Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
  • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/06—Coating with compositions not containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/12—Chemical modification
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31507—Of polycarbonate
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
  • Y10T428/31562—Next to polyamide [nylon, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/00—Stock material or miscellaneous articles
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  • Y10T428/31725—Of polyamide
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/31736—Next to polyester
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31725—Of polyamide
  • Y10T428/3175—Next to addition polymer from unsaturated monomer[s]
  • Y10T428/31757—Polymer of monoethylenically unsaturated hydrocarbon
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31786—Of polyester [e.g., alkyd, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31931—Polyene monomer-containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31855—Of addition polymer from unsaturated monomers
  • Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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  • Y10T428/31971—Of carbohydrate
  • Y10T428/31993—Of paper
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2926—Coated or impregnated inorganic fiber fabric
  • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
  • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
  • Y10T442/2926—Coated or impregnated inorganic fiber fabric
  • Y10T442/2992—Coated or impregnated glass fiber fabric

Definitions

• the present invention relates to the bonding assembly of a first substrate (Sl) made of thermoplastic elastomer polymer (abbreviated as TPE) or polyamide (abbreviated PA) homo or copolymer (abbreviated as coPA) and a second substrate (S2).
• the substrates (Sl) and (S2) may be of the same nature, that is to say in TPE or PA homo or coPA or may be of a different nature.
• Suitable treatments for creating such functionalization include (i) irradiating the surface of the material with an effective dosage of electromagnetic radiation, eg, ultraviolet, infrared, or visible radiation, and (ii) contacting the the surface of the material with various oxidizing reagents that may be gaseous, liquid, plasma, such as oxygen, ozone, peroxides, mixtures of oxygen-fluorine (O2 / F2), air mixtures / fluorine, fluorine mixtures, peroxide acids and the like.
• electromagnetic radiation eg, ultraviolet, infrared, or visible radiation
• various oxidizing reagents that may be gaseous, liquid, plasma, such as oxygen, ozone, peroxides, mixtures of oxygen-fluorine (O2 / F2), air mixtures / fluorine, fluorine mixtures, peroxide acids and the like.
• EP456972 relates to polyimides and not TPEs or PAs.
• the polyimide surface is functionalized by opening the imide functions onto which carboxylic functions are connected, which can then be combined with metal complexes.
• adhesion promoter The purpose of the adhesion promoter is to make these existing functions accessible and to accelerate their reactivity with isocyanates, in particular the isocyanates present in glues and / or aqueous primers.
• the two-component adhesives comprise a first component which is a hydroxylated organic resin in dispersion or solution in an organic solvent and / or in water and a second component (crosslinking agent) which is an isocyanate solution in an organic solvent or a pure isocyanate .
• a second component crosslinking agent which is an isocyanate solution in an organic solvent or a pure isocyanate .
• the present invention aims to solve these disadvantages and to propose simple and effective means for increasing the adhesion of an assembly by bonding the substrates (Sl) and (S2) defined below.
• the subject of the present invention is therefore the use of an activator and / or a mixture of adhesion promoters (A) on the surface of a substrate (Sl) made of thermoplastic elastomeric polymer (TPE) comprising chains formed of alternating between hard segments and flexible segments or in homo or coPA PA, for bonding said substrate (Sl) to another substrate (S2).
• a substrate made of thermoplastic elastomeric polymer (TPE) comprising chains formed of alternating between hard segments and flexible segments or in homo or coPA PA, for bonding said substrate (Sl) to another substrate (S2).
• the use is characterized in that the adhesion promoter (A) is chosen from catalysts which are involved in chemical reactions involving isocyanate functions.
• the use is characterized in that the adhesion promoter (A) is chosen from amine, metal salt, organometallic type catalysts and mixtures thereof.
• the use is characterized in that the substrate (Sl) is chosen from (a) polyether block and polyether block copolymers, (b) polyurethane block and polyether block copolymers, (c) polyamide block copolymers and polyether blocks and mixtures thereof.
• the method of surface treatment of a substrate (Sl) made of thermoplastic elastomeric polymer (TPE) or of homo or copolymer polyamide in order to promote the attachment of a primer (P) and / or an adhesive (C) for bonding said substrate (S1) to another substrate (S2) is characterized in that an adhesion promoter (A) is applied to the substrate (S1).
• the method is characterized in that a solvent-based or aqueous-based adhesion primer (A) is used.
• FIG. 1 An adhesive (C) for sizing the substrate (S2).
• the structure of FIG. 1 represents a substrate (S1) adhered at its surface (F1) to a substrate (S2) at its surface (F2) by means of an adhesive (C) and a adhesion promoter according to the invention.
• FIGS 3 and 4 show embodiments of the invention in which the structures comprise in their primer layer (P) or in their adhesive layer (C) of the adhesion promoter (A).
• FIGS. 5 and 6 show a substrate S1 or a substrate S2 (designated S1, 2 in the figures) glued before docking with or without a primer.
• TPE Thermoplastic elastomeric polymers
• thermoplastic elastomer polymer is meant a block copolymer having, alternately, so-called hard or rigid blocks or segments and so-called flexible or flexible blocks or segments.
• hard block and flexible block copolymer there may be mentioned respectively (a) block copolymers of polyesters and polyether blocks (also known as polyetheresters), (b) polyurethane block copolymers and polyether blocks (also called TPU abbreviation for thermoplastic polyurethanes) and (c) polyamide block and polyether block copolymers (also called PEBA according to IUPAC).
• polyetheresters are block copolymers of polyesters and polyether blocks. They consist of flexible polyether blocks which are the residues of polyetherdiols and rigid segments (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 acid with the OH functions of the polyetherdiol.
• 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 wherein n is an integer of 2 to 10.
• 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 12 carbon atoms.
• aromatic dicarboxylic acids examples 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, the acid ethylene bis (para-oxybenzoic), 1,3-trimethylene bis (p-oxybenzoic acid).
• glycols 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 ether glycol (PO3G) or polytetramethylene glycol (PTMG), dicarboxylic acid units such as terephthalic acid and glycol (ethane diol) or butane diol units, 1-4.
• PEG polyethylene glycol
• PPG polypropylene glycol
• PO3G polytrimethylene ether glycol
• PTMG polytetramethylene glycol
• dicarboxylic acid units such as terephthalic acid and glycol (ethane diol) or butane diol units, 1-4.
• the linking of polyethers and diacids forms the flexible segments whereas the linking of the glycol or butanediol with the diacids forms the rigid segments of the copolyetherester.
• the polyamide blocks 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 distributed units. These polymers can be prepared by the simultaneous reaction of the polyether and the precursors of the polyamide blocks.
• polyetherdiol, polyamide precursors and a chain-limiting diacid can be reacted.
• a polymer having essentially polyether blocks is obtained, polyamide blocks of very variable length, but also the various reagents reacted randomly which are distributed randomly (statistically) along the polymer chain.
• Three types of polyamide blocks can advantageously be used.
• the polyamide sequences 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.
• dicarboxylic acids examples include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic and octadecanedicarboxylic acids, and terephthalic and isophthalic acids, but also dimerized fatty acids. .
• diamines examples include tetramethylene diamine, hexamethylenediamine, 1,10-decamethylenediamine, dodecamethylenediamine, trimethylhexamethylenediamine, 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 ⁇ sophoronediamine (IPDA), 2,6-bis- (amiomethyl) -norbornane (BAMN) and piperazine (Pip).
• BCM bis (4-aminocyclohexyl) methane
• BMACM bis - (3-methyl-4-aminocyclohexyl) methane
• BMACP 2-2-bis
• PA blocks 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 are used.
• the 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 dicarboxylic acid having from 4 to 12 carbon atoms or diamine.
• lactams examples include caprolactam, oenantholactam and lauryllactam.
• 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.
• 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 dicarboxylic acid.
• the polycondensation is carried out at a temperature of 180 to 300 ° C.
• 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 the PA blocks and the PE blocks is known and described, for example in the European patent EP 1 482 011.
• the formation reaction of the PA block is usually between 180 and 300 0 C, preferably from 200 to 290 ° C.
• the pressure in the reactor is between 5 and 30 bars, 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.
• 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 will also be possible during the synthesis, at the time deemed most appropriate, to add one or more molecules used as an antioxidant, for example Irganox® 1010 or Irganox® 245.
• 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.
• lactam By way of example of lactam, mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines mention may be made of hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• cycloaliphatic diacids By way of example of cycloaliphatic diacids, mention may be made of 1,4-cyclohexyldicarboxylic acid.
• aliphatic diacids 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 - ⁇ , ⁇ diacids.
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• 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).
• BAMN isophoronediamine
• BAMN 2,6-bis (aminomethyl) norbornane
• 6_ denotes patterns resulting from the condensation of caprolactam.
• 6.6 denotes hexamethylenediamine units condensed with adipic acid.
• Pip. 10 denotes units resulting from the condensation of piperazine and sebacic acid.
• the proportions 32/24/24 / lead to a melting temperature of 122 to 137 ° C. 6. 6/6. 10/11/12 in which
• 6.6 denotes hexamethylenediamine condensed with adipic acid.
• 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.
• the polyamide blocks are obtained in the presence of a diacid or a chain-limiting diamine if polyamide blocks with acid or amine ends are desired. If the precursors already comprise a diacid or a diamine, it suffices, for example, to use it in excess.
• the polyether blocks can represent 5 to 85% by weight of the polyamide and polyether block copolymer.
• the polyether blocks consist of alkylene oxide units. These patterns can for example, ethylene oxide units, propylene oxide units or tetrahydrofuran units (which leads to polytetramethylene glycol linkages).
• PEG blocks are thus used, that is to say those consisting of ethylene oxide units, PPG blocks, ie those consisting of propylene oxide units, glycol polytrimethylene ether units (such copolymers with polytrimethylene blocks).
• ether are described in US Pat. No. 6,590,665), and PTMG blocks, ie those consisting of tetramethylene glycol units also called polytetrahydrofuran units.
• PEG blocks or blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A are used. 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.
• ethoxylated primary amines mention may be made of the products of formula:
• NORAMOX® from CECA and under the GENAMIN® brand from CLARIANT.
• 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 with 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.
• the molar mass in number Mn of the polyamide sequences is between 500 and 10,000 and preferably between 500 and 4000 except for the polyamide blocks of the second type.
• the mass Mn of the polyether sequences is between 100 and 6000 and preferably between 200 and 3000.
• polymers with polyamide blocks and polyether blocks whether from the copolycondensation of previously prepared polyamide and polyether blocks or from a one-step reaction, have, for example, an intrinsic viscosity of between 0.8 and 2.5 measured in metacresol. at 25 ° C for an initial concentration of 0.8 g / 100 ml.
• the polyamide block and polyether block copolymers may be prepared by any means for hanging the polyamide blocks and the polyether blocks.
• essentially two methods are used, one said in two steps, the other in one step.
• the polyamide blocks are first produced and then, in a second step, the polyamide blocks and the polyether blocks are bonded.
• 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.
• the PEBA copolymers have PA blocks PA 6, PA 12, PA 6.6 / 6, PA 10.10 and PA 6.14 and PE blocks PTMG, PPG, PO3G and PEG.
• Sl is selected from the previously defined PTEs and polyamide homo and copolymers.
• Sl and S2 may be identical or different, but in this case S2 is chosen from the previously defined PTEs, homopolymers and copolymers such as polyolefins, polyamines, polyesters, polyethers, polyesterethers, 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, natural or synthetic fabrics, in particular organic polymeric fiber fabrics such as polypropylene, polyethylene, polyesters, polyvinyl alcohol, polyvinyl acetate, polyvinyl chloride, polyamide, fabrics made from fiberglass and carbon fiber, as well as materials
• adhesion primer it may be based on organic solvent (s) or aqueous based.
• adhesive it may be based on organic solvent (s) or aqueous based.
• adhesion primer (P) based on solvent (s) or on a water-based base with a glue (C) based on solvent (s) or on aqueous base, knowing that the adhesion promoter ( A) can be either:
• the adhesion promoter (A) can be combined for the application of a adhesion primer (P) based on solvent (s) with low adhesion power but based on organic component (s) volatile (s) (abbreviated V.0.C) reduced (s) or water-based with a glue (C) based on solvent (s) or water-based.
• a adhesion primer P
• V.0.C organic component
• glue C
• the adhesion promoter (A) is advantageously chosen to be able to activate the surface of the substrate (Sl):
• the adhesion promoter (s) (A) may be able to react hot or cold.
• Cleaning solutions are those generally used to remove impurities, greases, foreign agents that can alter the adhesion of primers (P) and / or adhesives (C) to substrates.
• cleaning solutions may also contain additives such as wetting agents or detergents to promote the removal of pollutants and / or to improve the wettability of the supports.
• water-based cleaning solutions based on aliphatic organic solvents or based on aromatic solvents and their mixtures consisting of 2 or the 3 preceding solvents.
• 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 e.g ethyl ethers, THF, dioxane
• Aromatic Hydrocarbons (benzene, toluene, xylene, cumene).
• Petroleum solvents excluding aromatics: alkanes, alkenes.
• Organic solvents or water-based solutions based on organic solvents will be carefully chosen to minimize solvent emissions, reduce toxicity and ecotoxicity risks, and promote good solubility of the solvent. adhesion promoter and stability of the mixtures.
• the adhesion promoters (A) are chosen from the catalysts used in the chemical reactions involving the isocyanate functional groups. Mention may in particular be made of amine-type catalysts (secondary or tertiary amines), of the metal salt type or of the organo-metallic type.
• API 1- (3-aminopropyl) imidazole
• NMI N-methylimidazole
• DI 1,2-dimethylimidazole
• DABCO 1,4-diazol
• catalysts based on metal salts include those based on: Bi, Pb, Sn, Ti, Fe, Sb, U, Cd, Co, Th, Al, Hg, Zn, Ni, R 3 N, Ce, Mo, V, Mn, Zr, R 3 P.
• organo metallic are characterized by the association of metal bonding organic segments. Without being exhaustive, we quote for example:
• Dabco T12 Dabco T12
• Fomrez SUL-4 Fascat 4202
• Dabco T9 Dabco T9
• Fomrez C-2 and Cata Chek.
• the adhesion promoter (A) is present at 0.001 to 8%, preferably from 0.001 to 4% by weight relative to the total weight of the medium in which it is found to be the polymer or the coating (cleaning solution, primary and / or glue).
• Table 1 illustrate the present invention without, however, limiting its scope. In the examples, the following abbreviations are used.
• PEBA of PA12-PTMG type polyamide 12 - polytetramethylene glycol
• ARKEMA marketed by ARKEMA under the name "PEBAX® 5533”.
• PEBA of PA12-PTMG type polyamide 12 - polytetramethylene glycol
• ARKEMA marketed by ARKEMA under the name "PEBAX® 7033”.
• PEBAX® 7033 is harder than PEBAX® 5533.
• W104 water-based primer marketed by the company DONGSUNG under the name "Aquace® W104".
• (Dry extract - 30 min at 150 ° C. 40% by weight)
• (Dry extract - 30 min at 150 ° C. 83.5% by weight)
• Borchi Kat24 from Borchers Company is a Bismuth Carboxylate (Organo Metallic).
• Borchi KatVP244 from Borchers is a mixed Zinc and Bismuth Carboxylate (Organo Metallic).
• the substrates (Sl) and (S2) are plates of dimensions 100 x

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