Classifications

• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
  • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
  • C08G69/36—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino acids, polyamines and polycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
  • C08G69/40—Polyamides containing oxygen in the form of ether groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/005—Synthetic yarns or filaments
  • D04H3/009—Condensation or reaction polymers
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
  • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/04—Antistatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
  • C08L77/12—Polyester-amides

Definitions

• the present invention relates to a new process for manufacturing nonwoven surfaces.
• It relates more particularly to a process for manufacturing non-woven aces by the direct spinning process of continuous filaments arranged in the form of a sheet.
• Nonwoven surfaces are very widely used in numerous applications such as the production of surface coatings, for example. These surfaces are obtained according to several methods, such as the wet method which consists in suspending fibers in a liquid advantageously containing a product allowing the binding. These fibers are received on a collecting surface to produce a sheet which is calendered and dried to form the nonwoven surface.
• Another process also used is called the dry process. This process consists in forming a sheet with cut fibers, carded and put in the form of a veil, then the sheet is treated to give it cohesion. By this dry route, it is also possible to manufacture plies from continuous threads or filaments.
• This process consists in extruding one or more polymers through one or more dies to obtain several filaments which will be drawn by pneumatic means and deposited on a collecting surface to form a sheet.
• the cohesion of this sheet can be obtained by various methods such as impregnation with a resin or by thermobinding. In this case, some filaments are made from a polymer with a lower melting or softening point than those of other filaments. Cohesion is then obtained by heat treatment of the sheet.
• One of the aims of the present invention is, in particular, to remedy these drawbacks by proposing the use of a composition based on thermoplastic polymers, the composition having electrical conductive properties making it possible to avoid the disturbing effect of electrostatic charges.
• the present invention provides a method of manufacturing nonwoven surfaces by direct melt spinning of filaments of a composition based on thermoplastic polymers comprising a supply of the composition in a plurality of dies each comprising several spinning orifices.
• thermoplastic polymers supplied in the dies comprises a polymer matrix and / or an additive modifying polymer comprising recurring units corresponding to the following general formulas:
• Ri, R2, R3, R4 different or identical represent aliphatic, cycloaliphatic or aromatic hydrocarbon chains comprising from 2 to 18 carbon atoms
• R 5 represents a polyether radical of molecular weight between 400 and 200,000.
• a and B represents the groups CO, NH or O, when A represents CO, B represents NH or O and vice versa, and in that the polymer matrix comprises at least one of the repeating units I or II and at least one of the recurring units III or
• compositions have a volumetric electrical conductivity greater than or equal to 1.10 "9 S / cm, preferably between 5.10 " 9
• compositions having a volumetric electrical conductivity different from the above range for example less than 1.10 " 9
• the method of manufacturing the filaments can comprise a feeding of each filament into the pneumatic drawing device or a convergence of groups of filaments to form several multifilament threads which are fed into the pneumatic drawing device and then placed on a receiving surface to form a tablecloth.
• the filaments are made of an electrically conductive polymer composition, the electrostatic charges generated at the surface of the filaments between the die and the step of forming a sheet are removed very quickly.
• the filaments remain parallel to each other and can be entrained throughout the device before forming a sheet without dispersion and deviation from their path of travel.
• the compositions of the invention also make it possible to limit the formation of these electrostatic charges and therefore to limit the effects of dispersion of the filaments or of adhesion of these to the metal walls of the spinning apparatus and of production of the sheet.
• conductive polymer or composition should be understood to mean polymers or compositions which have a structure or components which confer a higher electrical conductivity than that of unmodified polymers or compositions. However, the level of the conductivity remains low and in particular allows the evacuation of the electrostatic charges which can form during the shaping of these polymers or compositions.
• thermoplastic polymers suitable for the invention are advantageously thermoplastic polymers belonging to the family of polyamides and polyesters.
• polyesters suitable for the process of the invention mention may be made of the conductive copolyesters obtained by polymerization of diacid and diol monomers, the diols being constituted by a mixture of alkylenediols such as glycol, butanediol or propanediol, with a polyoxyalkylenediol.
• thermoplastic polyamides suitable for, in particular, the first embodiment of the invention mention may be made of the copolyamides obtained by polymerization of usual diacid, diamine or lactam monomers.
• monomers having a particular structure are added to the usual monomers.
• These monomers advantageously have ether bridges in their structure and are preferably compounds containing a polyoxyalkylene chain and having reactive terminal functions before the functions of the other monomers, such as for example, amino, acid or hydroxyl functions.
• Such compounds comprising amino functions are in particular marketed by the company HUNTSMAN under the name JEFFAMINES.
• the thermoplastic polymer is, advantageously, a copolyamide comprising repeating units having polyoxyalkylene chains making it possible to obtain an increase in the electrical conductivity of the usual polyamides such as polyamide
• thermoplastic polymer of the first embodiment of the invention is a copolyamide comprising recurring units corresponding to general formulas I or II and III or IV
• the repeating unit of formula I corresponds to the product of the polymerization reaction between a diacid chosen from the group comprising succinic acid, adipic acid, terephthalic acid, isophthalic acid, decandioic acid, dodecandioic acid or their mixtures, and a diamine chosen from the group comprising hexamethylene diamine, 2-methyl pentamethylene diamine, metaxylilene diamine or their mixtures. This list is not exhaustive and other diacids or diamines may be used.
• the recurring unit of formula II corresponds to the polycondensation product of lactams or amino acids chosen from the group comprising caprolactam, aminoundecoic acid, aminododecanoic acid or mixtures thereof. Likewise, this list is not exhaustive and other lactams or amino acids can be used.
• the weight concentration of the recurring units of formula III or / and IV is between 0.5 and 5% by weight of all of the recurring units or of the mass of the polymer.
• Conductive polyamides meeting the above definition are described, for example, in patent application WO 94/23101. These polyamides are obtained using in particular as main and usual monomer lactams or amino acids such as for example, caprolactam, aminoundecanoic acid, aminododecanoic acid.
• the conductive thermoplastic polyamides can also be obtained by polymerization of a diamine such as hexamethylene diamine with a diacid such as adipic acid in the presence or not of a catalyst according to the conventional polymerization processes used for the manufacture of polyamide 6.6, for example.
• the polyoxyalkylene diamine monomer is added to the polymerization medium, either at the start with the diamine, diacid monomers or the salt formed by the diacid and diamine monomers or during the polymerization process such as, for example, before or during the step of evacuating the polymer to obtain the desired degree of polymerization.
• the composition comprises as majority or single component, the conductive thermoplastic polymer.
• the usual additives can be present, such as heat stabilization additives, additives for improving the resistance of the polymer to aging, such as anti-UV additives, pigments, dyes, matifiers, nucleators, or the like.
• the composition based on a thermoplastic polymer comprises a thermoplastic polymer and a modifying polymer additive making it possible to improve the electrical conductivity of the composition.
• This additive comprises in its structure at least one polyoxyalkylene chain.
• This additive will be called in the following text conductive additive for clarity and conciseness.
• the concentration of polymeric additive modifying in the composition is between 1% and 30% by weight relative to the weight of total composition, advantageously between 1% and 15% by weight. weight.
• the modifying polymer additive has a melt viscosity advantageously lower than that of the polymer matrix.
• the additive migrates to the surface of the wire.
• the surface properties of the latter are modified, in particular its properties of electrical conductivity.
• the compositions of this second embodiment of the invention are advantageously obtained by mixing the thermoplastic polymer with the modifying polymer additive and optionally other additives such as those listed above. This mixing can be carried out by all the conventional methods.
• One of the preferred methods is a mixture of these components in a worm comprising one or more screws and extruding through a die to form a rod. This rod is then cut to obtain granules of desired size and weight. These granules are used and fed, possibly after drying, in the installation for spinning and manufacturing nonwoven surfaces.
• polymeric modifier additive pure or in the form of a concentrated solution in a host polymer (masterbatch), in the molten thermoplastic polymer just before feeding. in the nonwoven spinning sector.
• the modifying polymer additive according to the invention advantageously comprises a thermoplastic structure, preferably of a similar nature to the structure of the thermoplastic polymer of the composition, and a structure comprising polyoxyalkylene chains.
• the thermoplastic structure can be a polyester or polyamide structure.
• polyesters as modifying polymer additives for the process of the invention, there may be mentioned the copolyesters obtained by polymerization of diacid monomers and diols, the diols being constituted by a mixture of alkylenediols such as glycol, butanediol or propanediol, with a polyoxyalkylenediol.
• polyamides suitable as modifying polymeric additives of the invention mention may be made of the copolyamides obtained by polymerization of usual diacid, diamine or lactam monomers . .
• monomers having a particular structure are added to the usual monomers.
• These monomers advantageously have ether bridges in their structure and are preferably compounds containing a polyoxyalkylene chain and having reactive terminal functions before the functions of the other monomers, such as for example, amino, acid or hydroxyl functions.
• Such compounds comprising amino functions are in particular marketed by the company HUNTSMAN under the name JEFFAMINES.
• the conductive or modifying polymer additive is obtained by polymerization of the monomers of the following formulas:
• Ri, R2, R3, different or identical represent aliphatic, cycloaliphatic or aromatic hydrocarbon chains comprising from 2 to 18 carbon atoms
• R 5 represents a polyether radical of molecular weight between 400 and 200,000
• B represents the COOH, NH 2 or OH functions, in the presence of a monofunctional chain-limiting compound.
• the polymerization is carried out in the presence of monofunctional compounds, limiting the length of the chains, according to known methods of manufacturing polymers.
• monofunctional compounds there may be mentioned monofunctional acids, monofunctional amines.
• acetic acid, propionic acid, benzylamine are preferred compounds.
• the concentration by weight of the monomers of formula VIII in the mixture of monomers is between 1 and 20% by weight of all the monomers, advantageously between 1% and 10%.
• Polyamides meeting the above definition are described, for example, in patent application WO 94/23101. These polyamides are obtained using in particular as main and usual monomer lactams or amino acids such as for example, caprolactam, aminoundecanoic acid, aminododecanoic acid.
• the modifying conductive or polymeric additive is advantageously a compound consisting of: at least one thermoplastic block and V at least one polyoxyalkylene block
• this compound comprises:> At least one thermoplastic polymer block formed by: A star or H macromolecular chain comprising at least one multifunctional heart and at least one branch or segment of thermoplastic polymer connected to the heart, the heart comprising at least three functions identical reagents and / or A linear macromolecular chain comprising a difunctional core and at least one segment of thermoplastic polymer connected to the core and At least one polyoxyalkylene block connected to at least part of the reactive ends of the block of thermoplastic polymer
• this compound comprises a block of thermoplastic polymer and at least one block of polyoxyalkylene.
• the thermoplastic polymer block comprises:> a star or H macromolecular chain comprising at least one multifunctional core and at least one branch or segment of thermoplastic polymer connected to the core, the core comprising at least three identical reactive functions and / or a chain linear macromolecular comprising a difunctional core and at least one segment of thermoplastic polymer connected to the core
• the polyoxyalkylene block or blocks are connected to at least part of the free ends of the thermoplastic polymer block in the following manner: at least one free end of the star or H macromolecular chain, chosen from the ends of a branch or segment of thermoplastic polymer and the ends of the multifunctional core, is connected to a polyoxyalkylene block and / or> at least one free end of the linear macromolecular chain, chosen from segment ends of thermoplastic polymer and the ends of the difunctional heart, is connected to a block of polyoxyalkylene; the two free ends of the linear
• This star polyamide is obtained by copolymerization from a mixture of monomers comprising: a) a multifunctional compound comprising at least three identical reactive functions chosen from the amine function and the carboxylic acid function b) monomers of general formulas (Xa) and / or (Xb) following:
• Z represents a function identical to the reactive functions of the multifunctional compound> Ri2
• R ⁇ represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, substituted or not, identical or different, comprising from 2 to 20 atoms of carbon, and possibly comprising heteroatoms
• Y is a primary amino function when X represents a carboxylic acid function
• Y is a carboxylic acid function when X represents a primary amino function
• carboxylic acid is meant carboxylic acids and their derivatives, such as acid anhydrides, acid chlorides, esters etc.
• amine is meant amines and their derivatives.
• star polyamides Processes for obtaining these star polyamides are described in patents FR 2,743,077 and FR 2,779,730. These processes lead to the formation of star macromolecular chains, possibly mixed with linear macromolecular chains.
• This star polyamide can also be obtained by melt-blending, for example in a worm-screw mixing system, of a polyamide of the type of those obtained by polymerization of lactams and / or amino acids, and of a multifunctional compound comprising at least three identical reactive functions chosen from the amine or carboxylic acid function.
• the polyamide is, for example, polyamide 6.
• Such processes for obtaining are described in patents EP 0.682.070 and EP 0.672.703.
• the multifunctional compounds, monomers at the origin of the star or H macomolecular chains of the first subject of the invention can be chosen from the compounds having a tree or dendritic structure. They can also be chosen from the compounds represented by formula (XI):
• RÎT -Q- (XI) m in which: • Ru is a hydrocarbon radical comprising at least two linear or cyclic, aromatic or aliphatic carbon atoms and which can comprise heteroatoms, • Q is a covalent bond or an aliphatic hydrocarbon radical comprising 1 to 6 carbon atoms, • Zi represents a primary amino radical or a carboxylic acid radical • m is an integer between 3 and 8. According to a particular characteristic of the invention, the radical Ru is either a cycloaliphatic radical such that the tetravalent radical of cyclohexanonyl, that is to say a radical 1, 1, 1 - triyle-propane, 1, 2,3-triyle-propane.
• radicals Rn suitable for the invention there may be mentioned, by way of example, trivalent phenyl and cyclohexanyl radicals, substituted or not, tetravalent diaminopolymethylene radicals with a number of methylene groups advantageously between 2 and 12 such as radical from EDTA
• the radical Q is preferably a methylene or polymethylene radical such as the ethylene, propylene or butylene radicals, or a polyoxyalkylene radical such as the polyoxyethylene radical.
• the number m is greater than or equal to 3 and advantageously equal to 3 or 4.
• the reactive function of the multifunctional compound represented by the symbol L ⁇ is a function capable of forming an amide function.
• polyfunctional compounds mention may be made of 2,2,6,6-tetra- ( ⁇ -carboxyethyl) cyclohexanone, diaminopropane - N, N, N ', N' tetraacetic acid of the following formula:
• nitrilotrialkylamines in particular nitrilotriethylamine, dialkylenetriamines, in particular diethylenetriamine, trialkylenetetramines and tetraaikylenepentamines, the alkylene preferably being ethylene, 4-aminoethyl-1, 8, octanediamine.
• n is preferably an integer equal to 3 or 4, in particular 3, and x is preferably an integer between 2 and 6 limits inclusive, preferably between 2 and 4 limits inclusive, in particular equal to 2.
• Each radical R 10 can be chosen independently of the others.
• the radical R 10 is preferably a hydrogen atom or a group - (CH 2 ) n -NH 2 .
• multifunctional compounds having 3 to 10 carboxylic acid groups preferably 3 or 4.
• compounds having an aromatic and / or heterocyclic ring for example benzyl, naphthyl, anthracenyl, biphenyl and triphenyl, or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoleine, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine.
• 3,5,3 ', 5'-biphenyltetracarboxylic acid acids derived from phthalocyanine and naphthalocyanine, 1, 3,5,7-naphthalenetetracarboxylic acid, acid 2,4, 6- pyridinetricarboxylic, 3,5,3 ', 5'-bipyridyltetracarboxylic acid, 3,5,3', 5'- benzophenonetetracarboxylic acid, 1, 3,6,8-acridinetetracarboxylic acid, more particularly still trimesic acid and 1,2,4,5-benzenetetracarboxylic acid.
• multifunctional compounds whose core is a heterocycle presenting a point of symmetry such as 1, 3,5-triazines, 1, 4-diazines, melamine, compounds derived from 2,3,5,6-tetraethylpiperazine, 1, 4-piperazines, tetrathiofulvalenes. Mention is more particularly made of 2,4,6-triaminocaproic acid-1,3,5-triazine (TACT).
• TACT 2,4,6-triaminocaproic acid-1,3,5-triazine
• the multifunctional compounds are chosen from 2,2,6,6-tetra- ( ⁇ -carboxyethyl) -cyclohexanone, trimesic acid, 2,4,6-tri- (aminocaproic acid) -1, 3,5-triazine and 4-aminoethyl-1, 8-octanediamine.
• the mixture of monomers at the origin of the star or H macromolecular chains of the invention may comprise other compounds, such as chain limiters, catalysts, additives, such as light stabilizers, thermal stabilizers, matifiers .
• the composition comprises as essential components a usual thermoplastic polymer such as a polyamide, polyester, and a conductive additive as described above.
• a usual thermoplastic polymer such as a polyamide, polyester, and a conductive additive as described above.
• suitable thermoplastic polymers mention may be made of polyamide 6, polyamide 6.6, their mixtures and copolyamides, polyamide 12, polyethylene glycol, polypropylene glycol, polybutylene glycol, their mixtures and copolyesters.
• the composition may comprise other components usually used in the manufacture of yarns or fibers such as heat stabilization additives, additives for improving the resistance of the polymer to aging, such as anti additives -UV, pigments, dyes, matifiers, nucleating agents.
• the nonwoven articles formed from the thermoplastic polymer compositions are produced by a conventional method of extruding the molten polymer composition through one or more dies to form a set of filaments. Such methods are described in particular in American patents 3,968,307; 4052146, 4406850, 4424257, 4424258, 4830904, 5534339, 5783503, 5895710, 6074590 and 6207276.
• the filaments are pneumatically stretched and deposited on a collective surface to form a sheet.
• the connection of the filaments of the sheet is carried out by any known means.
• the filaments leaving the dies remain parallel to each other and can be deposited after stretching on the surface in a homogeneous manner and with a regular distribution. Indeed, no repulsion is observed between the filaments and therefore no deviation from the direction of travel of the filaments.
• the filaments can have very varied cross-sectional shapes.
• one of the thermoplastic polymers must be a conductive polymer according to the invention.
• Examples 1 The manufacture of a polyamide PA 6.6 is carried out by adding to a polymerization reactor 3149 g of dry nylon salt (salt obtained by stoichiometric reaction between a molecule of adipic acid and a molecule of hexamethylene diamine) in 2941 g of water with 0.21 g of pure copper acetate monohydrate powder, 7.56 g of potassium bromide powder at 99.5% purity by weight, 3.96 g of phenylphosphonic acid at 98% purity by weight.
• dry nylon salt salt obtained by stoichiometric reaction between a molecule of adipic acid and a molecule of hexamethylene diamine
• This reaction mixture is heated to 112 ° C: the autogenous pressure of 1.2 bar absolute is then regulated to this value by distillation of water during a concentration phase until a temperature of 120 ° is obtained. vs. The reaction mixture is then heated to 215 ° C without distillation of water. At this temperature, the autogenous pressure reaches a value of 17.5 bar absolute and is regulated to this value by distillation of water during a pressure distillation phase until a temperature of 230 ° C. is obtained. When the temperature of the reaction mixture reaches a value of 220 ° C. during this distillation phase under pressure, 13.6 g of an aqueous suspension of titanium dioxide at 5% by weight are added.
• the pressure is reduced to atmospheric pressure during a decompression phase at the end of which the temperature of the reaction mixture reaches the value of 275 ° C.
• the reaction mixture is maintained at 275 ° C. in the finishing phase for 10 minutes: the polymer is then poured in the form of a rod, cooled and granulated by cutting the rods.
• the viscosity index of the polymer A obtained, determined from the granules, is 140 ml / g. It is determined by the implementation of the standardized method ISO EN 307.
• the amino and acid terminal groups are respectively measured at 43 and 76 meq / kg by potentiometry in a trifluoroethanol / chloroform solvent medium (50/50 by volume).
• the manufacture of a conductive copolyamide in accordance with the first embodiment of the invention is carried out using the procedure of Example 1a by additionally adding 3.57 g of pure adipic acid powder to the initial mixture of Nylon salt and 77.59 g of an aqueous solution of JEFFAMINE ED 2003 or XTJ - 502 to 70% by weight when the temperature of the reaction mixture reaches a value of 260 ° C during the decompression phase. Furthermore, the duration of the finishing phase is 45 minutes.
• the viscosity index of the copolymer obtained determined according to the method described in Example 1 is 139 ml / g.
• the amino and acid terminal groups are respectively measured at 43 and 77 meq / kg by potentiometry in a trifluoroethanol / chloroform solvent medium.
• the copolymer B obtained contains 2% by weight of repeating units corresponding to general formula III, that is to say to the JEFFAMINE monomers
• the manufacturing process is reproduced in an identical manner to Example 2 by introducing in this case 8.93 g of pure adipic acid powder and 193.98 g of an aqueous solution of Jeffamine ED 2003 or XTJ - 502 to 20 % in weight.
• the viscosity index of the polymer is 125 ml / g.
• the amino and acid terminal groups are respectively measured at 50 and 85 meq / kg by potentiometry in a trifluoroethanol / chloroform solvent medium.
• the copolymer C obtained contains 5% by weight of repeating units corresponding to the general formula III, that is to say to the JEFFAMINE monomers
• the reaction is carried out in a 7.5 liter autoclave. 1116.0 g of epsilon-caprolactam (9.86 mol), 57.6 g of 1,3,5-benzene tricarboxylic acid (0.27 mol), 1,826.4 g of JEFFAMINE® M2070 (0.82 mol ), 1.9 g of ULTRANOX® 236 and 3.5 g of a 50% aqueous solution (w / w) of hypophosphorous acid are introduced into the reactor. The autoclave is purged with dry nitrogen. The reactor is maintained under a light sweep of dry nitrogen. The reaction mass is gradually heated from 20 ° C to 200 ° C. The temperature of the reaction medium is then brought to 250 ° C.
• the assays of terminal groups show a content of residual acid functions of 16.8 meq / kg and of residual amino functions of 1.9 meq / kg.
• the 1 H NMR (Bruker 300 MHz) of a solution in a 1/1 mass mixture of deuterated trifluoroacetic acid and deuterated chloroform shows a residual content of caprolactam zero (not detectable) and an average degree of polycondensation of block PA6 of 8 , 4 by branches of the star. This additive is called Additive I.
• Example 5 manufacture of a composition D according to the invention
• Example 2 The procedure described in Example 2 is reproduced. However, pure adipic acid powder is not introduced. Furthermore, instead of the solution of Jeffamine ED 2003, 271.2 g of an aqueous solution at 20% by weight of the conductive additive I prepared according to Example 4 are introduced in this case. finish is 15 minutes.
• the viscosity index of the composition thus obtained and therefore of the thermoplastic polymer contained in the composition, determined according to the method indicated above is 149 ml / g.
• the amino and acid terminal groups are respectively measured at 39 and 71 meq / kg by potentiometry in a trifluoroethanol / chloroform solvent medium.
• Composition D thus prepared contains 2% by weight of conductive additive.
• Example 6 manufacture of a composition E according to the invention
• the manufacturing process is reproduced in an identical manner to Example 5 by introducing in this case 678 g of an aqueous solution at 20% by weight of conductive additive I produced according to Example 4.
• the finishing time is limited to 10 minutes.
• the viscosity index of the composition thus obtained and therefore of the thermoplastic polymer contained in the composition, determined according to the method indicated above is 152 ml / g.
• the amino and acid terminal groups are respectively measured at 40 and 71 meq / kg by potentiometry in a trifluoroethanol / chloroform solvent medium.
• Composition E thus prepared contains 5% by weight of conductive additive.
• Example 7 The compositions or polymers A, B, C, D, E made in the above examples are respectively dried and then remelted at 295 ° C and extruded through a die at a speed of 450 m / min and a mass flow rate of 430 g / h to form filaments of 12 dtex titer and combined to form threads comprising 14 filaments.
• the wires are drawn on a drawing bench according to a drawing ratio equal to 3.5 to lead respectively to the wires marked 7a, 7b, 7c, 7d
• the volume conductivity of these wires is measured according to the following protocol:
• the measurement of the Volume Conductivity of textile threads is carried out according to the so-called '2-point' measurement method.
• Several wires are arranged in parallel over a given length between conductive pads according to the diagram shown in Figure 1 attached.
• the measurement is carried out between two steel studs 1 20 mm apart.
• the number of wires going back and forth is generally 5, or 10 rows of wires in total (which corresponds exactly to 100 filaments, 1 wire being made up of 10 elementary filaments).
• the diameter of the studied wire is measured using a binocular magnifying glass, its exact length being measured with the caliper.
• the measurements are carried out on a KEITHLEY 617 conductivity meter, with an applied voltage of 100 volts, under temperature conditions of 20 ° C. and relative humidity of 50%.
• the electrical volume resistance is obtained by direct reading on the device.
• volume Conductivity ⁇ (unit: S. cm “1 or ⁇ " 1 .cm “1 ) is exactly the opposite of the Volume Resistivity.
• volume conductivity values found for these different wires are collated in the table below:
• polymers B and D make it possible to obtain a satisfactory behavior of the filaments by comparison with a behavior of repulsion of the filaments obtained by spinning of polymer A during the step of depositing the filaments in a web on a support surface, after the pneumatic drawing device.
• EXAMPLE 8 Manufacture of an Additive II in Accordance with the Invention
• a copolymer based on polyamide 6-6 is produced from 240.2 g of an aqueous solution of a hexamethylene diammonium salt concentrated to 64% by weight and to which are added: 6 mg of antifoam 12.945g of Jeffamine ED 600 (sold by the company Huntsmann) 3.453g of adipic acid. 0.345 g of acetic acid.
• the polyamide is manufactured according to the standard polymerization process comprising a step of concentrating the solution followed by a polycondensation step in a stirred autoclave reactor, with a phase of approximately 47 min of distillation under a pressure bearing of 17.5 bars for which the final temperature is 250 ° C, a decompression phase of approximately 36 min from 17.5 bars to 1 bar at final temperature of 273 ° C and a finishing phase of approximately 20 min for which the temperature final is 272 ° C.
• a copolymer based on PA6.6 with a viscosity index of 73 ml / g is obtained.
• Example 9 manufacture of an additive III according to the invention
• a polyamide 6-6 copolymer is made from 240.2 g of an aqueous solution of a hexamethylene diammonium salt concentrated to 64% by weight and to which are added: 5 mg of antifoam
• the polyamide is produced according to the following process in a stirred autoclave reactor: a step of concentrating the solution followed by a polycondensation step, with a phase of approximately 47 min of distillation under a bearing at a pressure of 17.5 bars for which the final temperature is 250 ° C.
• the polymerization is continued by a decompression phase from 17.5 bars to 1 bar which is interrupted at 10 bars in order to introduce 18.5 g of an aqueous solution of Jeffamine ED 2003 (sold by the company Huntsmann) at 70%, the mass temperature is maintained at 260 ° C.
• the decompression is complete, the decompression phase lasts about 50 minutes, the final temperature is 272 ° C.
• the finishing phase lasts about 20 min, the final temperature is 272.4 ° C.
• a copolymer based on PA6.6 with a viscosity index of 72 ml / g is obtained.
• Tests for carrying out the manufacture of fibers or threads were carried out using the polymer A of Example 1 without additive in accordance with the invention and with different concentrations of the additives II and III described in Examples 8 and 9, as indicated in table 1 below.
• additive II or III is added to polymer A in a single-screw extruder and extruded in the form of rods to form granules by cutting rods, according to known techniques.
• the compositions or polymer thus obtained are respectively dried then remelted at 295 ° C. and extruded through a die comprising 34 holes of 0.23 mm in diameter.
• the speed of the composition in the die holes is 19.4 m / min.
• the filaments are cooled at the outlet of the die by a cold air blower.
• the filaments are sucked into a suction system constituted by a launching gun usually used in spinning processes.
• the filaments are discharged from this pistol at a speed of 4000 m / min.
• the filaments undergo
• the jet of filaments is directed vertically on the surface of a cardboard inclined at approximately 45 ° to the vertical.
• the attachment of filaments to the surface of the cardboard is an indication of the presence of electrostatic charges.
• the electrostatic field present near the jet of filaments exiting the gun is also determined by positioning a staticmeter (device sold under the name Staticmeter model 212 by the company ELECTRO TECH-SYSTEMS), about 3 cm (1 inch) from the axis of the jet of filaments. This appliance is either earthed or not connected. Measurements are made in both configurations. The absence of electrostatic charges results in an electrostatic field close to zero.
• the results obtained with the compositions of the invention and a polyamide without additive are indicated in the table below:

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