EP2203309A2

EP2203309A2 - Method for producing a polymer laminate comprising a plasma processing activation step

Info

Publication number: EP2203309A2
Application number: EP08843874A
Authority: EP
Inventors: Bruno D'herbecourt; René-Paul EUSTACHE; Florence Sache
Original assignee: Arkema France SA
Current assignee: Arkema France SA
Priority date: 2007-10-22
Filing date: 2008-10-21
Publication date: 2010-07-07
Also published as: TWI471225B; WO2009056723A3; FR2922478B1; KR101506056B1; MX2010004354A; KR20100090271A; US20100288435A1; CN101909891B; CN101909891A; TW200936377A; WO2009056723A2; BRPI0818716A2; FR2922478A1; JP2011501710A

Abstract

The invention relates to a method for producing a laminate comprising at least two polymer layers, a layer (A) and a layer (B), which are fixed to each other by at least one aqueous-type adhesive polymer material layer (C). Said method is characterised in that: (a) it optionally consists of a step of pre-cleaning substrate layer (A) and/or substrate layer (B), by oxidising or reducing continuous atmospheric cold plasma processing pre-cleaning; (b) the plasma is either (i) oxidising or reducing when the layer is a polymer layer having a shore D of strictly between 35 and 60 or when the layer is a polymer layer having a shore D > or = 60 and the distance between the plasma source and the surface of the layer to be activated is < or = 3 cm, and (ii) the plasma is reducing when the layer is a polymer layer having a shore D > or = 60 and the distance between the plasma source and the surface of the layer to be activated is > 3 cm, substrate layers (A) and (B) being identical or different and formed by non-exudant polymers.

Description

PROCESS FOR PRODUCING POLYMERIC LAMINATE COMPRISING AN ACTIVATION STEP BY PLASMA TREATMENT

The present invention generally relates to a laminated product and in particular to the elements of a shoe, in particular a shoe sole, comprising at least two substrate layers, a substrate layer (A) and a layer substrate (B), said substrate layers being bonded to one another. The substrate layer (A) and / or the substrate layer (B) comprises at least one polymer, additive with at least one filler or non-additive, that does not exudate and chosen from (i) the polyamides (abbreviated PA) homo or copolymer, (ii) thermoplastic elastomers (abbreviated as TPE), chosen from PEBAs or copolymers with polyamide blocks and polyether blocks, TPUs or thermoplastic polyurethane polymers, COPEs or polyether block copolymers and polyester blocks and (iii) their mixtures . The polymers used to make the substrate layers (A) and (B) may be the same or different.

The substrate layers (A) and (B) are adhered to each other by means of at least one layer of an aqueous type adhesive material, that is either an adhesive material with a low content of organic solvent (<10% by weight of solvent based on the weight of the adhesive material) is free of organic solvent.

The present invention also relates to a method of manufacturing such a laminate and its use in the footwear industry, in particular for the manufacture of components of shoes for example soles and especially footwear soles.

During the last decade, materials based on PEBA copolymers, such as the materials marketed by Arkema under the Pebax® brand, have gradually become established in the field of high-end shoes, particularly sports shoes, thanks to their properties. mechanical and in particular their exceptional elastic return property. In general, the bonding of this type of substrate makes these materials PEBA, to make a laminate, requires the following operations:

cleaning the surfaces of the substrates to be bonded with an organic solvent such as methyl ethyl ketone (MEK),

- The application, generally with a brush, on at least the substrate of the substrate substrate surface of a primer composition.

drying in an oven of the primer layer;

- The application, usually with a brush, on the primer layer and also on the mating surface of the other substrate of a two-component polyurethane adhesive layer;

drying in an oven layers of glue;

- The docking of the two bonded substrates; and

- Pressing the assembly resulting from docking.

Generally, the primer compositions used are of two-component type and comprise: a first component which is a functionalized resin in solution in an organic solvent; and a second component which is an isocyanate or a mixture of isocyanates also in solution in an organic solvent and which has a crosslinking function. This component is also called "Hardener". It is added to the first component just before use. The two-component adhesives also comprise a first component which is an organic resin functionalized in dispersion or in solution in an organic solvent and / or in water and a second component also called "Hardener", which has a crosslinking function, and which is either at least one isocyanate or a solution of at least one isocyanate in a solvent.

During drying, both the primer compositions and the adhesives of the prior art lead to evaporation of a large amount of organic solvent. Thus, in the case of the manufacture of a shoe laminate, it is estimated that the average amount of glue used for a shoe is 5 g and that of the primary composition of 3 g, and it is possible to evaluate the solvent emission at 2.9g per shoe. Assuming a production of 10,000 shoes per day for a production unit, the total amount of solvent emitted by this unit is 29 kg per day.

On the other hand, the bonding quality of the systems of the prior art (expressed by the peel strength of the substrates) is far from optimal. Thus, if peel strengths of the order of 6 to 6.5 daN / cm are obtained with substrates of low hardness (shore D <35) to medium (35 <shore D <60), it is not necessary to achieves more than a peel force of about 3 daN / cm with high hardness substrates (shore D> 60). Pebax® 55-1 is therefore considered a substrate of medium hardness and Pebax® 70-1 is considered a substrate of high hardness. However, shoe manufacturers impose a peel strength of at least 3 daN / cm. It can thus be seen that bonding with the systems of the prior art is not sufficient in the case of the hardest polymers (shore D> 60). In addition, certain polymer grades tend to "exude" that is to say they generate on the surface of finished parts, a whitish deposit more or less important depending on the grade. This deposit may correspond to the presence of additives, impurities or oligomers, present in the polymer, which "go up" to the surface of the parts over time. This deposit is troublesome in the context of the bonding of elements between them and hampers the smooth running of said bonding.

The present invention therefore aims to provide a method of manufacturing a laminate as described above overcoming the disadvantages of the prior art. This method has the advantage, moreover, of being able to be continuous on a production line and to treat parts of shoe components of complex geometry with a 3-dimensional action.

We have now found a solution to these technical problems.

More particularly, it has now been possible to produce a laminate product comprising at least two layers of substrates: a layer of substrate (A) and a substrate layer (B) adhering to each other by means of at least one layer of an aqueous type adhesive polymer material with a peel force compatible with the use of such product laminated in components of shoes, said substrate layers being wholly or partly made of polymer of medium or high hardness (see definition above).

The nature of the substrate layers, the adhesive polymeric material and the method of manufacturing the laminate product will be described below in more detail.

With regard to the aqueous-type adhesive polymer material, also called aqueous adhesive (C) thereafter:

The adhesive polymeric material is a crosslinkable hot melt material. It is manufactured by the reaction of at least one functionalized prepolymer and at least one hardener comprising free isocyanate functions (-N = C = O) or blocked. In the latter case, the reaction will be done after unblocking said functions, just before use of the adhesive material. This is a two-component or one-component adhesive material as is known to those skilled in the art.

In general, the content of the hardener with free or blocked isocyanate functions represents 0.5 to 25% by weight, preferably 2 to 10% by weight relative to the total weight of the functionalized prepolymer.

In particular, the functionalized prepolymers of the crosslinkable hot melt materials that are suitable for the present invention are chosen from hydroxylated polyesters, hydroxylated polyethers and their mixtures.

The adhesive polymer material may also comprise one or more adjuvants in usual proportions, such as, for example: Stabilizers such as benzoyl chloride, phosphoric acid, acetic acid, p-toluenesulphonyl isocyanate,

• charges,

Concerning the aqueous primary:

The aqueous primer composition is chosen from those described above for aqueous adhesives. However, it is made more fluid by formulations known to those skilled in the art, for a better application to the substrate during its use. The aqueous primers may also be two-component compositions, the first component being a dispersion of a hydroxylated organic resin in water and the second component being at least one polyisocyanate in an organic solvent.

It is also possible to use single-component aqueous primers, in particular systems based on blocked isocyanates which are made reactive by a temperature increase.

Regarding the Substrates:

The substrate layer (A) and / or (B) comprises at least one polymer. As a polymer, mention may be made of PAs, homo or copolymers, and thermoplastic elastomers, in particular block copolymers. By way of example of a block copolymer, mention may be made of block copolymers of polyesters and polyether blocks (abbreviated COPE and also known as copolyetheresters), polyurethane block copolymers and polyether blocks or polyester blocks (also known as TPU abbreviations for thermoplastic polyurethanes). and copolymers having polyamide blocks and polyether blocks (also known as polyether block amide PEBA abbreviated as I ¹ IUPAC).

By "thermoplastic elastomer polymer (TPE)" is meant a block copolymer having, alternately, so-called hard or rigid blocks or segments and so-called flexible or flexible blocks or segments. By way of example of hard block and flexible block copolymer, there may be mentioned respectively (a) block copolymers polyesters and polyether blocks (also called COPE or copolyetheresters), (b) polyurethane block copolymers and polyether blocks or polyesters (also known as TPUs, abbreviation for thermoplastic polyurethanes) and (c) copolymers comprising polyamide blocks and polyether blocks (also called PEBA according to IUPAC I ^1).

With regard to COPE or copolyetheresters, they are polyether block copolymers and polyether blocks. They consist of flexible polyether blocks derived from polyether diols and rigid polyester blocks which result from the reaction of at least one dicarboxylic acid with at least one short chain-extending diol unit. The polyester blocks and the polyether blocks are linked by ester bonds resulting from the reaction of the acid functions of the dicarboxylic acid with the OH functions of the polyetherdiol. The linking of polyethers and diacids forms the soft blocks whereas the linking of the glycol or butanediol with the diacids forms the rigid blocks of the copolyetherester. The short chain extending diol may be selected from the group consisting of neopentyl glycol, cyclohexanedimethanol and aliphatic glycols of the formula HO (CH 2) n OH where n is an integer of 2 to 10.

Advantageously, the diacids are aromatic dicarboxylic acids having from 8 to 14 carbon atoms. Up to 50 mol% of the aromatic dicarboxylic acid may be replaced by at least one other aromatic dicarboxylic acid having 8 to 14 carbon atoms, and / or up to 20 mol% may be replaced by an aliphatic acid dicarboxylic acid having 2 to 14 carbon atoms.

Examples of aromatic dicarboxylic acids that may be mentioned include terephthalic acid, isophthalic acid, bibenzoic acid, naphthalene dicarboxylic acid, 4,4'-diphenylenedicarboxylic acid, bis (p-carboxyphenyl) methane acid, ethylene bis p-benzoic acid, 1-4 tetramethylene bis (p-oxybenzoic acid), ethylene bis (p-oxybenzoic acid), 1, 3-trimethylene bis (p-oxybenzoic) acid. By way of example of glycols, mention may be made of ethylene glycol, 1,3-trimethylene glycol, 1,4-tetramethylene glycol, 1,6-hexamethylene glycol, 1,3-propylene glycol, 1, 8 octamethylene glycol, 1,10-decamethylene glycol and 1,4-cyclohexylene dimethanol. The polyblock and polyether block copolymers are, for example, copolymers having polyether units derived from polyetherdiols such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene glycol (PO3G) or polytetramethylene glycol (PTMG). ), dicarboxylic acid units such as terephthalic acid and glycol (ethane diol) or butane diol, 1 - 4 units. Such copolyetheresters are described in patents EP 402 883 and EP 405 227. These polyetheresters are thermoplastic elastomers. . They may contain plasticizers.

Working on TPUs. mention may be made of polyetherurethanes which result from the condensation of flexible polyether blocks which are polyetherdiols and rigid polyurethane blocks resulting from the reaction of at least one diisocyanate which may be chosen from aromatic diisocyanates (eg MDI, TDI) and diisocyanates aliphatic (eg HDI or hexamethylenediisocyanate) with at least one short diol. The short chain extending diol may be chosen from the glycols mentioned above in the description of the copolyetheresters. The polyurethane blocks and the polyether blocks are connected by bonds resulting from the reaction of the isocyanate functional groups with the OH functions of the polyetherdiol.

Mention may also be made of polyesterurethanes which result from the condensation of flexible polyester blocks which are polyesterdiols and rigid polyurethane blocks resulting from the reaction of at least one diisocyanate with at least one short diol. The polyesterdiols result from the condensation of dicarboxylic acids advantageously chosen from aliphatic dicarboxylic acids having from 2 to 14 carbon atoms and glycols which are short chain-extending diols chosen from the glycols mentioned above in the description of the copolyetheresters. They may contain plasticizers. As regards PEBAs, they result from the polycondensation of polyamide blocks with reactive ends with polyether blocks with reactive ends, such as, inter alia: 1) polyamide blocks with diamine chain ends with polyoxyalkylene blocks with dicarboxylic chain ends.

2) polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends, obtained by cyanoethylation and hydrogenation of polyoxyalkylene aliphatic alpha-omega dihydroxylated blocks called polyether diols

3) Polyamide blocks with dicarboxylic chain ends with polyetherdiols, the products obtained being, in this particular case, polyetheresteramides.

The polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.

The polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine. The molar mass in number Mn of the polyamide blocks is between 400 and 20000 g / mol and preferably between

500 and 10000 g / mole.

Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units. Three types of polyamide blocks can advantageously be used.

According to a first type, the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and an aliphatic or aromatic diamine, in particular those having from 2 to 20 carbon atoms, preferably those having from 6 to 14 carbon atoms. Examples of dicarboxylic acids that may be mentioned include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .

Examples of diamines that may be mentioned include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, the isomers of bis (4-aminocyclohexyl) methane (BACM), bis - (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4-aminocyclohexyl) -propane (BMACP), and para-amino-di-cyclohexyl-methane ( PACM), and isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) and piperazine (Pip).

Advantageously, PA4.12, PA4.14, PA4.18, PA6.10, PA6.12, PA6.14, PA6.18, PA9.12, PA10.10, PA10.12, and PA10.14 blocks are used. PA10.18.

According to a second type, the polyamide blocks result from the condensation of one or more alpha omega-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine.

Examples of lactams include caprolactam, oenantholactam and lauryllactam.

As examples of alpha omega amino carboxylic acid, mention may be made of aminocaproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.

Advantageously, the polyamide blocks of the second type are made of polyamide 11, polyamide 12 or polyamide 6.

According to a third type, the polyamide blocks result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid. In this case, the polyamide PA blocks are prepared by polycondensation: linear or aromatic aliphatic diamine (s) having X carbon atoms;

- Dicarboxylic acid (s) having Y carbon atoms; and

comonomer (s) {Z} chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X 1 carbon atoms and at least one dicarboxylic acid having Y 1 carbon atoms, (X1, Y1) being different from (X, Y),

said one or more comonomers {Z} being introduced in a proportion by weight of up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all the polyamide precursor monomers;

in the presence of a chain limiter chosen from dicarboxylic acids; Advantageously, the dicarboxylic acid having Y carbon atoms, which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.

According to a variant of this third type, the polyamide blocks result from the condensation of at least two alpha omega aminocarboxylic acids or at least two lactams having from 6 to 12 carbon atoms or a lactam and an aminocarboxylic acid. not having the same number of carbon atoms in the possible presence of a chain limiter. As an example of aliphatic alpha omega amino carboxylic acid, mention may be made of the amino-caproic acid, amino-7-heptanoic acid, amino-11-undecanoic acid and amino-12-dodecanoic acid.

By way of example of lactam, mention may be made of caprolactam, oenantholactam and lauryllactam. As examples of aliphatic diamines, there may be mentioned hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine. By way of example of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid.

By way of example of aliphatic diacids, mention may be made of butanedioic acid, adipic acid, azelaic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid or dimerized fatty acid (these dimerized fatty acids preferably have a dimer content of at least 98% preferably they are hydrogenated, they are marketed under the trademark "PRIPOL" by the company "UNICHEMA", or under the brand name EMPOL by the company HENKEL) and the polyoxyalkylenes - α, ω diacids. As examples of aromatic diacids, mention may be made of terephthalic (T) and isophthalic (I) acids.

By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM) and 2-2-bis - (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM). Other diamines commonly used may be isophoronediamine (IPDA), 2,6-bis (aminomethyl) -norbornane (BAMN) and piperazine.

As examples of polyamide blocks of the third type, the following can be cited:

6.6 / 6 in which 6J3 denotes hexamethylenediamine units condensed with adipic acid. 6 denotes patterns resulting from the condensation of caprolactam. 6.6 / Pip.10 / 12 wherein 6J5 denotes hexamethylenediamine units condensed with adipic acid. Pip.10 denotes units resulting from the condensation of piperazine and sebacic acid.

VZ denotes patterns resulting from the condensation of lauryllactam.

The proportions by weight are respectively 25 to 35/20 to 30/20 to 30 / the total being 80 and advantageously 30 to 35/22 to 27/22 to 27 / the total being

80. For example, the proportions 32/24/24 / lead to a melting temperature of 122 to 137 ° C. • 6.6 / 6.10 / 1 1/12 in which 6J3 denotes hexamethylenediamine condensed with adipic acid. 6.10 denotes hexamethylenediamine condensed with sebacic acid. IJ. means units resulting from the condensation of aminoundecanoic acid. _12_ denotes patterns resulting from the condensation of lauryllactam.

The proportions by weight are 10 to 20/15 to 25/10 to 20/15 to 25, respectively, the total being 70 and preferably 12 to 16/18 to 25/12 to 16/18 to the total being 70.

For example the proportions 14/21/14/21 / lead to a melting temperature of 119 to 131 ° C.

The polyether blocks can represent 5 to 85% by weight of the polyamide and polyether block copolymer. The mass Mn of the polyether blocks is between 100 and 6000 g / mol and preferably between 200 and 3000 g / mol.

The polyether blocks consist of alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glycol linkages). PEG blocks (polyethylene glycol), that is to say those consisting of ethylene oxide units, PPG blocks (propylene glycol), ie those consisting of propylene oxide units, PO3G blocks (polytrimethylene glycol) are thus used. ) that is to say those consisting of glycol polytrimethylene ether units (such copolymers with polytrimethylene ether blocks are described in US Patent 6590065), and PTMG blocks ie those consisting of tetramethylene glycols units also called polytetrahydrofuran . It is advantageous to use PEG blocks or blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A. These latter products are described in patent EP 613 919. The polyether blocks may also consist of ethoxylated primary amines. These blocks are advantageously also used. By way of example of ethoxylated primary amines, mention may be made of the products of formula: H (OCH ₂ CH ₂ ) _m - N (CH ₂ CH ₂ O) _n - H

(CH ₂₎ _X

CH ₃ in which m and n are between 1 and 20 and x between 8 and 18. These products are commercially available under the NORAMOX® brand from CECA and under the GENAMI N® brand from CLARIANT. The ether units (A2) are, for example, derived from at least one polyalkylene ether polyol, in particular a polyalkylene ether diol, preferably chosen from polyethylene glycol (PEG), polypropylene glycol (PPG) and polytrimethylene glycol (PO3G ) polytetramethylene glycol (PTMG) and mixtures or copolymers thereof.

The flexible polyether blocks may comprise polyoxyalkylene blocks with NH ₂ chain ends, such blocks being obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy blocks known as polyether diols. More particularly, Jeffamines (e.g., Jeffamine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, see JP 2004346274, JP 2004352794 and EP1482011).

The polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends. They can also be mixed with polyamide precursors and a diacid chain limiter to make the polyamide block and polyether block polymers having statistically distributed patterns.

These polymers can be prepared by the simultaneous reaction of the polyether blocks and the precursors of the polyamide blocks. Preferably, the polycondensation is carried out at a temperature of 180 to 300 ^° C. For example, polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain.

It is also possible to react polyetherdiamine, polyamide precursors and a chain-limiting diacid. A polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain.

However, they can also be advantageously prepared by the condensation reaction of the polyether blocks with the polyamide blocks.

The catalyst is defined as any product which facilitates the bonding of polyamide blocks and polyether blocks by esterification or amidification. The esterification catalyst is advantageously a derivative of a metal selected from the group consisting of titanium, zirconium and hafnium or a strong acid such as phosphoric acid or boric acid. Examples of catalysts are those described in US Pat. Nos. 4,331,786, 4,115,415, 4,195,155, 4,839,441, 4,884,014, 4,230,838 and 4,332,920.

The general two-step preparation method of the PEBA copolymers having ester bonds between the PA blocks and the PE blocks is known and is described, for example, in the French patent FR 2,846,332. The general method for preparing the PEBA copolymers of the invention having amide bonds between PA blocks and PE blocks is known and described, for example in European Patent EP 1 482 011.

The formation reaction of the PA block is usually between 180 and 300 ^° C., preferably between 200 and 290 ^° C., the pressure in the reactor is between 5 and 30 bar and is maintained for about 2 to 3 hours. The pressure is slowly reduced by putting the reactor at atmospheric pressure, then the excess water is distilled for example for one hour or two. The carboxylic acid terminated polyamide having been prepared, the polyether and a catalyst are then added. The polyether can be added in one or more times, as can the catalyst. According to an advantageous form, the polyether is first added, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with the formation of ester bonds and elimination of water. As much water as possible is removed from the reaction medium by distillation, and then the catalyst is introduced to complete the bonding of the polyamide blocks and the polyether blocks. This second step is carried out with stirring, preferably under a vacuum of at least 6 mmHg (800 Pa) at a temperature such that the reagents and copolymers obtained are in the molten state. By way of example, this temperature can be between 100 and 400 ^° C. and most often 200 and 300 ^° C. The reaction is followed by measuring the torsion torque exerted by the molten polymer on the stirrer or by the measuring the electrical power consumed by the agitator. The end of the reaction is determined by the value of the target torque or power.

It is also possible to add during the synthesis, at the moment deemed most appropriate, one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245. As regards the preparation of polyamide block copolymers and polyether blocks, they can be prepared by any means for hanging polyamide blocks and polyether blocks. In practice, essentially two methods are used, one said in two steps, the other in one step.

In the two-step process, the polyamide blocks are first produced and then in a second step the polyamide blocks and the polyether blocks are bonded. In the one-step process, the polyamide precursors, the chain limiter and the polyether are mixed; a polymer having essentially polyether blocks, polyamide blocks of very variable length, but also the various reagents reacted in a random manner which are distributed randomly (statistically) along the polymer chain. Whether in one or two steps it is advantageous to operate in the presence of a catalyst. We can use the catalysts described in patents US 4,331,786, US 4,157,475, US 4,195,015, US 4,839,441, US 4,864,014, US 4,230,838 and US 4,332,920, WO 04 037898, EP 1262527, EP 1270211, EP 1136512, EP 1046675, EP 1057870, EP 1 155065, EP 506495 and EP 504058. In the one-step process, polyamide blocks are also produced, which is why it was written at the beginning of this paragraph that these copolymers could be prepared by any means of hanging polyamide blocks (PA block) and polyether blocks (PE block).

Advantageously, the PEBA copolymers have PA blocks in PA 6, PA 11, PA 12, PA 6.12, PA 6.6 / 6, PA 10.10 and PA 6.14 and PE blocks in PTMG, PPG, PO3G and in PEG.

The polyamides involved are homopolyamides or copolyamides. According to a first type, the polyamides come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.

Examples of dicarboxylic acids that may be mentioned include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .

Examples of diamines that may be mentioned include tetramethylenediamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, the isomers of bis (4-aminocyclohexyl) methane (BACM), bis - (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM), and isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (BAMN) and piperazine (Pip).

Advantageously, there are PA 4.12, PA 4.14, PA 4.18, PA 6.10, PA

6.12, PA 6.14, PA 6.18, PA 9.12, PA 10.10, PA 10.12, PA 10.14 and PA 10.18. According to a second type, the polyamides result from the condensation of one or more alpha omega-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine. Examples of lactams include caprolactam, oenantholactam and lauryllactam.

As examples of alpha omega amino carboxylic acid, there may be mentioned aminocaproic acid, amino-7-heptanoic acid, amino-11-undecaπoic acid and amino-12-dodecanoic acid. Advantageously, the polyamides of the second type are made of polyamide 11, polyamide 12 or polyamide 6. According to a third type, the polyamides result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid. In this case, in a first step, the polyamide PA blocks are prepared by polycondensation:

of the linear or aromatic aliphatic diamine or diamines having

X carbon atoms;

- Dicarboxylic acid (s) having Y carbon atoms; and - comonomer (s) {Z} chosen from lactams and alpha-omega aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X 1 carbon atoms and at least one dicarboxylic acid having Y1 carbon atoms, (X1, Y1) being different from (X, Y), - said one or more comonomers {Z} being introduced in a proportion by weight of up to 50%, preferably up to 20%, still more preferably up to 10% with respect to all of the polyamide precursor monomers;

By way of example of aliphatic alpha omega amino carboxylic acid, mention may be made of aminocaproic, amino-7-heptanoic, amino-1-undecanoic and amino-12-dodecanoic acids.

By way of example of lactam, mention may be made of caprolactam, oenantholactam and lauryllactam.

As examples of aliphatic diamines, there may be mentioned hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.

By way of example of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid.

As examples of polyamides of the third type, mention may be made of the following: PA6.6 / 6 wherein 6J3 denotes hexamethylenediamine units condensed with adipic acid. 6 denotes patterns resulting from the condensation of caprolactam.

PA6.6 / Pip.10 / 12 wherein 6J5 denotes hexamethylenediamine units condensed with adipic acid. Pip. 10 denotes units resulting from the condensation of piperazine and sebacic acid. 12 denotes patterns resulting from the condensation of lauryllactam. The proportions by weight are respectively 25 to 35/20 to 30/20 to 30 / the total being 80 and advantageously 30 to 35/22 to 27/22 to 27 / the total being 80. For example, the proportions 32/24 / 24 / lead to a melting temperature of 122 to 137 ° C.

PA6.6 / 6.10 / 11/12 wherein 6J3 denotes hexamethylenediamine condensed with adipic acid. 6.10 denotes hexamethylenediamine condensed with sebacic acid. IJ- denotes patterns resulting from the condensation of aminoundecanoic acid. .12_ denotes patterns resulting from the condensation of lauryllactam. The proportions by weight are 10 to 20/15 to 25/10 to 20/15 respectively, the total being 70 and preferably 12 to 16/18 to 25/12 to 16/18 to the total being 70. For example, proportions 14/21/14/21 / lead to a melting point of 1 19 to 131 ^° C.

Substrates (A) and (B) can be:

(a) identical, that is to say that the two substrates (A) and (B) consist of the same polymer (s) chosen from (i) the polyamides (abbreviated to PA) homo or copolymer, (ii) the thermoplastic elastomers (abbreviated as TPE), chosen from PEBAs or copolymers with polyamide blocks and polyether blocks, TPUs or thermoplastic polyurethane polymers, COPEs or block copolymers with polyethers and polyester blocks and (iii) their mixtures, or

- (b) different but of the same kind, that is to say that the substrates (A) and (B) are both block copolymers with blocks flexible polyether but with different hard blocks (eg the substrate (A) is made of PEBA and the substrate (B) is made of TPU, the substrate (A) is made of PEBA and the substrate (B) is made of COPE; (A) is TPU and substrate (B) is COPE), or alternatively - (c) different and of a different nature, that is to say, they do not fall into category (a) or in category (b), (eg: the substrate (A) is PEBA and the substrate (B) is leather, the substrate (A) is TPU and the substrate (B) is leather). In the latter case, when the substrate (A) is selected from PA and TPE as defined above, the substrate (B) is selected from the substrates (D). Mention may be made, as substrate (D), of homo or copolymer polymers such as polyolefins, polyamines, polyesters, polyethers, polyimides, polycarbonates, phenolic resins, crosslinked or uncrosslinked polyurethanes, in particular foams, poly (ethylene / vinyl acetate), natural or synthetic elastomers such as polybutadienes, polyisoprenes, styrene-butadiene-styrene (SBS), styrene-butadiene-acrylonitrile (SBN), polyacrylonitriles and also natural or synthetic fabrics. synthetic materials, such as fabrics made of polypropylene fibers, polyethylene fibers, polyesters, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyaramid, fiberglass and carbon fiber fabrics, and materials such as leather, paper and cardboard. - (d) different, one being PA, while the other being TPE.

All these materials can also be in the form of foam, where possible.

Concerning laminates: The following possibilities can be had in which, Primary (a) denotes an aqueous type primer, Primary (s) denotes an organic solvent type primer. The nature of the glue (E) depends on the nature of the substrate (B). It will be of aqueous type in the case where the substrate (B) is PA or TPE and may be of solvent type or aqueous type, preferably of the aqueous type in other cases.

Substrate (A) / Primal (a) / aqueous adhesive (C) / adhesive (E) / Primer (s) / substrate (B),

Substrate (A) / Primer (a) / aqueous adhesive (C) / adhesive (E) / Primer (a) Zsubstrate (B), • substrate (A) / Primer (a) / aqueous adhesive (C) / adhesive ( E) Zsubstrate (B),

• substrate (A) / aqueous adhesive (C) Z glue (E) / Primer (s) / substrate (B),

Substrate (A) / aqueous adhesive (C) / glue (E) / Primer (a) Zsubstrate (B),

• substrate (A) / aqueous adhesive (C) Z adhesive (E) / substrate (B)

The following possibilities may be of particular interest and are not limiting: homopolymer or copolyether / aqueous amine (C) / aqueous adhesive (C) / amine (a) / homopolymer or homopolymer or copolymer / primary copolymer (a) ) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPE o TPE / Primer (a) / aqueous adhesive (C) / aqueous adhesive (CyPrimaire (a) / TPE or PA homo or copolymer / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / primer

(a) / polymer (D) o TPE / aqueous adhesive (C) / aqueous adhesive (C) / polymer (D) o PA homo or copolymer / aqueous adhesive (C) / aqueous adhesive (C) / PA homo or copolymer o PA homo or copolymer / aqueous adhesive (C) / aqueous adhesive (C) ZTPE o TPE / aqueous adhesive (C) / aqueous adhesive (C) / TPE o PA homo or copolymer / aqueous adhesive (C) / aqueous adhesive (C) / polymer (D) o TPE / aqueous adhesive (C) / aqueous adhesive (C) / polymer (D)

Examples which may be mentioned are: PEBA / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPU or PEBA / Primer (a) / aqueous adhesive (C) / adhesive (E) ) / leather o PEBA / Primary (a) / aqueous glue (C) / glue (E) / polyurethane foam o PEBA / Primary (a) / water-based glue (C) / glue (E) / rubber o PEBA / Primary ( a) / aqueous adhesive (C) / glue (E) / non-woven polyolefin PA / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPU o PA / Primer (a) / aqueous adhesive (C) / adhesive (E) / leather o PA / Primer (a) / aqueous adhesive (C) / adhesive (E) / polyurethane foam o PA / Primer (a) / aqueous adhesive (C) / adhesive (E) / rubber o PA / Primer (a) / aqueous adhesive (C) ) / glue (E) / non-woven polyolefin o TPU / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPU o TPU / Primer (a) / aqueous adhesive (C) / glue (E) / leather o TPU / Primer (a) / water-based glue (C) / glue (E) / polyurethane foam o TPU / Primer (a) / water-based glue (C) / glue (E) / rubber o TPU / Primer (a) / water-based adhesive (C) / glue (E) / non-woven polyolefin

The substrate layers generally have a thickness of 0.4 to 5 mm.

With regard to exudation The detection of an exudate which is not always easy to observe visually, its quantification and possibly its identification can be carried out by infrared spectroscopy by means of the technique of surface analysis known as ATR mono-reflection.

The presence of an exudate is defined on the surface of a piece of polymer (plate, shoe sole element, ...) when, after being placed in close contact with the surface of the Germanium crystal of the accessory ATR mono-reflection and removed from the crystal, the piece leaves on the latter a deposit which can be obtained infra-red spectrum. Strictly speaking, there is exudation when an infra-red spectrum is obtained whose peak intensity is greater than twice the background noise, which corresponds to the detection limit of the infra-red spectrometer. The Germanium ATR crystal allows the analysis of deposits of very small thickness (fraction of micron) and the quantity more or less important of exudate can be estimated from the intensity of the lines expressed in Optical Density (OD) of the spectrum infra-red after subtracting a blank spectrum. The higher the spectral bands compared to the background noise, the more exudate is important. A grade of exuding polymer is defined here when, following the method described below, a deposit is obtained on the ATR crystal whose infra-red signal has lines of intensity greater than 0.005 optical density.

About the laminate manufacturing method> The laminate manufacturing method, according to the present invention, comprises the following steps:

(a) Optionally a pre-cleaning step of the substrate layer (A) and / or the substrate layer (B), in the form of a pre-cleaning by continuous atmospheric cold plasma treatment, oxidizing or reducing, (b) ) An activation step by continuous atmospheric cold plasma treatment of the substrate layer (A) and / or the substrate layer (B), said plasma being either

(i) oxidizing or reducing agent, in the case where said layer is made of polymer having a shore D strictly between 35 and 60 or in the case where said layer is made of polymer having a shore D> or = 60 and a distance between the plasma source and the surface of the layer to be activated <or = 3 cm,

(ii) reducing agent in the case where said layer is made of polymer having a Shore D> or = 60 and a distance between the plasma source and the surface of said layer to be activated> 3 cm,

(c) optionally a step of sizing the substrate layer (A) and / or the substrate layer (B) using an aqueous primer,

(d) a step of sizing said substrate layer (A) and / or said substrate layer (B) with an aqueous adhesive (C),

(e) A step of docking the substrate layers (A) and (B) so as to form a laminate.

(f) pressurizing the assembly obtained in (e), in a humid atmosphere; and (g) after removal of the press, recovering the laminate product. The pressure applied during the compressing stage is from 1 to 15 kg / cm ^2, preferably 3 to 10 kg / cm ² and the temperature is 20 ° C to 150 ° C. The presses used in the process of the invention are the conventional presses in the field of laminate manufacture. The humid atmosphere is preferably air at a relative humidity RH> 5%, preferably RH> 10% and better RH> 20%.

> Cold plasma treatment

A plasma is an electrically neutral gas whose species, atoms or molecules, are excited and / or ionized. A cold plasma is an ionized gas, in a state of thermodynamic non-equilibrium, of which only the electrons are carried at high temperature the other particles (ions, radicals, fragments of molecules, neutral neutrals) remaining at ambient temperature. Unlike thermal plasmas used in hot projection, cold plasmas are media that allow surface modifications (deposits, grafting, etching, etc.) at low temperature, without altering the substrates. The plasma is generated in a confined chamber, under a partial vacuum or at atmospheric pressure, into which a piasmagene gas is injected. One can generate a plasma in transferring energy to this gas by the action ^of an electric discharge. A discharge, that is a rapid conversion of electrical energy into kinetic energy, and energy ^excitation and ^ionization of atoms and molecules. The electrical energy supplied to the system is partly converted by the charged particles thus formed (electrons, ions) into kinetic energy. Because of their low mass, the free electrons generally recover ^the bulk of this energy and cause, by collisions with heavy particles of gas, their excitement or dissociation and therefore the maintenance of ^the ionization

Plasma treatment is mostly used to improve the wettability

(surface energy), the adhesion characteristics (inks, adhesives, etc.) and even anti-adhesion, the biocompatibility of the polymer surface. It is also used as a means of cleaning and cross-linking the surface layers of the polymer. The bombardment of the surface of the polymers by the energetic species created within the plasma leads to the rupture of the covalent bonds (cleavage of the macromolecular chains) and to the formation of free radicals. The latter react with the active species of plasma from which the surface of the materials results in the formation of functional chemical groups depending on the nature of the gas phase. This is called activation or surface functionalization.

1, Oxidative Plasmas

The oxidizing plasmas (C> ₂ , CO _2, H ₂ O ...) give rise to the formation of oxygenated functional groups (hydroxyl, carbonyl, carboxyl, peroxide, hydroperoxide, carbonate ...). Functionalization of the surfaces with hydrophilic groups of this type makes it possible to increase their softness and, in principle, their adhesion ability.

2, Reducing Plasmas In the same way, the reducing plasmas (N ₂ , N ₂ H ₂ , NH 3, etc.) give rise to the formation of hydrophilic groups, in particular amino groups (-NH, -Nhb, the case of plasmas NH3) or even arnide groups (-N-C = O). It should be noted that oxygenated groups are always present on the surface of the polymer materials treated in a nitrogenous plasma. Indeed, the free radicals created on the surface of these materials react with the residual oxygen species present in the reactor during the plasma treatment. Similarly, the free radicals still present on the surface of the materials after the treatment react with the oxygen in the atmosphere after the return of the treated samples. Obviously, plasma treatments in NO or NO2 atmosphere also give rise to the formation of both nitrogenous and oxygenated groups,

3, pre-cleaning plasma surfaces

Oxidizing and reducing plasmas and in particular O ₂ piasmas are commonly used to remove traces of organic contaminants on the surface of polymeric substrates as well as fragments of the polymer. (oϋgomers) weakly bound present on the surface of these same substrates. We speak of pre-cleaning plasma, it is a plasma treatment as described previously. ^The plasma oxidation leads to the dissociation of these species and the desorption of volatile compounds (CO, CO2, H2O ...) which are eliminated by your reactor pumping systems.

The examples below illustrate the present invention without limiting its scope. In the examples, unless otherwise indicated, all percentages and parts are by weight.

Pebax 55 and Pebax 70 used refer to polyamide blocks and polyether block copolymers whose characteristics are given in Table I below. These are PEBAs consisting of alternating blocks of PA 12 and PTMG.

TABLE I

Methodology for measuring exudate on the surface of a polymer:

1) Equipment: IRTF device equipped with a single-reflector ATR accessory with Germanium crystal: Nicolet 460 ESP spectrophotometer (thermo Fisher) equipped with the Thunderdome accessory (Spectra-Tech) with Germanium crystal.

Germanium allows the analysis of a depth of about one micron. It is therefore suitable for the analysis of very weak deposits.

2) Operating mode:

Place the surface of the sample to be analyzed against the Germanium crystal. Perform 5 successive presses using the anvil, each time moving the sample a few mm. Remove the sample and perform the spectrum of the deposit.

Spectral conditions:

- experience: Thunderdome

- number of acquisitions: 64 - resolution: 4 cm-1

- correction: ATR

- zero filling: 2 levels

The blank spectrum is carried out with the clean crystal The deposition or exudate spectra were measured on non-exuding, weakly exuding and exuding polymer (see FIG. 1).

Exemplary (Ex) and Comparative Examples (Cp)

PEBAX 55 and 70 described above may be of more than different types as defined below. We have : > type 1: PEBAX 70-1 and PEBAX 55-1 do not contain stabilizing additives,

> type 2: PEBAX 70-2 and PEBAX 55-2 contain a formulation of stabilizing additives that do not exude in bar surfaces,> type 3: PEBAX 70-3 and PEBAX 55-3 contain a formulation of stabilizing additives exuding on the surface of the bars.

Laminates were made as follows:

Optionally, an N2 / O2 plasma pre-cleaning is carried out in the case of Example 24 or a chemical pre-cleaning with MEK in the case of Comparative 22 or a pre-cleaning with soapy water in the case of Comparative 23;

Activation of the substrate (A) by atmospheric plasma treatment indicated in the following Table II; a coat of aqueous primer (Dongsung W104®) is applied with a brush to the surface of the substrate (A) intended to be joined together and dried in a ventilated oven (5 minutes at 70 ^° C.),

an aqueous adhesive (Dongsung W-01®) is applied to the surface of the substrate (A), previously covered with aqueous primer and dried in a ventilated oven (5 minutes at 70 ^° C.),

the MEK is pre-cleaned from the substrate (B);

a layer of solvent primer (Dongsung 171-2®) is applied with a brush to the surface of the substrate (B) to be joined and dried in a ventilated oven (3 minutes at 70 ° C.); aqueous adhesive (Dongsung W-01®) on the surface of the substrate (B), previously coated with a solvent primer and dried in a ventilated oven (5 minutes at 70 ^° C.),

The two substrates are docked at their glued surfaces and the whole is pressed under air for 1 minute at a pressure of 4 bar and at room temperature. The thickness of the glue joint (glue layers + primer layers) varies between 50 to 150 μm. The geometry of the final laminate is as follows: Width = 15 mm, Length = 100 mm, Thickness = 2 to 5 mm.

The parameters relating to the laminates (Examples and Comparative) as well as the results of the peel tests (standard ISO 11339, speed 100 mm / minute) are given in Table II.

Table II

^* Contaminated by a release agent introduced into the mold before injection of the polymer in said mold.

The results show that, whatever the hardness of the Pebax® used, high peel strengths well above 3 daN / cm are obtained thanks to the method of manufacturing laminates according to the invention.

Claims

A laminate manufacturing method comprising at least two polymer layers, a layer (A) and a layer (B) joined to each other by at least one layer of aqueous type adhesive polymer material (C), characterized in that it comprises:

(a) optionally a step of pre-cleaning the substrate layer (A) and / or the substrate layer (B), in the form of pre-cleaning by continuous atmospheric cold plasma treatment, oxidizing or reducing,

(b) an activation step by continuous atmospheric cold plasma treatment of the substrate layer (A) and / or the substrate layer (B), said plasma being either:

(d) a step of sizing said substrate layer (A) and / or said substrate layer (B) with an aqueous type adhesive polymer material (C),

(e) a step of docking the substrate layers (A) and (B),

(f) A step of pressing the assembly obtained in (e), in a humid atmosphere so as to form the laminate. the substrate layer (A) comprising one or more polymers, additive (s) with at least one filler or non-additive (s), said polymer (s) being chosen from polyamides, thermoplastic elastomers (TPE) and mixtures thereof, the substrate layers (A) and (B) being identical or different, the substrate layers (A) and (B) being made with non-exuding polymers.

2. Method according to claim 1, characterized in that the substrates (A) and (B) are identical, that is to say that the two substrates (A) and (B) consist of the same polymer (s) chosen (s). ) among (i) polyamides (abbreviated PA) homo or copolymer, (ii) thermoplastic elastomers (abbreviated to TPE), chosen from PEBA or polyamide block copolymers and polyether blocks, TPU or thermoplastic polyurethane polymers, COPE or copolymers with polyether blocks and polyester blocks and (iii) their mixtures.

3. Method according to claim 1, characterized in that the substrates (A) and (B) are different but of the same nature, that is to say that the substrates (A) and (B) are both block copolymers with soft blocks made of polyether but with different hard blocks.

4. Method according to claim 1, characterized in that the substrates (A) and (B) are different and different in nature, the substrate (A) being chosen from PA and TPE and the substrate (B) being chosen from the substrates (D) formed by the group (i) homo or copolymer polymers such as polyolefins, polyamines, polyesters, polyethers, polyimides, polycarbonates, phenolic resins, crosslinked or uncrosslinked polyurethanes, in particular foams , poly (ethylene / vinyl acetate), natural or synthetic elastomers such as polybutadienes, polyisoprenes, styrene-butadiene-styrene (SBS), styrene-butadiene-acrylonitrile (SBN), polyacrylonitriles and also (ii) ) natural or synthetic fabrics, in particular organic polymer fiber fabrics such that polypropylene fiber fabrics, polyethylene, polyesters, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyaramid, fiberglass fabrics and carbon fiber, as well as (iii) materials such as leather, paper and the cardboard.

5. Method according to claim 1, characterized in that the substrates (A) and (B) are different, one being PA, while the other being TPE.

6. Method according to one of the preceding claims, characterized in that said TPE or thermoplastic elastomers are chosen from

PEBA or copolymer with polyamide blocks and polyether blocks, TPU or copolymers with polyurethane blocks and polyether blocks, COPE or copolymers with polyether blocks and polyester blocks.

7. Method according to one of the preceding claims, characterized in that the adhesive polymer material (C) is a crosslinkable hot melt material manufactured by the reaction of at least one functionalized prepolymer and at least one hardener comprising free isocyanate functions (- N = C = O) or blocked.

8. Method according to claim 7, characterized in that the content of the free or blocked isocyanate functional hardener is 0.5 to 25% by weight, preferably 2 to 10% by weight relative to the total weight of the functionalized prepolymer.

9. The method of claim 7 or 8, characterized in that the functionalized prepolymers are selected from hydroxylated polyesters, hydroxylated polyethers and mixtures thereof.

10. Method according to one of the preceding claims, characterized in that the laminates are chosen from the structures:

• Substrate (A) / Primer (a) / Water Adhesive (C) / Adhesive (E) / Primer (s) / Substrate (B), • Substrate (A) / Primer (a) / Water Adhesive (C) / Adhesive (E) / Primary (a) / substrate (B),

Substrate (A) / primer (a) / aqueous adhesive (C) / adhesive (E) / substrate (B),

Substrate (A) / aqueous adhesive (C) / adhesive (E) / Primer (s) / substrate (B),

• Substrate (A) / Water Adhesive (C) / Adhesive (E) / Primer (a) / Substrate (B), • Substrate (A) / Water Adhesive (C) / Adhesive (E) / Substrate (B) Primer (a) designating an aqueous-type primer, the primer (s) designating an organic solvent-type primer, the aqueous adhesive (C) designating the aqueous-type adhesive polymer material (C), the adhesive (E) denoting an adhesive of aqueous type or an organic solvent type glue.

11. The method of claim 10, characterized in that the adhesive (E) is of aqueous type in the case where the substrate (B) is PA or TPE and solvent or aqueous type, preferably aqueous type in other cases.

12. Method according to one of claims 10 or 11, characterized in that the laminates are selected from the structures: o PA homo or copolymer / Primer (a) / aqueous adhesive (C) / aqueous adhesive

(CyPrimaire (a) / PA homo or copolymer, o PA homo or copolymer / Primer (a) / aqueous adhesive (C) / aqueous adhesive

(CyPrimary (a) / TPE, o TPE / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPE, o Homo PA or copolymer / Primer (a) / aqueous adhesive (C) ) / aqueous glue

(CyPrimary (a) / polymer (D), o TPE / aqueous adhesive (C) / aqueous adhesive (C) / polymer (D), o homopolymer or copolymer / aqueous adhesive (C) / aqueous adhesive (C) / PA homo or copolymer, o homopolymer or copolymer / adhesive aqueous (C) / aqueous adhesive (C) / TPE, o TPE / aqueous adhesive (C) / aqueous adhesive (C) / TPE, o homopolymer or copolymer / aqueous adhesive (C) / aqueous adhesive

(C) / polymer (D), o TPE / aqueous adhesive (C) / aqueous adhesive (C) / polymer (D), o PEBA / Primer (a) / aqueous adhesive (C) / aqueous adhesive (C) / Primer (a) / TPU, o PEBA / Primary (a) / aqueous glue (C) / glue (E) / leather, o PEBA / Primary (a) / aqueous glue (C) / glue (E) / polyurethane foam, o PEBA / Primer (a) / aqueous adhesive (C) / glue (E) / rubber, o PEBA / Primer (a) / aqueous adhesive (C) / glue (E) / nonwoven polyolefin,

13. A method of manufacturing a shoe component comprising a method of manufacturing a laminate according to one of the preceding claims.

14. The manufacturing method according to claim 13, characterized in that the constituent element is a shoe sole, preferably a sports shoe.