FR2740384A1 - Thermoplastic laminations used for ornamental finishes and protection - Google Patents

Abstract

Lamination, notably for decoration of a substrate, comprises at least three layers; C1 (outside), C2 (middle), and C3 (inside). C1 contains at least one polyamide; C2 contains at least one modified polyolefin; C1 and/or C2 eventually have at least one elastomer added; and C3 comprises at least one non-woven fibrous material. Also claimed are processes for manufacture of lamination, manufacture of articles incorporating lamination, and decoration of articles with the help of the lamination. Preferably C1 is formed from at least one thin sheet of polyamide, preferably chosen from Polyamide PA11 and/or PA6.12 and/or PA6. C2 is formed from at least one thin sheet of polyolefin or a copolymer of a polyolefin modified by an unsaturated derivative of a carboxylic acid; and it also comprises preferably 1-40, especially 9-35 wt.% at least one additive chosen from, preferably, polyamides and their mixtures and is especially a mixture of at least one polyamide and at least one polyolefin. In preference to C1 and C3, C2 also contains a contrast sheet comprising a contrast pigment.

Description

The present invention relates to the field of the decoration of various substrates made of metal, wood, thermoplastic thermosetting polymer or any other material used in the constitution of articles as diverse as varied and falling under: - the automotive sector, such as internal parts of vehicles,
type dashboard, armrests, storm doors, or even external parts
vehicles, such as fenders, doors, hubcaps, bumpers,
mirrors etc ....; - the appliance sector (small and large), such as razors,
refrigerators, scales, washing machines or others; - the sanitary sector, such as toilet lids,
cotton dispensers, shelves and towel rails; - the electronics sector, such as control cabinet facades,
control keys, synoptic tables; - the furniture sector with, for example, cupboards, windows
kitchen fronts, wall coverings and advertising panels; - and the sports sector, such as swimming fins,
sailing, boats, water skis, skateboards, alpine skis, background
or jump, monoskis, surfboards, as well as the patches that can be
associate, such as spatulas, heels, attachment platforms or others; - and finally the footwear sector and, in particular, that of molded parts.

 More specifically, the subject of the present invention is, on the one hand, the laminates, in particular of decoration, formed of several layers essentially made of thermoplastic material (s) and, on the other hand, some of the manufacturing processes of said laminates.

 In addition to the decoration, such laminates may also be intended for strengthening and protecting the substrates to which they apply.

 The present invention is also directed to a process for decorating substrates, in which the aforesaid laminates are used.

 In addition, the present invention relates to articles, such as skis or the like, incorporating such laminates for reinforcement and / or protection and / or decoration purposes.

 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, in order that the reinforcement and / or protection functions can be best satisfied, the structure and the nature of the materials constituting the laminates should be such that they resist: - chemical attack (solvent attacks - such than acetone - or acids), - to light and thermal aggressions (effects of yellowing, 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). It is important, moreover, that the decorations or ornaments, likely to be supported by said laminates, are chemically and thermally stable and resistant to 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.

 Without this being limiting, more specifically, in the context of this presentation, we will focus more specifically on essentially thermoplastic laminates that can be decorated using the sublimation ink transfer printing technique (sublimation). This technique has taken precedence over silkscreen printing, which is costly, rigid in its implementation and reducing the possibilities of aesthetic expression and the variety of colors that can be used. In addition, the screen printing involves solvents, which is not without damaging the environment.

It is in the sector of the decoration of sporting articles, of the ski kind, that appear the first thermoplastic decorative laminates. Thus, patent application FR 2 596 286 discloses a multilayer structure (bi or tri-layer) intended to be applied to the upper face of a ski and comprising a top layer C1 of polyamide PA-1 1, an intermediate layer C2 polyamide-polyether block copolymer (PEBA), of the type marketed under the names "PEBAX 2533 or 3533" by the Company
ATOCHEM, and an inner layer C3 constituted by a nonwoven material and intended to promote adhesion to the ski (substrate). This layer C3 textile element, woven or not, is not sufficient to significantly improve the bonding of the laminate and, in particular, the intermediate layer C2 PEBA, the substrate.En addition, it is observed that this type of PA-I1 / PEBA laminate exhibits a strong tendency to creep, a phenomenon that does not fail to occur during thermoforming, heat-sealing or (over) molding operations, in which the laminate is likely to be involved.

Concretely, this results in the appearance of side bead that must be eliminated, resulting in additional cost and poor finish. This is particularly true in the case of ski decoration.

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

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

According to another proposal and which is described in the patent application
FR 92-13 040, it is a question of bilayers whose outer layer C1 comprises an alloy of polyamide PA-6 and polyolefin, said alloy being completed by a compatibilizer formed by a (co) polyolefin modified. The latter is, for example, a maleic acid grafted (co) polyolefin or a copolymer of olefin and maleic acid, or else a polyolefin copolymer grafted maleic acid and polyamides. The inner layer C2 of this laminate comprises, in turn, a coextrusion binder useful for adhesion to the substrate and consisting of a (co) polyolefin grafted with maleic anhydride, eg: low density polyethylene (LDPE) , grafted maleic anhydride.

This patent application also discloses trilayer structures having opaque intermediate layers of PA-6, maleic vinyl ethylenecalcetate copolymer (EVAm) or alternatively ethylene / maleic polypropylene copolymer (EPRm).

These laminates have the characteristic of having a prohibitive cost for a viable industrial application.

Moreover, they have proved unsatisfactory as regards their ability to bond to the substrates. Indeed, the 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 an 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 C1 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 of alloy and the contrast intermediate layer PA is bad.

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

 In this state of knowledge, one of the essential objectives of the present invention is to provide a laminate, in particular for decorating a substrate, which satisfies the specifications of mechanical, thermal and chemical resistance, presented above.

 Another essential object of the invention is to provide a laminate having optimum properties of thermoforming, heat sealing, as well as extrusionability, flat extrusion, extrusion inflation, hot pressing, plaxing. hot, welding, bonding, thermo-adhesion, injection, injection-blow molding, compression, rotomolding, (on) molding.

 Another essential objective of the invention is to provide a laminate which can be decorated using sublimation ink transfer techniques (sublimation) and which make it possible to obtain high quality, temperature-stable and UV-resistant ornaments resistant to chemical attack and mechanical stresses; said laminate to include, at the same time, materials promoting the penetration of sublimable inks during printing (non-migration).

 Another essential objective of the invention is to provide a laminate that can be universally decorated by any accessible decorative technique.

 Another essential objective of the invention is to provide a laminate that is compatible with the greatest number of substrates, both in terms of the structure and in terms of the nature of the materials to be associated, in particular, it is important that the laminate is perfectly secured, for example by thermal adhesion to the substrate.

 Another essential object of the invention is to provide a laminate, in particular for decorating a substrate, which is economical and which is easy to manufacture and / or to incorporate in and / or fix on the substrate.

 Another essential objective of the invention is to provide a process for decorating a substrate using the laminate referred to above, this process being easy to implement and inexpensive.

 Another essential objective of the invention is to provide substrates and articles decorated using the aforesaid laminate, which are resistant and whose decor is aesthetic and durable.

After having set these objectives, the Applicant had the merit of highlighting, in a completely surprising and unexpected manner, and after numerous studies and tests, that it is necessary to associate at least three layers to realize the laminated: - the outer layer Cl being made of polyamide, notwithstanding the unfavorable prejudices
weighing on this material in this technical context, - the intermediate layer C2 being modified polyolefin, despite the weaknesses
presumed of this type of material (polypropylene), - the inner layer being a nonwoven composite, judiciously selected, - and, finally, C3 interpenetrating C2.

It follows that the present invention relates to a laminate characterized by:
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:
* Cl comprises at least one polyamide;
C2 comprises at least one modified polyolefin,
C1 and / or C2 being optionally added with at least one
elastomer;
and C3 comprises at least one nonwoven fibrous material.

 Thanks to this combination of materials organized in a particular multilayer configuration, the laminate according to the invention amply meets the specifications expected for this type of product.

 In particular, the polyamide or the polyamide mixture of the outer layer C1 is resistant to abrasion, impact and scratching and, moreover, has a gloss and transparency quite satisfactory, even after sublimation printing. within said layer C ,. However, the choice of these polyamides was not self-evident, given their known lack of moisture recovery, a defect at the origin, on the one hand, significant dimensional variations for parts made from this material and on the other hand, a significant decrease in their mechanical properties. Polyamides are also criticized for being sensitive to solvents or other acidic chemicals. It is to the merit of the Claimant not to have taken into account all these unfavorable prejudices.

 The same goes for other negative a priori, attached this time to polypropylenes and according to which the mechanical strength (in particular the cold shock and the abrasion resistance), as well as the resistance thermal of these products are low.

Despite this, the material selected for the intermediate layer C1 is a modified polyolefin.

Finally, the layer C3, which is advantageously closely related to the layer C2, plays a key role in the adhesion capacity of the laminate on multiple substrates. The C3 layer shares this role in the adhesion with the layer C2. C3 and C2 intervene, mainly and respectively, physically and chemically in adhesion. C3 and C2 form a complex which makes it possible to bind the laminate on substrates of various natures.

For the purposes of the present invention, the laminate concerned can be likened to either a film (film) or a sheet; knowing that according to the book "Modem Plastic
Encyclopedia ", we reserve the term of film to flat objects whose thickness is less than 250 C1 and the term of sheet to objects of greater thickness and up to several millimeters In the present description, one will use, indifferently, these terms to designate any of the products, ie the laminate as a whole or the different layers, or even sub-layers, which may constitute it, for reasons of convenience and simplification.According to the technology employed, the laminates have a thickness between 5 llm and 5 min plus.

 The laminates according to the invention are easily heat-formable and decoratable by sublimation. They can therefore be used to reinforce, protect or decorate various substrates, especially as they present a very interesting combination of properties of thermal resistance, chemical resistance and low sensitivity to water absorption phenomena.

 According to a preferred arrangement of the invention, the layer C1 is formed by at least one polyamide film, the latter preferably being chosen from aliphatic polyamides, alone or mixed with one another, polyamide PA-11 and / or or PA-6, 12 and / or amorphous PA6 being particularly preferred.

It therefore appears that the polyamide used for Cl can be any polyamide, copolyamide, aliphatic and / or aromatic, optionally containing a third of monomers present in proportions not substantially modifying the properties of said polyamide.

Examples of polyamides which can be used are crystalline or semi-crystalline polyamides, amorphous or semi-amorphous, both aliphatic and aromatic, pure or in mixtures with one another, or mixed with fillers. The polyamide blends can be crystalline / crystalline, amorphous / amorphous or crystalline / amorphous mixtures.

Examples of aliphatic semi-crystalline polyamides are, without limitation, polyamides: PA-6; PA-1 1; PA-12; PA4.6; PA-6.6; PA-6.9; PA-6.10; PA-6.12; PA-10, 12; PA-12, 12; PAMXK, 6; copolyamides PA6 / PA12; 11 / NHAU, BACM, 6; BACM, 10; BACM, 12; BMACM, 12; PA-6, PA-6.6; and mixtures thereof. Examples of semi-crystalline aliphatic polyamides are non-limiting polyamides PA6; PAîl; PA12; PA4.6; PA6.6; PA6.9; PA6,1O; PA6, 12; PA10.12; PA12,12;
PAMXD, 6; copolyamides PA6 / PA12; 11 / NHAU; BACM, 6; BACM, 10
BACM, 12; BMACM, 12; PA6, PA6, 6; and their mixtures. Examples of aromatic semi-crystalline polyamides are polyamides: PA6 / 6 T; PA6,6 / 6, T
PA6, T / 6, I; PA6 / 6, T / 6, I; PAl 1/6, T: 12/6, T; and their mixtures. Examples of amorphous polyamides are PASA (of the Applicant), PEBA (known under the name "PEBAX") and polyamides: PA6, I; 6 / BMACP, I; 6 / BAMN, T 11) BMACM, I; 11'BMACM, T / BMACM, I; 11 / BACM, I / IPDA, I; 12 / BMACM, I; 12ABACM, T / BACM, I; 12 / BMACM, T / BMACM, I; 12 / BACM, I / IPDA, I; 6, T / 6,
I / BACM, I; 6, T / 6, I / BACM, T / BACM, I; TMHMDA, T; and their mixtures.The third monomers, which can be used in combination with the abovementioned polyamides, are lactam or amino acid type monomers, or any other type of polymerizable monomer with polyamides, to form, for example, block polymers based on amide sequences, with other features.

It is also possible to mix, with the polyamides described above, elastomer compositions whose role is known in any polymer matrix and whose object is to reduce the flexural modulus, to increase the impact resistance. These elastomers may be present in amounts of up to 50% by weight, preferably from 5 to 25% by weight, relative to the final composition. By way of example of such elastomers, mention may be made of: maleated ethylene and polypropylene (EPRm), particularly
preferred by the Applicant, containing 0.1 to 2% by weight of maleic anhydride, copolymers of ethylene, propylene and maleic diene (EPDMm), copolymers of ethylene, (meth) acrylate, alkyl (such as methyl acrylate,
ethyl, N-butyl) and, optionally, maleic anhydride containing from 2 to 40% by
weight of alkyl (meth) acrylate and from 0.01 to 8% by weight of anhydride relative to
total weight of the copolymer.

The amounts of elastomers added are e.g. between 5 and 25%, preferably between 5 and 15%.

 With the polyamide compositions described above, various other constituents may be incorporated, such as fillers, pigments or dyes, various additives.

By way of example of fillers, mention may be made of fibers or glass beads, carbon fibers, aramids, talcs, silica, calcium carbonate, kaolin, ceramics, salts and oxides. metal, such as aluminum powder, manganese powder, ferrite powder, titanium oxide.

In general, up to 50% by weight of these fillers can be incorporated in relation to the polyamide. Preferably, the filler is up to 40% by weight.

By way of examples of additives, mention may be made of agents for protection against ultraviolet radiation, brightening agents, release agents, antistatic agents, protection agents against thermal degradation.

 The polyamide compositions can be prepared in one go, 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 of between 230 and 300 OC. The compositions obtained are, in most cases, in the form of granules with an average diameter of less than 5 mm. It is also possible to prepare the polyamide compositions in several times, for example by dilution, this dilution step being, moreover, to be implemented at the same time of the extrusion, when the proportions of the constituents are respected.

Certain additives (dyes, release agents or lubricants, etc.) may be incorporated by mixing the mixture in the melting or dry state with the granules obtained.

 In addition to their mechanical strength and sublimation properties, these polyamides have the advantage of being able to be painted with the commonly used techniques: lightweight flame retardant or polyamide-type primer, for example, without excluding the proven polyolefin paint techniques: flaming for example, or plasma treatment.

Another advantage of the polyamide layer Cl according to the invention is to allow sublimation temperatures sufficiently high to ensure good penetration of all usable sublimable inks and thus ensure a good quality of decoration.

 With regard to the layer C2, it is preferably formed by at least one layer of modified polyolefin or modified polyolefin copolymer with an unsaturated carboxylic acid derivative.

The 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 the patent
US Pat. No. 4,452,942, to record 1-graft an unsaturated carboxylic acid derivative (for example, maleic anhydride) onto
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 / 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 modified (co) polyolefins are given, without limitation, in the following patents: EP 0 210 307,
EPO 033 220, EP 0 266 994, FR 2 132 780, EP 0 171 777, US P4758477, US Pat. No. 4,762,890, US Pat. No. 4,966,840, US Pat. No. 4,452,942 and US Pat. No. 3,658,948.

Among these modified (co) polyolefins, commonly used in numerous combinations, the following products will preferably be chosen: - 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 in admixture) 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 trademarks
ATOCHEM: OREVAC 18302, OREVAC 18212, OREVAC PP-C, OREVAC
PP-CHV, as well as under the following ExxON brands: EXXELOR 1015 and 1015 F, EXXELORPE 805 and 808, EXXELOR VA 1801, 1803, 1810 and 1820.

The layer Cz thus formed by the modified (co) polyolefins described above, does not flow, is perfectly compatible with Cl and actively participates in the adhesion of the laminate to various substrates in combination with C3.

With regard specifically to the compatibility of C2 with Cl, it is conceivable to optimize it according to the invention, by providing that the layer C2 comprises at least one functional additive of polymer nature, preferably chosen from polyamides and their mixtures . In practice, this additive is advantageously of the same nature as the polyamide (s) of C1,
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.

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.

 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.

 The laminate according to the invention may comprise, according to another advantageous variant, at least one contrast film belonging to one of the layers C1 to C3, preferably to 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.

 With regard to C3, it should be pointed out that it is highly preferable that it be formed by at least one layer of nonwoven composite fibrous material comprising fibers embedded in a polymer matrix, said fibers preferably being polymer, and more preferably still, cellulose modified 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 90% of the total thickness of C3, and in that the emergent portion of C3 has a thickness at least 30 μm, preferably at least 40 μm and more preferably between 40 and 70 μm.

In fact, on this thickness layers C2 and C3 are intimately mixed with each other and form what can be called a junction zone. 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.

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 material constituting C3 (it being specified that C3 may be formed from one or more sheets) has sufficient elongation 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 one of its preferred embodiments, the laminate according to the invention is characterized in that:
. Cl comprises at least one polyamide PAl 1 and / or PA6.12 film,
and / or amorphous PA6, C1 being preferably transparent;
C2 comprises at least one polypropylene film modified with
maleic anhydride, C2 being preferably colored,
C1 and / or C2 being optionally added with EPRm and / or dEPDm;
and C3 comprises a nonwoven film made from cellulose fibers
embedded in a polyester and / or polyolefin matrix.

With regard to the thicknesses of the various layers C1, C2, C3 and the total thickness of the laminate according to the invention, it should be pointed out that:
0.1 <ecl <1.5 mm, preferably 0.1 <eCI S 1 mrn;
0.1 <eC2 <1 mm, preferably 0.15 <eC2 <0.5 mm;
1.10-3 mm <ec3 <5.10-2 mm, preferably between 1.10-2mm <ec3 <15.10-2 mm.

 The thickness Cc2 given above includes the thickness of the layer C2 proper and the thickness of the intermediate junction zone in which C2 and C3 are intimately mixed with each other.

 Because of their easy implementation, their good mechanical properties (in particular cold impact resistance, resistance to abrasion, notch and tear), their great chemical inertness (no known solvents), of their dimensional stability between -40 and + 150 ° C, their good aging behavior, their very good adhesion and decorative properties (thermal resistance, creep resistance), and their exceptional gloss, the compositions according to the The invention can be used in a wide variety of forms (molded or extruded parts, films and extruded sheets) for the protection, decoration or reinforcement of various objects.

 After sublimation decoration, the outer layer remains bright. In addition, this brightness can be reactivated by non-oxidizing flaming which causes a surface recrystallization of the polymer. This gives a protective film and decor that can be easily restored and can find a high gloss.

According to another of its aspects, the present invention also aims to manufacture the laminate described supra, both as an individualized building element and part of a set or an article comprising said laminate therein. In other words, this corresponds in the first case to a decorating laminate, decorated or decorated, in particular by sublimation, and intended to be fixed on a substrate, such as a ski, for ornamental purposes in particular. In the second case, the laminate, decorated or decorated, is not physically isolated but is an integral part of the article which provides the reinforcement and / or protection and / or decoration of said article.

Thus, the process according to the invention for manufacturing the at least three-layer laminate (each of the layers consisting of at least one film), as described above, is characterized in that it consists essentially of:
. to produce and bind to one another the layers C1 and C2 by
(Co) extrusion,
. and applying the C3 layer on the C2 layer
softened, preferably out of the extrusion before solidification of
C2, so that C3 binds to C2 by heat-sealing or welding
while penetrating into C3 over at least a portion of the thickness of C3.

The layers and the possible sub-layers C1 and C2 can be obtained according to known extrusion techniques, such as flat extrusion calendering,
Extrusion-plaxing, extrusion-blow molding, etc ...

 In practice, the extrusion temperatures of the polyamide and modified (co) polyolefin sheets or films of the C 1 and C 2 layers, respectively, are generally 20 to 60 ° C higher than the melting point of the polymers concerned.

 With respect to C3, the nonwoven composite fibrous material is obtained by traditional nonwoven manufacturing technologies, such as yarn / bound.

 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 ...

Thus, a variant of the above process consists essentially of:
to produce and / or implement the C1 to C3 layers in isolation,
. 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, welding.

 According to another case mentioned above, the laminate can be included directly in articles or parts shaped by molding or extrusion. These shaped parts, for example profiles, can be multi-injected or coextruded, so as to obtain a composite part in a single operation.

This is the reason why the present invention also relates to a method for manufacturing articles incorporating the above described laminate and 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 use, for the assembly of the aforesaid elements, 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.

 For the assembly of these different subsets layers or sublayers C "C2, C3 between them and with the rest of the article can be resorted to hot pressing or other heat-bonding treatment: heat-bonding , welding, plaxing, overmolding, etc.

 According to another embodiment of incorporating or fixing at least one layer of the laminate according to the invention in or on a substrate, the layer or layers, assembled or not, are placed inside a mold for the production of the desired finished article, then forming the one or more layers or the laminate with the mold die punch, and finally injecting molten plastic material, which adhesion, the layer or layer or laminate with the rest of the material constituting the article.

 As indicated above, the laminates according to the present invention can be decorated according to the sublimable ink transfer printing technique and, in particular, according to the processes described in patent FR-A-2 387 793. The decoration of these materials can also be performed according to other techniques, such as screen printing, painting or varnishing, heat transfer, pad printing, inkjet, laser marking, it being understood that all these decoration techniques can be applied to all films of the present invention and all articles deriving in all their forms.

Preferably, the decoration of the laminate, for example by sublimation, is performed after assembly of the three layers knowing that C is preferably translucent and C2 advantageously opaque. Thus, the invention also provides a method of decorating a substrate consisting essentially of adorning the laminate as described above, for example by sublimation printing technique, a decoration, and fixing the laminate thus adorned on a substrate, by any known and appropriate means.

 This preferred mode of decoration does not, however, exclude the various other possibilities of embodiment of the ornament, including those made after joining the laminate on the substrate or after completion of the finished article incorporating the laminate.

According to another alternative, the decor may be printed in or under the layer C, even before its assembly with the other layers C2, C3 constituting the laminate according to the invention. This alternative corresponds to a variant of the method according to the invention for decorating a substrate with the aid of the laminate described above, in which:
first we fix to the substrate the ouches C2 and C3, the intimate bond
between these two layers being or not previously carried out,
The layer C1, decorated or not, is then secured to the layer C2.

 and where appropriate we decorate C1.

 Another object of the present invention is constituted by any substrate comprising at least one laminate, as described above. Preferably, the substrate is coated with the laminate according to the invention.

The nature of the substrate can be very varied. They may be, for example, polyamides, polyolefins, epoxy resins, polyester resins, metals (steel, aluminum, etc.), woods and the like, copolymers of ethylene and of vinyl alcohol, polyurethane foams, low density and high density polyethylenes and their alloys based on polyester, polymers based on styrenic bases (in particular ABS and PS), PVC and PVC compounds or even thermoplastic elastomers.

The fields of application for which these substrates arise, which may be associated with the laminates according to the invention, are numerous. Of particular note are: - the automobile sector with, for example, the production of internal parts of
vehicles, such as all or part of the dashboard, armrests, storm door, etc., the
production of external parts of vehicles with, for example, wings, doors,
wheel trims, bumpers, mirrors, etc .; - household appliances (small and large) with, for example, making razors,
refrigerators, scales, washing machines or others, - the field of sanitary, with the realization of toilet lids, dispensers
of cotton, shelves and towel rails, - in electrical engineering, for example, the construction of façades before
control cabinets, control buttons, synoptic tables, etc., - the field of furnishing: closet doors, windows, kitchen fronts,
wall coverings, advertising boards, - the field of sports with, for example, the creation of decorations or protection
on fins, windsurf boards, boat decks, water skis, boards
casters, downhill or cross-country skis, monoski, surf and patches, such as
spatulas or heels, attachment platforms or the like.

Among the areas of application of the shaped parts, mention will be made, 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 of very different sizes, by
example monograms, control keys, bumper elements, etc.

- the field of household appliances with the manufacture of control keys,
decoration elements in super-structure, etc.

- the field of furniture with, for example, the gluing of elements of
handling or decor, etc.

 Finally, as understood, the present invention also includes the use of a laminate, as described above, in particular for the decoration and / or the reinforcement and / or the protection of substrates, preferably according to the technique of sublimation printing.

 The invention will be better understood with the aid of the following examples which describe the manufacture of several laminates according to the invention, as well as their incorporation and / or their attachment in or on substrates of the alpine or Nordic skis kind.

EXAMPLES
EXAMPLE 1 1.1: Manufacture of the laminate according to the invention
In a flat coextrusion machine, equipped with det: x extruders A and B, a die
bilayer (width 500 mm) with adjustable lips, a sheet is made
tricouche comprising: o an outer layer C1 polyamide PA11 type R12 SAN BESNO TL
marketed by ELF ATOCHEM and whose indicative characteristics are given
hereinafter: - density. 1.03 - notched Charpy impact strength
(ISO 179 standard) 50 Kjoules / m2 - balanced flexion modulus at 23 OC
50 / O HR (ISO 178 standard). 1000 MPa - equilibrium moisture content 50% RH, 23 "C .. 0.9% - melting point (ASTM D789) 183-187 C o a C2 layer based on ::
To 100 parts by weight of maleic anhydride grafted polypropylene of the type
OREVAC PP-C from ELF ATOCHEM, having indicative characteristics
following: - density (ISO 1183) .. 0.89 - melting temperature (by DSC according to ISO R1218) .. 151 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) 122 C and added with EPRm.

15 parts by weight of a functional additive formed by a polyamide alloy
PA6 (60%) and polypropylene (40%) brand ORGALLOY RS 6000
(ELF ATOCHEM) and following indicative characteristics: - Melt Flow Index (235 "C, 2.16 kg) .... 4 to 9 - density ... 1.04 to 1.05 - notched Charpy impact strength
(ISO Standard 179) .... . 15-27 KJoules / m2 - flexural modulus at 23 OC
50% RH (ISO 178 standard) .. 1300-1600 MPa - equilibrium moisture content 50% RH,
230 C ... .. 1.2-1.5% - flection point (ISO R1218) .. ... . 220 C
A and 5 parts by weight of a NEOSAR dye masterbatch of the Company
Clariant.

The extrusion conditions are as follows: - extruder A - polyamide (RILSAN):
extruder diameter 45 mm
length / diameter ratio. . 22/1
extrusion temperature C. . 210/230/240/240 - extruder B - OREVAC PP-EPRm + ORGALLOY RS 6000 + NEOSAR Blend:
extruder diameter .. 45 mm
length / diameter ratio. . 24/1
extrusion temperature C. . . 180/190/210/220
The gap of the die is set at 3 mm, the calender spacing is 2.5 mm. The temperature of the die is 250 to 260 C.

The temperatures of the calendering rollers are: upper roll 70 "C
median roll .............. 45 C
lower roller ... . . . 500 C
On leaving the extruder, the C3 layer is made of cellulose (fibers) / polyester (matrix) composite (DEXTER AOD68).

A three-layer sheet of 0.8 mm thickness, comprising 0.250 mm of
RILSAN BESNO TL (Cl) and 0.5 mm of OREVAC PP C (C2) and 0.05 mm of C3 emerge with a draft speed of 5 m / min.

1.2. Decoration of the laminate obtained in 1.1. adhesion of the multilayer obtained
The decoration of the upper face of the outer layer of the laminate obtained 1.1.1 is performed by the known sublimable ink transfer printing technique. Reference is made to FR-A-2 387 793 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.

1.3. Fixing Decorated Laminate to a Substrate and Evaluation
It is carried out by hot pressing between temperatures of 130 ° C to 150 ° C for 3 to 5 Finally, an assembly 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 17.8 N / mm by delamination.
PAl 1 / PP-C.

EXAMPLE 2 2.1. Decoration of a hot Dar Dlalaee substrate 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. Tear resistance evaluation
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 3.1. Fabrication of 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 CLAVANT Company.

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 - equilibrium flexion modulus at 23 OC
50 HR (ISO 178) .. 1400 Pa - heat distortion temperature (HDT) .. 96 ° C - melting point (ASTMD789) ... 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 the conservation of the colors of the decoration of the square plates before and after assembly of the laminate on 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 at = 0.1.

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

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

3.3. Evaluation of the tear 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.

EXAMPLE 4 4.1. Realization of a trilayer according to the invention 4.1.1. The three constituent layers of the laminate in question are the following: o C1 = modified PA 11 of the RILSAN MB 3800 type from the Elfatochem Company, this PAl l
modified having the following properties: - tensile modulus (1SO 1184) .... 590 MPa - density. . 1, 029 MPa - elongation at break (ISO 1184). 18% - melting point (ASTM D789). .. 1780 C.

C2 C2 = 100 parts by weight of a polyethylene-modified polyethylene of the type
OREVAC 18302 of ELF ATOCHEM whose indicative characteristics are the
following: - density (ISO 1183) ... 0.91 - Melt Flow Index (ASTM D1238) .. 0.89 g / 10 minutes - melting point (ISO R1218) ... 117 "C - Shore A hardness ( ISO R868) 48 - modulus of elasticity in tension (ISO T527) .. 44 MPa
# 15 parts by weight of a PA6 (60%) / polyethylene (40%) alloy of the type
ORGALLOY LE 6000 by ELF ATOCHEM with
the indicative characteristics are as follows: - density (ISOR1183) ... . . 1.00-1.05 - notched Charpy impact strength
(ISO 179 standard). .. 50-60 KJoules / m2 - flexural modulus at 23 C-50% RH
(ISO 178 standard) .... 1000-1100 MPa - equilibrium moisture content 50% RH, 230 C .. 1.2-1.5%
a and 6 parts by weight of a NEOSAR masterbatch of the Company
CLAMART -> C3 layer of non-woven composite fibrous material (cellulosic fibers / matrix
polyester) brand DEXTER AO D68.

4.1.2. The extrusion is carried out under conditions identical to those of Example 1.

A trilayer is obtained consisting of the outer layer C1 of modified PAl 1 having a thickness of approximately 0.3 mm, of an intermediate layer C2 of maleated PE + alloy PA6 / PE + dye, of thickness of the order 0.250 mm.

and an inner layer C3 cellulose composite (fibr.esypolyester (matrix) of emergent thickness of the order 0.05 mm.

 4.2. Decoration of the tricouche Cf Example 1.2.

 43. Production of artides decorated by overmoulding of the laminate according to 4.1. and 4.2.

4.2 mm rectangular plates of 200 mm × 50 mm are cut into the laminate according to 4.2.

These decorated rectangular plates are then positioned in the form of a rule mold of 180 mm x "30 mm, which rule has on its outer face an embossed inscription and a recessed one .Then a polyetheresteramide is injected into the mold. trade name PEBAX 5533SN01.

PEBAX polyetheresteramide has the following characteristics: - density (ASTM D792) .... 1.01 - melt flow index (Melt Flow Index,
2350 C, 1 kg, 2 mm die) (ASTM D1238) 5 - bending modulus (ASTM D790) ... 170 MPa - hardness (ASTM D2240) ... 55 - melting point (ASTM D3418) ... 159 C
The operating conditions of the injection are as follows; - temperature 0 C ... 230/240/260 - sheet threshold 0.5 x 0.3 mm
We thus obtain rules with a decoration of high graphic quality and perfectly integrated with the sin of the rules.

4.4. Resistance to tearing of articles thus decorated
A peel test is performed as before. Values of the order of 12.9 N / mm are obtained.

An alternating bending test with an initial notch of 2 mm leads to a resistance greater than 50 000 flexions.

The modification of PAl 1 and the use of OREVAC 18302 modified PA / PE, makes it possible to obtain a more flexible film and thus to improve alternating flexural strength.

Claims (18)

CLAIMS:  1 - Laminate, in particular for decorating a substrate, characterized:  in that it comprises at least three layers, respectively exteme  C1, intermediate C2 and internal C3, with reference to the substrate to which said  laminate is intended to be associated,  and in that:  C1 comprises at least one polyamide;  C2 comprises at least one modified polyolefin,  C1 and / or C2 being optionally added with at least one  elastomer;  and C3 comprises at least one nonwoven fibrous material.  2 - Laminate according to claim 1, characterized in that the layer C1 is formed by at least one polyamide film, the latter preferably being chosen from aliphatic polyamides, alone or mixed with one another, polyamide PAl 1 and / or the PA6. 12 and / or the amorphous PA 6 being particularly preferred.  3 - laminate according to claim 1 or claim 2, characterized in that the layer C2 is formed by at least one modified polyolefin film or a modified polyolefin copolymer with an unsaturated carboxylic acid derivative.  4 - Laminate according to any one of claims 1 to 3, characterized:  in that the layer C2 comprises at least one functional additive of  polymeric nature, preferably chosen from polyamides and their  mixtures, this additive being more preferably still an alloy  at least one polyamide and at least one polyolefin;  and in that this functional additive is present in a quantity  less than 50% by weight, preferably between 1 and 40% by weight.  weight and, more preferably still, between 9 and 35%  weight, relative to the mass of the modified polyolefin + additive mixture  functional.  5 - Laminate according to claim 3 or claim 4, characterized in that the modified polyolefin of the layer C2 is obtained by polymerization of:  A - a monomer of ethylene, alpha-olefin or diolefin,  B - at least one comonomer chosen from vinyl esters of acid  saturated carboxylic acid, saturated or unsaturated mono and dicarboxylic acids, the monomer preferably being present in at least 50% by weight of the weight of the modified polyolefin.  6 - Laminate according to any one of claims 1 to 5, 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.  7 - Laminate according to any one of claims 1 to 6, characterized in that the layer C3 is formed by at least one layer of nonwoven composite fibrous material, comprising fibers embedded in a polymer matrix, said fibers being preferably , 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.  8 - Laminate according to any one of claims 1 to 7, 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 and in that the emergent portion of C3 has a thickness of at least 30 μm, preferably at least 40 μm and more preferably still between 40 and 70 μm.  9 - Laminate according to claim 8, characterized in that 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.  10 - Laminate according to any one of claims 1 to 9, characterized in that:  e C1 comprises at least one polyamide PAl 1 and / or PA 6,12 film;  and / or amorphous PA.6, Cl being preferably transparent;  C2 comprises at least one polypropylene film modified with  maleic anhydride, C2 being preferably colored,  e C1 and / or C2 possibly being supplemented with EPRm and / or  EPDM;  and C3 comprises a nonwoven film made from cellulose fibers  embedded in a polyester and / or polyolefin matrix.  11- A method of manufacturing a laminate according to any one of claims 1 to 10, characterized in that it consists, essentially:  e to produce and bond to one another the layers C1 and C2 by  (Co) extrusion,  e and to apply by hot pressing the layer C3 on the layer C2  softened, preferably out of the extrusion before solidification of  C2, so that C3 binds to C2 while entering C3 on at  least part of the thickness of C3.  12- A method of manufacturing a laminate according to any one of claims 1 to 10, characterized in that it consists essentially:  e to produce and / or implement the C1 to C3 layers in isolation,  e to assemble C2 and C3 by hot pressing, ensuring that they  interpenetrate as prescribed in claim 8,  then to join the subassembly C2 / C3 to C1 by hot pressing,  thermo-adhesion, gluing or welding.  13 - Process for manufacturing articles incorporating the laminate according to any one of claims 1 to 10, characterized in that it consists, essentially:  e to implement, as building elements 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.  14 - Process for decorating a substrate, characterized in that it consists essentially in adorning the laminate according to any one of claims 1 to 10 of a decoration and fixing the laminate thus adorned on a substrate.  15 - Method for decorating a substrate, using a laminate according to any one of claims 1 to 10, characterized in that:  firstly, the layers C2 and C3 are fixed to the substrate in the intimate connection  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.  16 - Process according to claim 14 or 15, characterized in that the decoration is performed by sublimable ink transfer printing technique.  17- Substrate comprising at least one laminate according to any one of claims 1 to 10.  18 - Use of a laminate according to any one of claims 1 to 10, in particular for the decoration and / or reinforcement and / or protection of substrates, preferably in the sublimable ink transfer printing technique.