BRPI0712965A2 - adhesion activator intended to be applied on an elastomeric thermoplastic polymer or powder substrate and corresponding surface treatment and bonding process - Google Patents

Abstract

ADHESION ACTIVATOR INTENDED TO BE APPLIED ON AN ELASTOMERIC THERMOPLASTIC POLYMER SUBSTRATE OR PA AND SURFACE TREATMENT PROCESSES AND CORRESPONDING ADHESION. The present invention relates to the assembly by gluing a first substrate (S1) in elastomeric thermoplastic polymer (abbreviated TPE) or in homo polyamide (abbreviated PA) or copolymer (abbreviated coPA) and a second substrate (S2). The substrates (S1) and (S2) can be of the same nature, that is, in TPE or in homo PA or coPA, they can be of different nature. In general, the substrates (S1) in elastomeric thermopiastic polymer (TPE) are assembled by gluing with other substrates (S2) by means of glues or adhesives with organic solvent, also called glues with two-component polyurethane solvents.

Description

ADHESION ACTIVATOR TO BE APPLIED ON A SUBSTRATE IN ELASTOMERIC THERMOPLASTIC POLYMER OR PA AND SURFACE TREATMENT PROCESSES AND CORRESPONDENT MOUNTING

The present invention relates to the gluing assembly of a first substrate (S1) into an elastomeric thermoplastic polymer (abbreviated TPE) or a homo or copolymer (abbreviated coPA) and a second substrate (S2). The substrates (S1) and (S2) may be of the same nature, that is, in TPE or homo PA or coPA may be of a different nature.

Silicones are strongly excluded from substrates (S1) and (S2).

WO / 14146 relates to the bonding of a silicone material. Such bonding is enhanced by treating the surface of said silicone in such a way as to change the surface character of said material. The treatment consists in at least partially functionalizing the surface of the material with reactive chemical functions, for example, hydroxyl, carboxylic or both. Suitable treatments for creating such functionalization include (i) irradiating the surface of the material with an effective dosage of electromagnetic radiation, for example ultraviolet, infrared, or visible radiation, and (ii) contacting the surface of the material with various reagents. oxidants which may be gaseous, liquid, plasma such as oxygen, ozone, peroxides, oxygen-fluorine (02 / F2) mixtures, air / fluoride mixtures, fluorine mixtures, peroxide acids and the analogous products. EP456972 refers to polyimides and not to TPE or PA. The surface of the polyimide is functionalized by opening the imide functions on which the carboxylic functions are branched which can then be combined with the metal complexes.

These documents are very different from our invention in that, in our case:

- Existing functions already exist on the TPE or PA polymer. We have not created any new functionality on the TPE or PA substrate; and

The adhesion activator aims to make existing functions accessible and accelerate their reactivity with isocyanates, particularly isocyanates present in adhesives and / or aqueous primers.

In general, the elastomeric thermoplastic polymer (TPE) substrates (SL) are assembled by gluing with other substrates (S2) by means of glues or adhesives with organic solvent, also called bicomponent polyurethane type solvent adhesives.

Bonding this type of substrate (Sl) onto substrate (S2) requires the following operations in order:

cleaning surfaces of substrates (S1) and (S2) to be bonded with an organic solvent such as methyl ethyl ketone (MEK);

applying, generally with a brush, to at least the contact surface of the substrate (SL) in polyamide-block-polyether copolymer of a generally solvent-based primary composition layer;

- kiln drying of the primer layer; - application, usually with a brush, on the primer layer and also on the contact surface of the other substrate (S2) of a two-component adhesive layer;

- kiln drying the glue layers;

- approximation of the two bonded substrates (S1) and (S2); and

press the resulting assembly together.

Primer compositions used are generally two-component compositions whose first component is a solution of a resin functionalized in an organic solvent and the second component (crosslinker), which is added to the first component shortly before use, is an isocyanate or isocyanate mixture. also in solution in an organic solvent. This step of primer application implies that emissions of organic solvents into the atmosphere.

Bicomponent adhesives comprise a first component which is a hydroxylated organic resin in dispersion or solution in an organic solvent and / or water and a second component (crosslinker) which is an isocyanate solution in an organic solvent or a pure isocyanate. In the case of an organic solvent glue, a new solvent emission is generated.

During these different steps (primer and / or glue application step and drying step), it has been estimated that about 30 kg of organic solvents from the use of a primer and a solvent-based glue are emitted during assembly of 10000 shoes, where there are multiple problems in terms of air pollution, toxicity but also in terms of extra costs.

The present invention aims to solve these drawbacks and proposes simple and efficient means for increasing adhesion of a glue assembly of the substrates (S1) and (S2) defined below.

The present invention therefore relates to the use of an activator and / or a mixture of adhesion activators (A) on the surface of an elastomeric plastic thermopolymer (TPE) substrate (S1) having chains formed of alternating hard segments. and flexible segments or in homo PA or coPA, in view of gluing assembly of said substrate (S1) onto another substrate (S2). Increased adhesion is achieved by the presence of one and / or a mixture of adhesion activators (A) on the substrate surface (F1) (S1) and / or the interface between sibstrate (S1) and primer (P). of adhesion in the case of a primer bonding or between substrate (S1) and glue (C) in the case of a primer-free bonding (P).

The invention is directed to the use of an adhesion activator (A) to react (i) with the functional groups of at least one polymer of a substrate (S1) and / or (ii) to complex the chains of at least one. a polymer of said substrate (S1) at the level of a bonding surface (F1) of a substrate (S1) comprising at least one elastomeric thermoplastic polymer (TPE) which comprises a sheath formed of an alternation of hard segments and flexible segments, or at least one homo or copolymeric polyamide in view of gluing assembly of said substrate (S1) to another substrate (S2).

According to one embodiment, the use is characterized by the fact that adhesion activator (A) is chosen from the catalysts that intervene in chemical reactions involving isocyanate functions.

According to one embodiment, the use is characterized by the fact that the adhesion activator (A) is chosen from amine type, metal salt type, organometallic type catalysts and mixtures thereof.

According to one embodiment, the use is characterized by the fact that the substrate (S2) is of the same nature as (Sl).

According to one embodiment, the use is characterized by the fact that substrate (Sl) and substrate (S2) are of a different nature, knowing that (S2) is chosen from (TPE), homopolymers and copolymers. , such as polyolefins, polyamines, polyesters, polyethers, polyesters, polyamides, polycarbonates, phenolic resins, cross-linked polyurethanes or not, in particular foams, poly (ethylene vinyl acetate), natural elastomers or such as polybutadienes, polyisoprenes, styrene butadiene styrene (SBS), styrene butadiene acrylonitrile (SBN), polyacrylonitriles, natural or synthetic fabrics, especially fabrics in organic polymer fibers such as fabrics polypropylene fibers, polyethylene, polyesters, polyvinyl alcohol, vinyl polyacetate, polyvinyl chloride, polyamide, woven glass or carbon fiber fabrics such as leather, paper and cardboard.

According to one embodiment, the use is characterized in that the substrate (S1) is chosen from (a) the polyester block and polyether block copolymers, (b) the polyurethane block and polyether block copolymers, (c ) copolymers with polyamide blocks and polyether blocks and mixtures thereof.

The invention has also dealt with a surface treatment process of an elastomeric thermoplastic polymer (TPE) or homo or copolymer polyamide substrate (S1) in order to favor the approximation of a primer and / or glue on a bonding surface (F1 ) of said substrate (S1) with another substrate (S2), characterized in that an adhesion activator (A) is included in the polymer forming substrate (S1).

According to one embodiment, the surface treatment process of an elastomeric thermoplastic polymer (TPE) or homo or copolymer polyamide substrate (S1) in order to favor the approximation of a primer (P) and / or glue ( C) in view of the gluing assembly of said substrate (S1) to another substrate (S2), it is characterized in that an adhesion activator (A) is applied to the substrate (S1).

According to one embodiment, the surface treatment process of a substrate (S1) is characterized in that the adhesion activator (A) is included in a mixture comprising at least one cleaning solvent which is applied to the substrate. bonding surface (F1) of substrate (S1) in view of gluing assembly of said substrate (S1) to another substrate (S2).

According to one embodiment, the surface treatment process of a substrate (S1) is characterized by the fact that the adhesion activator (A) is included in an adhesion primer layer (P) which is applied on the surface. bonding surface (F1) of the substrate (S1) to another substrate (S2).

According to one embodiment, the surface treatment process of a substrate (S1) is characterized in that the adhesion activator (A) is included in a glue layer (C) which is applied to the surface of the substrate. bonding (F1) the substrate (S1) in view of the gluing assembly of said substrate (S1) to another substrate (S2).

According to one embodiment, the process is characterized in that the adhesion activator (A) is applied alone or in admixture with a degreasing solvent and / or an adhesion primer (P) and / or an adhesive. (C) on the bonding surface (F1) is the substrate (S1).

According to one embodiment, the process is characterized in that the solvent based or aqueous based adhesion activator (A) is used.

According to one embodiment, the process of gluing a substrate (S1) in elastomeric thermoplastic polymer (TPE) or homo or copolymeric polyamide to a substrate (S2) characterized in that it is a bonding surface (F1) of substrate (S1) by the process as defined above and mounting the two substrates (S1) and (S2) by their two bonding surfaces (F1) and (F2), at least one of which is glued

The invention also relates to a bonded set of two substrates (S1) and (S2), especially two-layered shoe soles (S1) and (S2), one being at least one elastomeric thermoplastic polymer (TPE) or a homo or copolymeric polyamide having been activated by an adhesion activator (A) as defined above.

According to one embodiment, the glued set of two substrates (Sl) and (S2) is obtained according to the assembly process defined above.

The invention also relates to a bonding assembly kit of an elastomeric thermoplastic polymer or homo or copolymeric polyamide substrate (S1) to another substrate (S2) comprising:

The. a adhesion activator (A) as defined above and

B. possibly an adhesion primer (P); and

ç. a glue (C) for bonding the substrate (S1) and comprising:

- possibly an adhesion primer (P); and

- a glue (C) for bonding the substrate (S2).

The structure of Figure 1 represents a substrate (S1) bonded at its surface (F1) to a substrate (S2) at its surface (F2) by means of a glue (C) and an adhesion activator according to with the invention.

The structure of figure 2 comprises an additional adhesion primer relative to figure 1 between the adhesion activator (A) and the glue (C).

Figures 3 and 4 illustrate embodiments of the invention in which the structures comprise in their primer layer (P) or in their glue layer (C) the adhesion activator (A).

Figures 5 and 6 represent a substrate S1 or a substrate S2 (designated SI, 2 on the figures) glued prior to approach with or without primer.

The invention thus relates to the use of an adhesion activator (A) for:

(i) reacting with the functional groups of at least one polymer of a substrate (S1) at the level of a bonding surface (F1) of said substrate (S1) and / or

(ii) complexing the chains of at least one polymer of said substrate (S1) at the level of said bonding surface (F1) of said substrate (S1), said polymer of said substrate (S1) being chosen from:

- elastomeric thermoplastic polymers (TPE) which comprise a chain formed of an alternation of hard segments and F1 segments, and

- homo or copolymeric polyamides, in view of the gluing assembly of said substrate (S1) to another substrate (S2).

By "elastomeric thermoplastic polymer (TPE)" is meant a block copolymer having alternately said hard or rigid blocks or segments and said flexible or soft blocks or segments.

As an example of hard block and F1 block copolymer, respectively, (a) polyester block and polyether block copolymers (also called polyethers), (b) polyurethane block and polyether block copolymers (also called TPU for short term thermoplastic polyurethanes) and (c) polyamide block and polyether block copolymers (also called PEBA according to IUPAC).

In the case of polyesters (a), they are the copolymers with polyester blocks and polyether blocks. They are made up of flexible polyether blocks which are the remains of polyetheriols and rigid segments (polyester blocks) resulting from the reaction of at least carboxylic diacid with at least one short chain lengthening diol moiety. The polyester blocks and the polyether blocks are linked by the ester bonds that result from the reaction of acidic acid functions with the polyethericol OH functions.

The chain-elongating short diol may be selected from the group consisting of neopentylglycol, cyclohexanedimethanol and the aliphatic glycols of the formula HO (CH2) nOH where η is an integer from 2 to 10.

Advantageously, the diacids are aromatic dicarboxylic acids having from 8 to 14 carbon atoms. Up to 50 mol% of the dicarboxylic aromatic acid may be substituted for at least one other dicarboxylic aromatic acid having from 8 to 14 carbon atoms, and / or up to 20 mol% may be substituted for a dicarboxylic aliphatic acid having from 2 to 12 carbon atoms. carbon.

Examples of dicarboxylic aromatic acids include terephthalic, isophthalic, bibenzoic acid, dicarboxylic naphthalene, 4,4'-diphenylenedicarboxylic acid, bis (p-carboxyphenyl) methane, ethylene bis p-benzoic acid 1-4 tetramethylene bis (p-oxybenzoic acid), ethylene bis (for oxybenzoic acid), 1,3-trimethylene bis (p-oxybenzoic acid). As an example of glycols, 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. Polyester block and polyether block copolymers are, for example, copolymers having polyether polyol derived moieties, such as polyethylene glycol (PEG), polypropylene glycol (PPG), polytrimethylene ether glycol (P03G) or polytetramethylene glycol (PTMG) ), the carboxylic diacid moieties, such as terephthalic acid and the glycol (ethane diol) or butane diol moieties 1-4. Chaining of polyethers and diacids forms the flexible segments while chaining glycol or butane diol with diacids forms the rigid segments of the copolyester. Such copolyester esters are described in EP 402,883 and EP 405,227. These polyethers are the thermoplastic elastomers. May contain plasticizers.

In the case of TPU (b), they result from the condensation of flexible polyether blocks, which are the remains of polyetheriols and polyurethane rigid blocks resulting from the reaction of at least one diisocyanate with at least one short diol. The chain-lengthening short diol may be chosen from the glycols cited above in the description of the polyethers. Polyurethane blocks and polyether blocks are linked by the bonds that result from the reaction of isocyanate functions with the OH functions of polyetherum.

Further mention may be made of polyesterurethanes, for example those comprising diisocyanate moieties, amorphous diol polyester derivative moieties and portions of a short chain lengthening diol. May contain plasticizers.

In the case of PEBA (c), they result from the copolycondensation of reactive end polyamide sequences with reactive end polyether sequences, such as, among others:

1) Polyamide sequences with chain ends diamines with polyoxyalkylene sequences with dicarboxylic chain ends.

2) Polyamide sequences with dicarboxylic chain ends of the polyoxyalkylene sequences with diamine chain ends obtained by cyanoethylation and hydrogenation of aliphatic dihydroxylated alpha-omega polyoxyalkylene sequences called polyetheriols.

3) Polyamide sequences with dicarboxylic chain ends with the polyetherols, the products obtained being, in this specific case, polyetherestamides. The copolymers of the invention are advantageously of this type.

Polyamide sequences with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting carboxylic diacid.

The polyamide sequences with diamine chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain limiting diamine.

Polymers with polyamide blocks and polyether blocks may also comprise randomly divided portions. Such polymers can be prepared by simultaneously reacting the polyether and polyamide block precursors.

For example, polyamediol, polyamide precursors and a chain limiting diacid may be reacted. A polymer is obtained having essentially the polyether blocks, the polyamide blocks of very variable length, but also the different reactants having reacted randomly which are randomly (statistically) distributed along the polymeric chain.

Polyetheramine, polyamide precursors and a chain limiting diacid may also be reacted. A polymer is obtained having essentially the polyether blocks, the polyamide blocks of very variable length, but also the different reactants having reacted randomly which are randomly (statistically) distributed along the polymeric chain.

Advantageously three types of polyamide blocks can be used.

According to a first type, the polyamide sequences come from the condensation of a carboxylic diacid, 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 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 include tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine7 trimethylhexamethylene diamine, bis (4-aminocyclohexyl) -methane (3- (BACM)) isomers. methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis- (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-cyclohexyl methane (PACM), and isophoronadiamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine (Pip).

Advantageously, there are the blocks 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 10.14 and PA 10.18.

According to a second type, polyamide sequences 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 carboxylic acid having from 4 to 12 atoms. carbon or a diamine.

Examples of lactams include caprolactam, oenantolactam and laurylactam.

Examples of alpha omega amino carboxylic acid include aminocaproic, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids.

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

According to a third type, the polyamide sequences result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one carboxylic diacid.

In this case the polyamide PA blocks are prepared during a first step by polycondensation:

. of the linear or aromatic aliphatic diamines having X carbon atoms;

. the carboxylic diacids or acids having Y carbon atoms;

of the {z} comonomer (s) chosen from lactams and alpha-omega-aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having X1 carbon atoms and at least one carboxylic diacid having Y1 carbon atoms , (XI, Yl) being different (from Χ, Υ),

said or said {z} comonomers introduced in a weight ratio of up to 50%, preferably up to 20%, even more advantageously up to 10% with respect to the set of polyamide precursor monomers;

in the presence of a chain limiter chosen from carboxylic diacids; then

During a second step, the polyamide PA blocks obtained are reacted with PE polyether blocks in the presence of a catalyst.

Advantageously, the carboxylic diacid having Y carbon atoms is used as a chain limiter, which is introduced in excess of the stoichiometric ratio of the diamine (s).

Preferably, the polycondensation is conducted at a temperature of 180 to 300 ° C. 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 chosen 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 4,331,786, US 4,115,475, US 4,195,015, US 4,839,441, US 4,864,014, US 4,230,838 and US 4,332,920.

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

The PA block formation reaction is usually carried out at 180 to 300 ° C, preferably 200 to 290 ° C, the pressure in the reactor is set at 500 to 3000 KPa, and is maintained for about 2 to 3 hours. The pressure is slowly reduced by placing the reactor at atmospheric pressure, then distilling off excess water, for example for an hour or two.

The carboxylic acid end polyamide having been prepared, then the polyether and a catalyst are added. The polyether may be added once or several times in the same manner to the catalyst. In an advantageous manner, the polyether is added at once, the reaction of the OH ends of the polyether and the COOH ends of the polyamide begins with ester bond formation and water elimination. As much water as possible is removed from the reaction medium, then the catalyst is introduced to terminate the bonding of the polyamide blocks and the polyether blocks. This second step is carried out under agitation, 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 may be from 100 to 400 ° C and generally 200 to 300 ° C. The reaction is followed by measuring the torsional torque exerted by the molten polymer on the stirrer or by measuring the electrical power consumed by the stirrer. The end of the reaction is determined by the value of the target torque or power.

You may also add during the synthesis, at the most appropriate time, one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245.

According to an alternative 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 one lactam and one aminocarboxylic acid not having the same number. carbon atoms in the eventual presence of a chain limiter.

As an example of aliphatic alpha omega amino carboxylic acid, amino-7-heptanoic, amino-11-undecanoic and amino-12-dodecanoic acids can be cited.

As an example of lactam, caprolactam, oenantolactam and laurylactam may be cited.

Examples of aliphatic diamines include hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylene diamine.

As an example of cycloaliphatic diacids, 1,4-cyclohexyldicarboxylic acid may be cited.

Examples of aliphatic diacids include butane-dioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic acids, dimerized fatty acids (these dimerized fatty acids preferably have a dimer content of at least 98%; They are preferably hydrogenated and are marketed under the brand name "PRIPOL" by the company "UNICHEMA" or under the brand name EMPOL by the company HENKEL) and the polyoxyalkylenes-α, ω diacids.

By way of example, aromatic diacids include terephthalic (T) and isophthalic acids (I).

Examples of cycloaliphatic diamines include bis (4-aminocyclohexyl) methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane isomers (BMACM), and 2- 2-bis- ( 3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM). Other commonly used diamines may be isophoronadiamine (IPDA), 2,6-bis- (aminomethyl) -norbornane (BAMN) and piperazine.

Examples of polyamide sequences of the third type include: - 6.6 / 6

6.6 means hexamethylenediamine moieties condensed with adipic acid.

6 denotes portions resulting from condensation of caprolactam.

- 6.6 / Pip. 10/12 in which 6.6 designates hexamethylenediamine moieties condensed with adipic acid.

Pip 10 means the portions resulting from the condensation of piperazine and sebacic acid.

12 designates the portions that result from condensation of laurylactam.

The weight ratios are respectively 25 to 35/20 to 30/20 to 30 / o total being 80 and advantageously 30 to 35/22 to 27/22 to 27 / o total being 80.

For example, the ratios 32/24/24 / lead to a melting temperature of 119 to 137 ° C.

- 6.6 / 6.10 / 11/12 in which

6.6 means hexamethylenediamine condensed with adipic acid.

6.10 means hexamethylenediamine condensed with sebacic acid.

11 designates the portions that result from condensation of aminoundecanoic acid.

12 designates the portions that result from condensation of laurylactam.

The weight ratios are respectively 10 to 20/15 to 10 to 20/15 to 25 the total being 70 and advantageously 12 to 16/18 to 25/12 to 16/18 to 25 the total being 70.

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

Polyamide blocks are obtained in the presence of a chain-limiting diacid or diamine if either the polyamide blocks with acid or amine ends. If the precursors already comprise diacid or a diamine, it is sufficient, for example, to overuse. Polyether blocks may represent 5 to 85% by weight of the polyamide and polyether block copolymer. The polyether blocks are made up of alkylene oxide moieties. These portions may be, for example, ethylene oxide portions, propylene oxide portions or tetrahydrofuran (leading to polytetramethylene glycol chains). PEG blocks, ie those consisting of ethylene oxide portions of the PPG blocks, ie those consisting of propylene oxide portions, the polytrimethylene ether glycol portions (of such copolymers with the polytrimethylene ether blocks are described). US 6590065), and PTMG blocks, i.e. those consisting of tetramethylene glycol moieties also called polytetrahydrofuran. PEG blocks or bisphenol oxyethylation blocks such as bisphenol A are advantageously used. These latter products are described in EP 613.919.

The polyether blocks may also be comprised of ethoxylated primary amines. These blocks are advantageously used as well. Examples of ethoxylated primary amines include:

<formula> formula see original document page 21 </formula>

where m and η are from 1 to 20 and χ from 8 to 18. These products are commercially available under the trademark N0RAM0X® by CECA and under the GENAMIN® trademark of CLARIANT.

The amount of polyether blocks in such polyamide block and polyether block copolymers is advantageously from 10 to 70% by weight of the copolymer and preferably from 35 to 60%.

The polyethericol blocks are either used such that they are copolycondensed with the carboxylic-tipped polyamide blocks, or are amines to be transformed into polyether diamines and condensed with the carboxy-tipped polyamide blocks. They may also be mixed with the polyamide precursors and a diacid chain limiter to make the polymers with polyamide blocks and polyether blocks having the statistically divided portions.

The spring mass in number Mn of the polyamide sequences is from 500 to 10000 and preferably from 500 to 4000 except for polyamide blocks of the second type. The mass Mn of the polyether sequences is from 100 to 6,000 and preferably from 200 to 3,000.

These polyamide block and polyether block polymers derived from the copolycondensation of previously prepared polyamide and polyether sequences or a one-step reaction have, for example, an intrinsic viscosity of between 0.8 and 2.5 measured in metacresol at 25 ° C to an initial concentration of 0.8 g / 100 ml.

This is the preparation of copolymers with polyamide blocks and polyether blocks, which can be prepared by any means which allows the addition of polyamide blocks and polyether blocks. In practice, essentially two processes are used one said in 2 steps, the other in one step.

In the two-step process the polyamide blocks are manufactured and then a second step is added to the polyamide blocks and the polyether blocks. In the one-step process the polyamide precursors, the chain limiter and the polyether are mixed; A polymer is then obtained having essentially the polyether blocks, the polyamide blocks of very variable length, but also the different reactants having a random reaction which are randomly (statistically) distributed along the polymeric chain. Whether in one or two steps it is advantageous to operate in the presence of a catalyst. Catalysts described in US 4,331,786, US 4,115,475, US 4,195,015, US 4,839,441, US 4,864,014, US 4,230,838 ET US 4,332,920, WO 04 037898, EP 1262527, EP 1270211, EP 1136512, EP 1046675, EP 1057870, EP 1155065, EP 506495 and EP 504058. In the one-step process the polyamide blocks are also manufactured, because it was written at the beginning of this paragraph that such copolymers could be prepared by any medium that adds the polyamide blocks (PA block) and the polyether blocks (PE block).

Advantageously, the PEBA copolymers have PA blocks in PA 6, PA 12, PA 6.6 / 6, PA 10.10 and PA 6.14 and PE blocks in PTMG, PPG, P03G and PEG.

SL is chosen from the predefined TEPs and the polyamide homo and copolymers. S1 and S2 may be identical or different, but in this case S2 is chosen from previously defined homopolymer and copolymer TEPs such as polyolefins, polyamines, polyesters, polyethers, polyesters, polyimides, polycarbonates, phenolic resins, non-crosslinked polyurethanes, in particular foams, poly (ethylene vinyl acetate), natural or synthetic elastomers such as polybutadien, polyisoprene, styrene butadiene styrene (SBS), styrene butadiene acrylonitrile (SBN), polyacrylonitriles, natural or synthetic fabrics, especially organic polymeric fiber fabrics, such as polypropylene, polyethylene, polyester, polyvinyl alcohol, vinyl polyacetate, polyvinyl chloride, polyamide fiber fabrics, fiberglass and carbon fiber fabrics , as well as materials such as leather, paper and bellied paper. All of these materials may also be foamed when this is possible.

With regard to the adhesion primer (P), it may be the organic solvent (s) base or the aqueous base.

With regard to glue (C), it may be the organic solvent (s) base or the aqueous base.

One can therefore have a combination of solvent based (S) or aqueous based adhesion primer (P) with a solvent (s) or aqueous based glue (C), knowing that the adhesion activator ( A) can be:

- deposited at the adhesion interface level, ie between Substrate (Sl) and primer (P) or glue (C);

- incorporated into the adhesion primer (P) and / or the glue (C) whereby it should in this case be able to migrate to the interface between the Substrate (Sl) and the primer or glue.

Adhesion activator (A) may be combined by applying a solvent based adhesion primer (P) with poor adhesion power, but the volatile organic component (s) base (abbreviated) VOC) reduces either the aqueous base with a glue (C) the solvent base (s) or the aqueous base.

Adhesion activators can comprise several components.

The adhesion activator (a) is advantageously chosen to be able to activate the substrate surface (Sl):

(i) reacting with functional groups of the polymer or at least one substrate polymer (S1) when it comprises a mixture of polymers and / or reacting with functional groups of primer (P) and / or glue (C); and / or

- (ii) complexing the polymer chains or at least one substrate polymer (Sl) when it comprises a mixture of polymers and / or complexing the primer polymer chains (P) and / or complexing the glue polymer chains (Ç); and

- catalyze the bonding reaction.

Functional groups may be, for example, of the type -OH, -COOH, -NH2, = NH, = C = O, epoxide function, the list being non-exhaustive.

The adhesion activator (s) may be capable of reacting to hot or cold.

Adhesion activator (a) may be introduced into the cleaning solution or polymer by an isolation operation or with the aid of a master mix containing the adhesion promoter or during polycondensation of the TPE or by incorporation by dry mixing during transformation of the modeled parts.

The adhesion activator (A) may be incorporated into the coating in contact with (Sl) provided that the adhesion activator (A) may react with the polymer of (Sl), the coating being defined as the cleaning solution, the primer (P) and / or the glue (C). The interface of adhesion to the contact surface between the substrate (Sl) and the coating is called.

The solution of incorporating adhesion activator (A) in the cleaning solution is a preferred solution.

Cleaning solutions are those generally used to remove impurities, grease, foreign agents that may alter the adhesion of primers (P) and / or adhesives (C) on substrates.

These cleaning solutions may also contain additives such as wetting agents or detergents to promote the elimination of polluting products and / or to improve the wettability of the substrates.

For example, water-based, aliphatic organic solvent-based or aromatic solvent-based cleaning solutions and mixtures thereof consisting of 2 or 3 preceding solvents may be mentioned.

The main solvent groups are:

• ketones (eg acetone, methyl ethyl ketone).

• Alcohols (eg methanol, ethanol, isopropanol, glycols).

• Esters (eg acetates, agrosolvents).

• Ethers (eg ethyl ethers, THF, dioxane).

• Glycol ethers.

• Aromatic hydrocarbons (benzene, toluene, xylene, cumene).

• Oil solvents (non-aromatic: alkanes, alkenes).

• Halogenated hydrocarbons: (chlorinated, brominated or fluorinated).

• Specific solvents (amines, amides, terpenes).

Organic solvents or water-based and organic solvent-based solutions will be properly chosen to minimize solvent emissions, reduce the risks associated with toxicity and ecotoxicity and promote good adhesion activator solubility and stability of mixtures.

Certain solvents and / or so-called functional solvent mixtures have been shown to play the role of adhesion activator (A) and allow to increase the adhesion of aqueous primers and / or aqueous adhesives on thermoplastic polymer (TPE) supports. This is the case of butanol / butanediol mixtures. The simple presence of this type of solvent and activator according to the invention with the substrate interface allows to increase the initial adhesion level as well as the permanence of the reactivity of this surface treatment.

Because this solution allows you to increase the activation time of the surfaces to be glued, it gives the assembler more flexibility by giving him the means to manage each step of assembly of the pieces to be glued, as well as their handling and packaging.

Adhesion activators (A) are chosen from the catalysts used in chemical reactions that imply isocyanate functions. Particular mention may be made of amine type catalysts (secondary or tertiary amine), metallic salts type or organometallic type catalysts.

As an amide catalyst, for example, diethylamine (DEA), diethanolamine, dimethylethanolamine, triethylamine (TEA), triethanolamine (TEOA), triisopropanol amine (TIPA), triethylenediamine (TEDA), dimethylaminepropylamine (DMAPA), dimethylamine (DMACHA), Triethylenetetramide, Triisopropylamine, Ν, Ν, Ν, N1 tetraethylethylenediamine, Ν, Ν, N1, N'-tetramethyl-1,3-butanediamine, 2,2'bis (dimethylamineethyl) ether (BDMAEE), 1- ( 3-aminipropyl) imidazole (API), N-methylimidazole (NMI), 1,2-dimethylimidazole (DMI), imidazole, 1,4-diazole (2.2.2) bicyclooctane (DABCO), N-methyl, N-ethylmorpholine .

As catalysts based on metal salts, we can mention, for example, those based on: Bi, Pb, Sn, Ti, Fe, Sb, U, Cd, Co, Th, Al, Hg, Zn, Ni, R3N , Ce, Mo, V, Mn, Zr, R3 P.

Taken in a broad sense the organometallic ones are characterized by the association of metal bonding organic segments. Non-exhaustive, for example, are tin dibutyldilaurate, tin acetate octoate, tin oleate, tin 2-ethylhexanoate, tin dibutyldilauryl mercaptide, tin dibutyldiacetate, lead naphthenate, stearate. tin oxide (SnO) reaction products or tin dibutyloxide reaction products with a carboxylic acid having from 1 to 20 carbon atoms, monobutyl tin hydrate oxide, butyl chlorine dihydroxide tin, butyl tris (2-ethylhexoate) tin, butyl stannic acid, tin dioctyl dilaurate, tin dioctyl maleate, tin oxalate, zinc carboxylates, bismuth carboxylates, organometallic compounds, zirconium diketones with diketones such as 2,4-pentanedione, ethylacetoacetate, chlorocyclopentadiene, dibenzoylmethane, 3-ethylacetylacetone, 1,1,1-trifloroacetylacetone, dibenzoylmethane benzoylacetone, benzoylacetone, triacetylmethane 2,2,6,6-tetramethyl-3,5-heptanedione, 6-methyl-2,4-heptanedione, 6-methyl-2,4-heptanedione, 2,4-pentanedione, 2,2-dimethyl-6,6,7,7,8,8-heptafluoro-3,5-octanedione, 6-methyl-2,4-heptanedione, 2,2-dimethyl-6,6,7 7,8,8-heptafluoro-3,5-octanodione, 6-methyl-2,4-heptanedione and butanol, 6-methyl-2,4-heptanedione and ethyl acetyl acetate, 6-methyl-2, 4-heptanedione and 2 acetocyclopentanone, 6-methyl-2,4-heptanedione and dibenzoylmethane and hafnium dichetonates, zirconium butoxide, molybdenum and / or tungsten with an oxidation state of at least +4, bismuth 2- ethylhexanoate, stannic organic compounds (IV), ammonium molybdate, lithium molybdate, sodium molybdate, cesium molybdate, potassium molybdate, rubidium molybdate, ammonium paramolybdate (NH4) 6Mo7024. 4H20, molybdenyl bisacetylacetonate MoO2 (C5H7O5) 2, molybdenum dioxide tetramethylheptadionate MoO2 (TMHD) 2, molybdenum alkoxides formed of 1,2-, 1,3-, or 1,4-diols such as ethylene glycol , propylene glycol or 1,4-butanediolmolybdic acid, molybdenum oxides, molybdate tetraethylammonium, sodium tungsten, magnesium molybdate, calcium molybdate, tungsten acid, lithium tungsten, phosphotungstic acid , +6 oxidized molybdenum and / or tungsten based compounds, at least +4 oxidized vanadium based compounds, ammonium vanadate, lithium vanadate, sodium vanadate, potassium vanadate, lithium orthovanadate, sodium orthovanadate, potassium orthovanadate, magnesium vanadate, calcium vanadate, vanadyl (IV) acetylacetonate VO (C5H7O5) 2 / vanadyl bistetramethylheotadionate VO (TMHD) 2, vanadic acid naphtha, zinc, lead octoate, lead tributyltin oxide, Zr (OBu) 4, Ti (OBu) 4, cobalt naphthenate, zirconium naphthenate, Bu2Sn (OCH3) 2, VO (OBu) 3, OCt2SnO, Ph3SnOH, cobalt acetylacetonate, Al dionates, Mn dionates, Ni dionates, Co dionates, Iron monocarboxylates, Iron acetate, Iron isobutyrate, Iron trifluoroacetate.

Particular mention may be made of Dabco T12, Fomrez SUL-4, Fascat 4202, Dabco T9, Fomrez C-2 and Cata Chek.

Adhesion activator (A) is present at 0.001 to 8%, preferably 0.001 to 4% by weight relative to the total weight of the medium in which the polymer or coating (cleaning solution, primer and / or glue).

The following examples (Table 1) illustrate the present invention without, however, limiting the scope. In the examples, the following abbreviations are used.

Substrates:

5533: PEBA Type 2 - PTMG (polyamide 12-polytetramethylene glycol), marketed by the ARKEMA Company under the name "PEBAX® 5533".

7033: PEBA type 2-PTMG (polyamide 12-polytetramethylene glycol), sold by the ARKEMA Company under the name "PEBAX® 7033".

PEBAX® 7033 is harder than PEBAX® 5533. Solvent: MEK: methyl ethyl ketone

Primers:

W104: water-based primer marketed by DONGSUNG Company under the name "Aquace® W104".

(Dry extract-30 min at 150 ° C = 40% by weight)

ARF-40® crosslinking agent marketed by Dongsung. (Dry extract-30 min at 150 ° C = 83.5% by weight)

Dply 165: solvent primer marketed by DONGSUNG Company under the name "D-Pli® 165" (Dry extract-30 min at 150 ° C = 10% by weight)

RFE® crosslinking agent marketed by Bayer. (Dry extract-30 min at 1500C = 26.9% by weight)

Membership Activator:

Borchi Kat22 of the Borchers Society is a Zinc Carboxylate (Organometallic).

Borchi Kat24 of the Borchers Society is a Bismuth Carboxylate (Organometallic).

Borchi KatVP244 of the Borchers Society is a Zinc and Bismuth Carboxylate in Mixture (Organometallic).

Glue:

WOl: aqueous glue marketed by DONGSUNG Company under the name "Aquace® WOl". (Dry Extract-30

Mn 150 ° C = 46.9 wt%)

ARF-40® crosslinking agent marketed by Dongsung.

The tests were performed using the following material:

- press on A524 (WKD 029 with maximum pressure set (indication 78,4 to 147,1 Pa (8 to 15 kg / cm2);

- Heraeus greenhouse at A524 (FGE 138) with 70 ° C, ventilated;

- ISO 34 cutters;

- pneumatic press for cutting samples.

General operating mode of assembly:

The substrates (Sl) and (S2) are plates with dimensions 100 χ 100 χ 1 mm.

> Substrate Preparation (Sl)

- Cleaning (in comparative examples) or adhesion activator cleaning (in the examples according to the invention) by a solvent or solvent mixture containing a smooth face adhesion activator of the substrate (Sl);

Cleaning time: 10 to 30 s

- drying 2 minutes at room temperature (unless otherwise indicated);

- application of aqueous W104 primer (+ 5% ARF-40® crosslinking agent) to the brush;

- drying 5 minutes at 700C in ventilated oven;

- cooling 2 minutes at room temperature;

applying the aqueous glue W01 (+ 5% ARF-40® cross-linking agent) to the brush;

- drying: 5 minutes at 70 ° C in a ventilated oven.

> Substrate Preparation (S2)

- MEK solvent cleaning of a smooth face of the

substrate S2;

Cleaning time 10 to 3Os.

- drying 2 minutes at room temperature;

applying Dply 165 primer (+ 5% RFE® crosslinking agent) to the brush; - drying 3 minutes at 70 ° C in a ventilated oven;

- cooling 2 minutes at room temperature;

applying the aqueous WO1 (+ 5% ARF-40® crosslinking agent) glue to the brush;

- drying 5 minutes at 70 ° C in a ventilated oven.

TABLE 1

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Claims (11)

Use of an adhesion activator (A) for: (iii) reacting with the functional groups of at least one polymer of a substrate (Sl) at the level of a bonding surface (F1) of said substrate ( Sl) and / or (iv) complexing the chains of at least one polymer of said substrate (Sl) at the level of said bonding surface (F1) of said substrate (Sl), said polymer of said substrate (Sl) being - elastomeric thermoplastic polymers (TPE) which comprise a chain formed of an alternation of hard segments and flexible segments, and - the homo or copolymeric polyamides for gluing assembly of said substrate (Sl) to another substrate (S2). Use according to claim 1, characterized in that the adhesion activator (A) is chosen from the catalysts that intervene in chemical reactions involving isocyanate functions. Use according to claim 1 or 2, characterized in that the adhesion activator (A) is chosen from amine type, metal salt type catalysts, organometallic type and mixtures thereof. Use according to any one of claims 1, 2 or 3, characterized in that the substrate (S2) is of the same nature as the substrate (Sl). Use according to any one of claims 1, 2 or 3, characterized in that the substrate (Sl) and the substrate (S2) are of a different nature, knowing that (S2) is chosen from (TPE), homopolymers and copolymers such as polyolefins, polyamines, polyesters, polyethers, polyesters, polymers, polycarbonates, phenolic resins, cross-linked polyurethanes or not, especially foams, poly (ethylene vinyl acetate) , natural or synthetic elastomers such as polybutadienes, polyisoprenes, styrene butadiene styrene (SBS), styrene butadiene acrylonitrile (SBN), polyacrylonitriles, natural or synthetic fabrics, especially organic polymeric fiber fabrics such as polypropylene, polyethylene, polyester, polyvinyl alcohol, vinyl polyacetate, polyvinyl chloride, polyamide fiber fabrics, glass fiber or carbon fiber fabrics o, as well as materials such as leather, paper and cardboard. Use according to any one of claims 1, 2, 3, 4 or 5, characterized in that the substrate (Sl) is chosen from (a) the polyester block and polyether block copolymers, (b) the polyurethane block and polyether block copolymers, (c) polyamide block and polyether block copolymers and mixtures thereof. 7. Surface treatment of an elastomeric thermoplastic polymer (TPE) or homo or copolymeric polyamide substrate (Sl) in order to favor the approximation of a primer (P) and / or a glue (C) in view of Glue assembly refers to substrate (S1) to another substrate (S2), characterized in that an adhesion activator (A) is applied to the substrate (S1). Process according to Claim 7, characterized in that the adhesion activator (A) is applied alone or in admixture with a degreasing solvent and / or includes an organic solvent-based adhesion primer (P). or the aqueous base and / or includes in a glue (C) on the sizing surface (F1) the substrate (S1) in view of the gluing assembly of said substrate (S1) to another substrate (S2). A process for gluing a substrate (S1) into an elastomeric thermoplastic polymer (TPE) or a homo or copolymeric polyamide having a bonding surface (F1) to a substrate (S2) having a bonding surface (F2) characterized by that the bonding surface (F1) of the substrate (S1) is treated by the surface treatment process as defined in any of claims 7 or 8, and that the two substrates (S1) and ( S2) by their two bonding surfaces (F1) and (F2), at least one of which has been bonded. Glued assembly of two substrates (S1) and (S2), characterized in that it was obtained according to the assembly process according to claim 5. 11. A two-substrate bonded set (S1) and (S2), characterized in that they are especially soles with two layers of substrate (S1) and (S2), at least one being an elastomeric thermoplastic polymer (TPE) or a homo polyamide or copolymer having been activated by the use of an adhesion activator (A) according to one of claims 1, 2, 3, 4, 5 or 6.