (C2 +
C23), and 0.05 mm C3 emerge, with a pulling speed of 8 m / min.

 1 - 3. Decoration of the C1 monolayer sheet obtained in 1 - 1.

The decoration is made on the inside of C1 according to 1-1. and performed by the known sublimable ink transfer printing technique.

Reference will be made to FR.A.2387.793 for the general sublimation printing methodology.

In summary, a decorative film is produced comprising ornamental patterns consisting of sublimation pigment inks applied to this support film (e.g.

paper), according to OFFSET technologies.

The pigment transfer operation on the stratified induced layer C is carried out by means of a press equipped with a heating plate.

Three parameters intervene: the temperature of the heating plate is 185 C.

The duration of the pressing is 1 minute and a half.

The applied pressure is 3 to 5 bars.

This transfer operation provides a laminate decorated with an ornamental pattern whose appearance has not been changed. This integrated and indelible decoration does not alter the initial resistance to UV, chemical agents and abrasion. The surface appearance of the laminate has also not been altered.

1 - 4. Fixation of C1 on C2 and evaluation
The internally decorated C1 sheet and the C2 sheet on the OREVAC PPC portion are made by hot pressing between 140 and 1600 ° C. and for 1 to 3 minutes.

This gives a C1 decorated interior C1 and C2 laminate with a decoration protected by the C1 layer of 0.6 mm.

It is verified that the adhesion between the two layers is good by a "T" peel test performed on test pieces 50 mm wide and 250 mm long. The primer is made by a cutter. An average of five tests is obtained of 13.4 N / mm by delamination PAl 1 / PP-C.

1 - 5. Fixing Decorated Laminate to a Substrate and Evaluation
Hot-pressing between 130.degree. C. and 150.degree. C. for 3 to 5 minutes is carried out on a glass fiber-reinforced epoxy or polyester structure. It is verified that the adhesion between layers is good by a "T" peel test performed on test pieces 50 mm wide and 250 mm long. The primer is made by a cutter. An average of five tests is obtained of 18.9 N / mm, by PA11 / PP-C delamination.

Example 2 (FIGURE 1)
2 -1. Decoration of a substrate by hot-lamination of a decorated laminate
The film has the same composition as in Example 1. It is applied by heat-setting at a temperature between 130 and 150 ° C for 3 to 5 min on a piece of wood composite slatted with phenolic binder.

2 -2. Evaluation resistance to tearing
A peel test, identical to that of Example 1, is carried out and a peel value of a layer of wood of the order of 12.5 N / mm is obtained.

Example 3 (FIGURE II
3 - 1. Making an article molded with a decorative laminate
The film used is a decorated film of the same type as that of Example 1 with the exception of the layer C2 which comprises 5 parts by weight of masterbatches of metallic dyes imitation paint (Iceberg gray Ref CLARIANT 71 39 546 * A) instead of 5 parts by weight of NEOSAR masterbatch of the Company
Clariant.

In this decorated film are cut square rectangular plates of 200 mm × 50 mm.

These decorated plates are then positioned in plan of a rule mold of 180 mm x 30 mm, having on its outer face a relief inscription and a recessed. Polypropylene APPRYL 3050MNI is then injected.

Polypropylene APPRYL (homopolymer) has the following characteristics: - density. . . . 0.095 melt flow index (Melt Flox Index) 5 - bending modulus at equilibrium at 23 ° C
50 HR (ISO 178 standard) .. 1400 Pa - hot deformation temperature (HDT). 96 ° C - melting point (ASTM D789) ... 163 C
The operating conditions of the injection are the following: - temperature 210/230/245 - sheet threshold 0.5 x 0.3 mm thick.

3 - 2. Evaluation of color retention of plate decoration
square before and after joining the laminate to the substrate
The control colorimeter used is: MINOLTA COLOR READER CR10.

The parameters measured are the LAB: L = clarity, a = redovert and b = blue-yellow.

The variations of the LAB before and after molding are the following: AL = 0.5, Aa = 0.2 and Ab = b = Q1.

These results show that the colors of the decoration obtained by sublimation, are particularly preserved. There is no significant loss or degradation of color; induced by the molding heat treatment.

This reflects the particular qualities of the laminate according to the invention.

3 - 3. Evaluation of the peel strength of the decorated molded article obtained
in 3 - 1.

A peel test is performed as before. Values of the order of 12.4 N / mm are obtained.

Examples 4 - POLYCARBONATE (FIGURE 21
4 - 1. In a flat coextrusion machine equipped with two extruders A and
B is made to manufacture a two-layer sheet comprising
EXTRUDER A:
An external sub-layer (100) in PAl 1 of the BESNOTL type
The extrusion conditions are as follows: - extruder A - polyamide (RILSAN):
extruder diameter 45 mm
ratio length / diameter .. 22/1
extrusion temperature C .. 210/230/240/240
EXTRUDER B:
An underlayer (110) in Figure 2 based on E / EA / AM of the LOTADER 3410 type of
ELF ATOCHEM having the following characteristics:
- Fusion point . 95 C
- comonomer content 19%
- VICAT point 63 C - flexural modulus .. 1200 C
Extrusion conditions - extruder B -:
extruder diameter ... 45 mm
length / diameter ratio. 24/1 extrusion temperature "C i 180/190/210/220
The gap of the die is set at 3 mm, the spacing of the calenders is 2.5 mm. The temperature of the die is 250 to 260 OC.

The temperatures of the calendering rollers are:
upper roll ... 70 "C
median roll 45 "C
lower roll. . . 50 C
On leaving the die, a two-layer sheet 0.2 mm thick (100) = 0.1 and (110) = 0.1 is obtained.

4 - 2. In a flat monolayer extrusion machine, extrusion of a sheet
of 0.5 mm in POLYCARBONATE type MAKROLON 3100 of the Company
BAYER
At the extrusion outlet, the hot-lamination of the layer obtained at 4 -1 is carried out. on the sheet obtained in (4 -2). There is obtained a sheet C1 tn-layer 0.7 mm thick comprising a layer (100) in Figure 2 of RILSAN BESNOTL (thickness: 0.1 mm) a layer (110) in Figure 2 LOTADER 3410 (thickness = 0.1 mm) and a layer (120) in Figure 2 of MAKROLON 3100 (thickness 0.5 mm).

4 - 3. Co-extrusion of a C2 E'EA / AM monolayer LOTADER 3410 +
NEOSAR dye.

At the extruder outlet, a layer C3 of fibrous nonwoven composite type DEXTER AOD68 (thickness 0.25 mm) is lined.

This layer C3 emerges over a thickness of 0.04 to 0.07 mm.

 4 - 4. Decoration of the tri-layer sheet C1 obtained in 4 - 2.

The decoration is carried out as described in Example 1 - 3 on the inside of the polycarbonate underlayer (120).

4 - 5. Fixation of the layer C1 obtained in 4 - 2. on the bilayer C2 / C3 obtained
in 4.3. and evaluation
This fixing operation is carried out as described above in 1.4.

An internal decorated laminate is thus obtained consisting of:

<tb> - <SEP> 0.1 <SEP> mm <SEP> from <SEP> RILSAN <SEP> BESNOTL <SEP> (100) <SEP> 1
<tb> - <SEP> 0.1 <SEP> mm <SEP> of <SEP> LOTADER <SEP> 3410 <SEP> (110) <SEP> 1 <SEP> (C1) <SEP>
<tb> - <SEP> 0.5 <SEP> mm <SEP> of <SEP> MAKROLON <SEP> 3110 <SEP> decorated <SEP> (120) <SEP> J
<tb> - 0.25 mm LOTADER 3410 white + DEXTER AOD68 (C2 / C3)
4 - 6. Fixing Decorated Laminate (C1 / C2 / C3) to a Substrate and Evaluation
Hot-pressing between 130.degree. C. and 150.degree. C. for 3 to 5 minutes is carried out on an epoxy or polyester reinforced fiberglass structure. It is verified that the adhesion between layers is good by means of a test. "T" peel made on specimens 50 mm wide and 250 mm long. The primer is made by a cutter. An average of five tests is obtained of 12.8 N / mm, by PA1 1 / PP-C delamination.

EXAMPLE 5- PETG
5 - 1.

In a flat coextrusion machine equipped with two extruders A and B, a two-layer sheet [sublayer (210) and (22) is produced in FIG. 3].

The methodology and materials are the same as those described above in 4 - 1. except that the underlayer (220) of the extruder A is internal, while the underlayer (210) of the extruder B is intermediate within the outer layer C1.

5 - 2. In a flat monolayer extrusion machine, extrusion of a sheet
0.5 mm PETG co-polyester of the KODAR type marketed by
EASTMAN KODAK
At the extrusion outlet, oxidizing flaming of the inner face of the PETG underlayer (200) is carried out to be applied to the 210/220 bilayer according to 5 - 1.

5 - 3. Co-extrusion of LOTADER 3410 + type C2 E / EA / AM monolayer
NEOSAR dye
At the extruder outlet, a layer C3 of fibrous nonwoven composite type DEXTER AOD68 (thickness 0.25 mm) is lined.

This layer C3 emerges over a thickness of 0.04 to 0.07 mm.

5 - 4. Decoration of the sub-layer (220) of the subassembly 210/220 obtained in
5- 1. and assembling the subassembly 210/220 decorated with the underlayer 200
nammed on its inner side according to 5 - 2.

The decoration of the inner face of the underlayer (220) is performed simultaneously with the lining of the flamed PETG underlayer (200) on the underlayer (210).

This decoration is carried out as described in Example 1 -3., On the inner face of the sub-layer (220) PAl 1 (RILSAN BESNO TL).

A three-layer sheet of
- 0.5 mm PETG
- 0.1 LOTADER 3410
- 0.1 BESNOTL decorated
5 - 5. Fixation of the layer C1 obtained in 5 -4. on the bilayer C2 / C3 obtained
in 5 -3. and evaluation
This fixing operation is carried out as described in 1 - 4.

This gives an internal decorated laminate consisting of

<tb> - <SEP> 0.5 <SEP> mm <SEP> PETGKODAR (200) <SEP> 1
<tb> - <SEP> 0.1 <SEP> mm <SEQ> LOTADER <SEP> 3410 <SEP> (210) <SEP> 1 <SEP> (C1)
<tb> - <SEP> 0.1 <SEP> mm <SEP> RILSAN <SEP> BESNOTIL <SEP> decorated <SEP> (220) <SEP> J
<Tb>
- 0.25 mm LOTADER 3410 white + D68 (C2 / C3)
5 - 6. Fixing Decorated Laminate to a Substrate and Evaluation
Hot-pressing between 130.degree. C. and 150.degree. C. for 3 to 5 minutes is carried out on a glass fiber-reinforced epoxy or polyester structure. It is verified that the adhesion between layers is good by a "T" peel test performed on test pieces 50 mm wide and 250 mm long. The primer is made by a cutter.On obtained (average of five tests) a value of 11.4 N / mm, by delamination PA11 / PP-C.

EXAMPLE 6: BARRIER FILM (FIGURE 4)
6 - 1. Extrusion of the transparent monolayer sheet C1.

We proceed as described in 1 - 1. with the same materials
6 - 2. Manufacture of the subassembly 300 / C2dC3 forming C2 / C3
Extrusion of a bi-layer C2 forming and consisting of: - a sub-layer (300) in PPC having 0.15 mm thick and white color; - a C2b underlay in RILSAN BESNOTIL of thickness = 0.15 mm
At the exit of the extruder, a layer C3 of nonwoven fibrous composite of the DEXTER AOD 68 type (thickness 0.25 mm) is lined.

This layer emerges over a thickness ranging from 0.03 mm to 0.07 mm.

 6 - 3. Decoration of the sheet C1 obtained in 6.1.

The decoration of this sheet C1 PAl l + PASA is performed on the inner face thereof as described in 1-3.

6 - 4 Fixing 6 -1. on 6 -2. and evaluation
The internally decorated C1 sheet and the C2 sheet on the OREVAC PPC portion are made by hot pressing between 140 and 1600 ° C. and for 1 to 3 minutes.

This gives a C1 decorated interior C1 and C2 laminate with a decoration protected by the C1 layer of 0.6 mm.

It is verified that the adhesion between the two layers is good by a "T" peel test performed on test pieces 50 mm wide and 250 mm long. The primer is made by a cutter. An average of five tests is obtained of 13.4 N / mm, by delamination PAl l / PP-C.

This gives an internal decorated laminate consisting of
- 0.6 mm Clear RINSAN + PASA mixture decorated front
internal (C1)

<tb> - <SEP> 0.1 <SEP> mm <SEP> PPC <SEP> white <SEP> iC2 / C3) <SEP>
<tb> - <SEP> 0.25 <SEP> mm <SEP> RILSAN <SEP> BESNOTL <SEP> white <SEP> + <SEP> D68 <SEP> J
<Tb>
6 - 5. Fixing Decorated Laminate to a Substrate and Evaluation
Hot-pressing between 130.degree. C. and 150.degree. C. for 3 to 5 minutes is carried out on a glass fiber-reinforced epoxy or polyester structure. It is verified that the adhesion between layers is good by a "T" peel test performed on test pieces 50 mm wide and 250 mm long. The primer is made by a cutter. An average of five tests is obtained of 17.6 N / mm, by PA11 / PP-C delamination.

Claims (20)

CLAIMS:  1 - Laminate, especially for decorating a substrate, characterized:  . in that it comprises at least three layers, respectively external  C1, intermediate C2 and internal C3, with reference to the substrate to which said  laminate is intended to be associated,  and in that:  * C, comprises at least one (co) polymer, is substantially  transparent and has a thickness greater than or equal to  300 Clam, preferably 400 lm and more preferably  between 500 and 2000 clam,  C2 comprises at least one (co) polymer chosen from  (co) modified or unmodified polyolefins and mixtures thereof;  and C3 comprises at least one fibrous nonwoven material.  2- laminate according to claim 1, characterized in that the transparent Cl layer is formed by at least one film made from a material M1 selected from the following list:  (co) amorphous polyamides, (co) polyamides semi-aromatic, (co) polyamides 6/12 amorphous or non (co) polyamides PAl 1 and PA12,  polycarbonates,  polyolefins terephthalates, preferably polyethylene terephthalates, polyolefins terephthalates, preferably polyethyleneterephthalates, polyolefins, terephthalates, preferably polyethylene terephthalates,  alloys and / or mixtures of the above (co) polymers.  3 - Laminate according to claim 2, characterized in that at least one of the constituent materials of C1 is formed by at least one alloy:  . an amorphous (co) PA or not selected from the following compounds  PA6; PA 11; PA 12; PA 4.6; PA 6.9; PA 6.10; PA 6.12; PA 10.12; PA 12.12; PA MXD, 6; PA 6 / PA12; PA 11 / NHAU, BACM6 11 / NHAU, BACM6;  PA BACM, 10; PA BACM, 12; BMACM PA, 12; PA 6 / 6.6; and their  mixtures, PA 11 and / or 12 being preferred;  . an aromatic and / or semi-aromatic PA is selected from  (co) PAs: PA 6 / 6T; PA 6.6 / 6, T; PA 6, T / 6, I; PA 6/6, T / 6, I  PA 1 1/6, T; PA 12/6, T; PASA and their mixtures, PASA being  prefer;  said alloy optionally further comprising at least one bonding agent.  4 - Laminate according to any one of claims 1 to 3, characterized in that the layer C2 is formed by one or more sheets, made from a material M2 selected from the following list:  . olefinic terpolymers, blocks or statistics, preferably  statistics, the constituent monomers of said terpolymers being  preferably chosen from mono- and / or diolefins; the esters  vinyl esters of saturated carboxylic acid, mono- and  unsaturated dicarboxylic acids, their esters and their salts, anhydrides  saturated or unsaturated dicarboxylic acids and more preferably  still, among the following monomers: ethylene, propylene, butene,  pentene, hexene, heptene, octene, vinyl acetate, (meth) acrylate  alkyl, linear or branched C, -C6, (meth) acrylic acid, anhydride  maleic acid and mixtures thereof, said monomers being  possibly be modified, preferably by anhydride residues  maleic.  . mixtures and / or alloys of the aforesaid (co) polymers.  polyethylene grafted with inorganic salts;  . monomers, preferably of the polyolefin type, advantageously  maleic anhydride being particularly preferred;  homo or copolymers of modified ethylene and / or propylene  maleic;  carboxylic groups preferably derived from anhydride  said homo or copolymers possibly being modified by  pentene, hexene, heptene, octene and mixtures thereof;  selected from the following list: ethylene, propylene, butene,  . homo or olefinic copolymers whose monomers are  5 - Laminate according to any one of claims 1 to 4, characterized in that it comprises an inner layer C3 intended to be in contact with the substrate and formed by one or more sheets of nonwoven composite fibrous M3 material comprising fibers included in a polymer matrix, said fibers preferably being of polymer and, more preferably still, of modified or unmodified cellulose, and the constituent polymer of the matrix being preferably selected from synthetic (co) polymers and more preferably still, among (co) polyesters and / or (co) polyolefins.  6 - Laminate according to any one of claims 1 to 5, characterized in that the layers C2 and C3 interpenetrate over a given thickness representing more than 50% preferably more than 60% and more preferably still between 70 and 90% of the total thickness of C3, so as to form a hybrid layer C23,  and in that the emergent portion of C3 has a thickness of at least 30 clam, preferably at least 40 clam, and more preferably still between 40 and 70 m.  7 - Laminate according to any one of claims 1 to 6, characterized in that the film, from which C3 is obtained, has a rich fiber face and the other face rich in matrix, the latter being the one that is put in contact with C2 before the interpenetration between C2 and C3.  8 - Laminate according to any one of claims 1 to 7, characterized in that the C1 layer comprises within it a decoration (D) made of inks and in that the essence of these decorative inks is closer to the inner face of C1 than its outer face.  9 - Laminate according to any one of claims 1 to 8, characterized in that it comprises at least one contrast film belonging to one of the layers C1 to C3, preferably C2, and comprising at least one pigment of contrast.  10 - Laminate according to any one of claims 1 to 9, characterized in that C1 is constituted by a bilayer comprising two sub-layers C11 and C12 of material M1, C11 being preferably (co) polyamide and C12 preferably being alloy or mixture of aliphatic (co) polyamide and semi-aromatic (co) polyamide.  11 - Laminate according to any one of claims 1 to 10, characterized in that Cl comprises at least one sheet (120) transparent material M1, preferably polycarbonate, coated with at least one transparent protective coating formed:  at least one lower film (110) intended to be in contact with the upper face of the polycarbonate film (120) and chosen from the same materials M2 as those constituting C2,  and at least one upper film (100) made of (co) polyamide (s), advantageously selected from the materials M1 to PA according to claim 2 and / or the following aliphatic (co) polyamide (s) M1:  PA6; PA 11; PA 12; PA 4.6; PA 6.9; PA 6.10; PA 6.12; PA  10.12; PA 12.12; PA MXD, 6; PA 6 / PA12; PA 1 1 / NHAU, BACM6;  PA BACM, 10; PA BACM, 12; BMACM PA, 12; PA 6 / 6.6; and their  mixtures, PA 11 and / or 12 being preferred;  12 - Laminate according to any one of claims 1 to 10, characterized in that Cl comprises at least one film (200) of material M2, preferably polyolefin terephthalate, said film being assembled by its lower face to the layers C2, C23, C3 by means of a bonding laminate comprising:  at least one upper adhesive transparent film (210) made from a material M3 as defined in claim 4,  and at least one transparent lower film (220) made from a material M1 as defined in claim 2, and M1 as defined in claim 11.  13 - Laminate according to any one of claims 1 to 10, characterized in that C2 is formed:  - by at least one film (300) made of M2 material according to the  claim 4  at least one barrier film C2b preferably made of  M2b corresponding to the same definition as those given for M1 in  claim 2 and for M11 in claim 10, M2b being able to  also be chosen from (co) polymers  EVOH ethylene / alcoholavinyl, polycarbonates.  thermo-adhesion, gluing or welding.  then to join the subassembly C2 / C3 to C1 by hot pressing,  interpenetrate as prescribed in claim 6,  . to assemble C2 and C3 by hot pressing, ensuring that they  to produce and / or implement the C1 to C3 layers in isolation,  14 - A method of manufacturing articles incorporating the laminate according to any one of claims 1 to 13, characterized in that it consists essentially:  15 - Process for manufacturing articles incorporating the laminate according to any one of claims 1 to 13, characterized in that it consists, essentially:  . to be implemented as building blocks to be  assembled together and with the substrate, the different layers  constituting the laminate, singly or pre-assembled,  and to use, for the assembly, at least one of the techniques  extrusion, flat extrusion, inflation extrusion,  hot, hot plax, welding, bonding, heat-adhesion, injection,  injection-blow molding, compression, rotomoulding, (on) molding.  16 - Process for decorating a substrate, characterized in that it consists, essentially, to adorn the laminate according to any one of claims 1 to 13 of a decoration and to fix the laminate thus adorned on a substrate.  17 - Process for decorating a substrate, using a laminate according to any one of Claims 1 to 13, characterized in that:  First, the layers C2 and C3 are fixed to the substrate  between these two layers being or not previously carried out,  and the layer C1, decorated or not, is then secured to the layer C2.  . and where appropriate we decorate C1.  18 - Process according to claim 16 or 17, characterized in that the decoration is performed by sublimable ink transfer printing technique.  19- Substrate comprising at least one laminate according to any one of claims I to 13.  20 - Use of a laminate according to any one of claims 1 to 13, in particular for the decoration and / or the reinforcement and / or the protection of substrates, preferably in the sublimable ink transfer printing technique.