Classifications

• • D—TEXTILES; PAPER
  • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
  • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
  • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
  • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
• • 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
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/02—Polyalkylene oxides
• • 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
• • 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
  • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
  • D01F6/82—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from polyester amides or polyether amides
• • 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
• • 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
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/12—Copolymers
  • C08G2261/126—Copolymers block
• • 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
  • Y10T428/249921—Web or sheet containing structurally defined element or component
• • 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.]
  • Y10T442/30—Woven fabric [i.e., woven strand or strip material]
• • 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.]
  • Y10T442/40—Knit fabric [i.e., knit strand or strip material]
• • 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.]
  • Y10T442/50—FELT FABRIC
  • Y10T442/56—From synthetic organic fiber
• • 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.]
  • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]

Definitions

• the subject of the present invention is a refreshing textile material, comprising synthetic fibers made of elastomeric thermoplastic polymer.
• Texttile or “textile” means any material made from fibers or filaments and any material forming a porous membrane characterized by a length / thickness ratio of not less than 300;
• Fiber means any synthetic or natural material characterized by a length / diameter ratio of not less than 300;
• filament means any fiber of infinite length
• Textiles include fiber mats (dressings, filters, felt), wicks (dressings), threads (sewing, knitting, weaving), nonwovens, web veils "Nets, (net), knits (straight, circular, fullyfashioned) fabrics (traditional, jacquard, multiple, double sided, multi axial, 2D and a half, 3D), and many others.
• Synthetic fibers made of thermoplastic polymer currently used to make cooling textiles have several disadvantages: they tend to swell when they are impregnated with an aqueous medium and their cooling capacity is not sufficiently intense or durable. It is therefore necessary to modify these fibers or textiles obtained from these fibers so that they acquire a detectable or sufficient cooling capacity.
• the methods used consist either in performing a chemical surface treatment of the textile, or more commonly in adding an absorbent polymer to the fiber matrix.
• This polymer Absorbent has the ability to increase its volume by absorbing water to form a gel that restores a cooling effect by natural evaporation of water, after which the gel returns to its original volume.
• the cold produced is a "wet” cold, giving an uncomfortable "wet” sensation, even sticky.
• Absorbents commonly used are, for example, polyacrylate crystals, especially crosslinked sodium polyacrylates.
• the level of stability of these cooling agents is not guaranteed. Their denaturation can be observed at temperatures above 100 ° C., and sometimes at temperatures of the order of 40 or 60 ° C. Textiles comprising these agents should not be machine washed but by hand, with detergent or frozen products.
• the object of the present invention is therefore to provide cooling textile materials with an intense and lasting cold effect, which have a sufficient level of stability with respect to water (do not swell on contact with water) and with respect to temperatures ( can withstand ambient temperatures in the range of -60 ° C to 150 ° C, preferably -40 ° C to 140 ° C.
• the object of the present invention is in particular to provide a simple method of manufacturing such textile materials, comprising as few steps as possible, which does not alter the dimensional stability or the flexibility of the textile materials, nor their softness, and which makes use of preferably bio-sourced raw materials.
• the subject of the present invention is therefore the use of a hydrophobic polyether block and polyamide block copolymer (PEBA) for the manufacture of a textile material (of melting temperature Tf) capable of cooling after contacting said material with an aqueous medium having a temperature in the range of 15 ° C to Tf-20 ° C, said medium comprising at least 85% by weight of water relative to the weight of aqueous medium, preferably at least 90% of water, preferably at least 95% water relative to the weight of medium; said PEBA comprising from 20 to 80% by weight of polyamide blocks and from 80 to 20% by weight of polyether blocks, preferably from 30 to 70% by weight of polyamide blocks and from 70 to 30% by weight of polyether blocks, and having a saturation water absorption of less than 6% by weight, preferably less than 3%, according to ISO 62, relative to the weight of PEBA.
• PEBA hydrophobic polyether block and polyamide block copolymer
• said textile material is such that it cools to a temperature below room temperature for at least 15 minutes after said contacting, preferably for at least 30 minutes, preferably for at least one hour, preferably during at least two hours, the ambient temperature being in the range of 10 to 80 ° C, preferably 10 to 50 ° C, preferably 15 to 40 ° C.
• said material is such that it has accelerated and prolonged desorption and evaporation properties of said aqueous medium in the form of cold gas with a temperature below room temperature, preferably below 20 ° C.
• said material is in the form of a porous membrane, a woven fabric or a nonwoven fabric.
• said material comprises fibers and / or filaments and / or particles based on said PEBA.
• the present invention also relates to a method for cooling the skin of a human being, comprising the application on said skin of a cooling textile material impregnated with an aqueous medium, either naturally (for example by sweat) or by voluntary supply (for example water, an active ingredient, in particular a cosmetic, pharmaceutical or medical ingredient, a moisturizer, etc.), said material comprising at least 10% by weight, preferably at least 30% by weight, preferably at least 50% by weight, preferably at least 80% by weight, ideally 100% by weight, of a hydrophobic polyether block and polyamide block copolymer (PEBA); said material having a melting temperature Tf such that Tf-20 ° C is higher than the ambient temperature; said PEBA comprising from 20 to 80% by weight of polyamide blocks and from 80 to 20% by weight of polyether blocks, preferably from 30 to 70% by weight of polyamide blocks and from 70 to 30% by weight of polyether blocks, by relative to the weight of PEBA, and having a saturation water absorption of less than 6% by weight, preferably less than 3%
• the subject of the present invention is also a textile material, in particular useful for the implementation of this cooling process, characterized in that it comprises a hydrophobic polyether block and polyamide block copolymer (PEBA) comprising from 20 to 80% by weight. weight of polyamide blocks and 80 to 20% by weight of polyether blocks, preferably 30 to 70% by weight of polyamide blocks and 70 to 30% by weight of polyether blocks, based on the weight of PEBA; and which has a water absorption at saturation less than 6%, preferably less than 3% according to ISO 62, relative to the weight of PEBA.
• PEBA hydrophobic polyether block and polyamide block copolymer
• the subject of the present invention is a refreshing textile material comprising a textile material as defined above, impregnated with an aqueous medium comprising at least 85% by weight of water, preferably at least 90% of water, of preferably at least 95% water, relative to the weight of aqueous medium, the temperature of the aqueous medium being in the range of 15 ° C to Tf-20 ° C, Tf being the melting temperature of the textile material, the content hydrophobic PEBA mass representing at least 10% of the total mass of the cooling textile material.
• said PEBA is mixed with at least one filler and / or at least one pigment and / or at least one additive.
• said textile comprises synthetic fibers obtained from bio-resourced raw materials.
• said textile further comprises natural fibers, artificial fibers made from natural raw materials, mineral fibers, metal fibers and / or synthetic fibers other than hydrophobic PEBA fibers.
• said textile is manufactured solely from bio-resourced raw materials.
• said textile comprises at least one structure chosen from:
• At least one predominantly hydrophobic textile material layer comprising at least 10% hydrophobic PEBA superimposed on at least one layer of predominantly hydrophilic textile material; and or sandwich structures based on said layers;
• said textile is a felt, a veil, a net, a filter, a film, a gauze, a cloth, a bandage, a wipe, a layer, a fabric, a knit, an article of clothing, a garment, pantyhose, stockings, in particular compression stockings, a bedding article, an article of furniture, a napkin, a packaging, a curtain, a cockpit liner, a functional technical textile, a geotextile, and / or a agrotextiles.
• the present invention also relates to the use of a textile according to the invention in the medical field, cosmetics, hygiene, luggage, clothing, clothing, household equipment or home, the furniture, carpets, automotive, industry, including industrial filtration, cooling systems, ventilation, air conditioning, agriculture and / or building.
• PEBA polyether block copolymers and polyamide blocks
• polyamide blocks with dicarboxylic chain ends with polyoxyalkylene blocks with diamine chain ends obtained by cyanoethylation and hydrogenation of polyoxyalkylene aliphatic alpha-omega dihydroxylated blocks called polyether diols
• Polyamide blocks with dicarboxylic chain ends with polyetherdiols the products obtained being, in this particular case, polyetheresteramides.
• the polyamide blocks with dicarboxylic chain ends come, for example, from the condensation of polyamide precursors in the presence of a chain-limiting dicarboxylic acid.
• the polyamide blocks with diamine chain ends come for example from the condensation of polyamide precursors in the presence of a chain-limiting diamine.
• the molar mass in number Mn of the polyamide blocks is between 400 and 20000 g / mol and preferably between 500 and 10000 g / mol.
• Polymers with polyamide blocks and polyether blocks may also comprise randomly distributed units.
• Three types of polyamide blocks can advantageously be used.
• the polyamide blocks come from the condensation of a dicarboxylic acid, in particular those having from 4 to 20 carbon atoms, preferably those having from 6 to 18 carbon atoms and an aliphatic or aromatic diamine, in particular those having 2 to 20 carbon atoms, preferably those having 6 to 14 carbon atoms.
• dicarboxylic acids examples include 1,4-cyclohexyldicarboxylic acid, butanedioic, adipic, azelaic, suberic, sebacic, dodecanedicarboxylic, octadecanedicarboxylic acids and terephthalic and isophthalic acids, but also dimerized fatty acids. .
• diamines examples include tetramethylenediamine, 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 isophoronediamine (IPDA), 2,6-bis (aminomethyl) norbornane (B AMN) and piperazine (Pip).
• BCM bis (4-aminocyclohexyl) methane
• BMACM bis - (3-methyl-4-aminocyclohexyl) methane
• BMACP 2-2-bis (3-methyl-4-aminocyclo
• PA4.12, PA4.14, PA4.18, PA6.10, PA6.12, PA6.14, PA6.18, PA9.12, PA10.10, PA10.12, and PA10.14 blocks are used.
• the polyamide blocks result from the condensation of one or more alpha omega-aminocarboxylic acids and / or one or more lactams having from 6 to 12 carbon atoms in the presence of a dicarboxylic acid having from 4 to 12 carbon atoms or a diamine.
• lactams 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 blocks of the second type are made of polyamide 11, polyamide 12 or polyamide 6.
• the polyamide blocks result from the condensation of at least one alpha omega aminocarboxylic acid (or a lactam), at least one diamine and at least one dicarboxylic acid.
• polyamide PA blocks are prepared by poly condensation:
• comonomer or ⁇ Z ⁇ comonomers chosen from lactams and alpha-omega-aminocarboxylic acids having Z carbon atoms and equimolar mixtures of at least one diamine having XI carbon atoms and at least one dicarboxylic acid having Yl carbon atoms, (XI, Yl) being different from (X, Y),
• said one or more comonomers ⁇ Z ⁇ being introduced in a proportion by weight of up to 50%, preferably up to 20%, even more advantageously up to 10% relative to all the polyamide precursor monomers;
• the dicarboxylic acid having Y carbon atoms which is introduced in excess with respect to the stoichiometry of the diamine or diamines, is used as chain limiter.
• 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.
• 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.
• lactam mention may be made of caprolactam, oenantholactam and lauryllactam.
• aliphatic diamines there may be mentioned hexamethylenediamine, dodecamethylenediamine and trimethylhexamethylenediamine.
• 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 EMPOL by the company HENKEL) and Polyoxyalkylenes - ⁇ , ⁇ diacids.
• aromatic diacids mention may be made of terephthalic (T) and isophthalic (I) acids.
• cycloaliphatic diamines By way of example of cycloaliphatic diamines, mention may be made of the isomers of bis- (4-aminocyclohexyl) -methane (BACM), bis (3-methyl-4-aminocyclohexyl) methane (BMACM), and 2-2-bis - (3-methyl-4-aminocyclohexyl) propane (BMACP), and para-amino-di-cyclohexyl methane (PACM).
• the other diamines commonly used can be isophoronediamine (IPDA), 2 / 6-bis- (aminomethyl) -norbornane (BAMN) and piperazine.
• polyamide blocks of the third type As examples of polyamide blocks of the third type, the following can be cited:
• 6.6 denotes hexamethylenediamine condensed with adipic acid.
• 6.10 denotes hexamethylenediamine condensed with sebacic acid.
• 11 denotes units resulting from the condensation of aminoundecanoic acid.
• 12 denotes patterns resulting from the condensation of lauryllactam.
• the polyether blocks can represent 5 to 85% by weight of the polyamide and polyether block copolymer.
• the mass Mn of the polyether blocks is between 100 and 6000 g / mol and preferably between 200 and
• the polyether blocks consist of alkylene oxide units. These units may be, for example, ethylene oxide units, propylene oxide or tetrahydrofuran units (which leads to polytetramethylene glycol linkages).
• PEG blocks polyethylene glycol
• PPG blocks propylene glycol
• PO3G blocks polytrimethylene glycol
• PTMG blocks ie those consisting of tetramethylene glycol units also called polytetrahydrofuran.
• the PEBA copolymers may comprise in their chain several types of polyethers, the copolyethers may be block or statistical. It is also possible to use blocks obtained by oxyethylation of bisphenols, such as, for example, bisphenol A. These latter products are described in patent EP613919.
• the polyether blocks may also consist of ethoxylated primary amines.
• ethoxylated primary amines mention may be made of the products of formula:
• the flexible polyether blocks may comprise polyoxyalkylene blocks with NH 2 chain ends / such blocks obtainable by cyanoacetylation of aliphatic polyoxyalkylene aliphatic alpha-omega dihydroxy blocks called polyether diols.
• polyether diols More particularly, Jeffamines (for example Jeff amine® D400, D2000, ED 2003, XTJ 542, commercial products of Huntsman, also described in JP2004346274, JP2004352794 and EP1482011) can be used.
• the polyetherdiol blocks are either used as such and copolycondensed with polyamide blocks having carboxylic ends, or they are aminated to be converted into polyether diamines and condensed with polyamide blocks having carboxylic ends.
• the general two-step preparation method for PEBA copolymers having ester bonds between PA blocks and PE blocks is known and is described, for example, in French patent FR2846332.
• the general method for preparing the PEBA copolymers of the invention having amide linkages between PA blocks and PE blocks is known and described, for example in European Patent EP1482011.
• the polyether blocks can also be mixed with polyamide precursors and a diacid chain limiter to make the polyamide block and polyether block polymers having statistically distributed units (one-step process).
• PEBA designation in the present description of the invention relates as well to PEBAX® marketed by Arkema, Vestamid® marketed by Evonik®, Grilamid® marketed by EMS, Kellaflex® marketed by DSM or to any other PEBA from other suppliers.
• hydrophobic PEBA is intended to mean PEBA which both have a saturation water absorption of less than 6% by weight, preferably less than 3% according to ISO 62, with respect to the weight of PEBA and comprising from 20 to 80% by weight of polyamide blocks and from 80 to 20% by weight of polyether blocks, preferably from 30 to 70% by weight of polyamide blocks and from 70 to 30% by weight of polyether blocks.
• the PEBA copolymers have PA blocks in PA 6, PA 11, PA 12, PA 6.12, PA 6.6 / 6, PA 10.10 and / or PA 6.14, preferably PA 11 and / or PA blocks. 12; and PE blocks made of PTMG, PPG and / or PO3G.
• PEBAs based on PE blocks consisting mainly of PEG are to be included in the range of hydrophilic PEBAs.
• PEBA based hydrophilic PEBA-based textile materials that do not meet the hydrophobic PEBAS criteria defined above are not able to cool under the conditions of use or the process of the present invention, as shown in Table 1 below, and may even on the contrary swell in contact with water.
• Figure 1 is a photograph of a web ("web" weight of 80 g / m2) in three increasing enlargements (1, 2 and 3). The last enlargement shows how, on the water surface of PEBA hydrophobic fibers (PA12-PTMG), water disperses into tiny microdroplets less than 20 ⁇ m, or even less than 10 ⁇ , which causes their evaporation extremely fast, thanks to their low surface tension. This evaporation is caused by a heat transfer directly between these droplets and the ambient air, the hydrophobic PEBA used according to the invention being poor heat conductor. It is in particular the heat transfer of the skin towards these droplets, on the surface of a textile according to the invention, which gives a sensation of "dry cold” surprising.
• PA12-PTMG PEBA hydrophobic fibers
• the hydrophobic PEBA is mixed with at least one filler and / or at least one pigment and / or at least one additive.
• the polymer matrix of the PEBA may in particular comprise additives.
• Said additives may be, for example, reinforcing fillers, flame retardants, UV protective agents, UV stabilizers, thermal stabilizers, pigments, lubricants, antioxidants, flow improvers , flowability, film-forming agents, film-forming aids, gums, semi-crystalline polymers, preservatives, and mixtures thereof.
• additives may be, for example, reinforcing fillers, flame retardants, UV protective agents, UV stabilizers, thermal stabilizers, pigments, lubricants, antioxidants, flow improvers , flowability, film-forming agents, film-forming aids, gums, semi-crystalline polymers, preservatives, and mixtures thereof.
• any other type of additive used in the textile field is also conceivable.
• the present invention relates in particular to the use of said hydrophobic PEBA for the manufacture of textile materials, such as yarns, fibers, filaments (monofilaments or multifilaments), films, membranes, porous membranes, woven or non-woven fabrics.
• the present invention also relates to the manufacture and use of melted hydrophobic PEBA particles to adhere them to the surface of textile materials in a durable (wash-resistant) manner.
• the hydrophobic PEBA mass content represents at least 10%, preferably at least 30%, preferably at least 50%, preferably at least 80%, or ideally 100%, of the total weight of the textile according to the invention.
• Tf is called the melting temperature of the textile material. It may be for example in the range of 100 to 170 ° C.
• Said PEBA or thermoplastic matrix compositions based on said PEBA can be formed into textile material directly after the polymerization, without intermediate stages of solidification and remelting. They may also be shaped into granules, intended to be remelted for final definitive shaping, for example for the manufacture of molded textile articles or for the manufacture of yarns, fibers and / or filaments.
• melt spinning processes can be used in particular by passing the composition of the invention through dies comprising one or more orifices.
• spinning processes or spinning-drawing or spinning-drawing-texturing integrated or not whatever the spinning speed.
• the yarns can be produced by high speed spinning, spinning speed greater than or equal to 3000 m / min, preferably greater than or equal to 4000 m / min.
• Such methods are often referred to as POY (partialy oriented yarn), FOY (fully oriented yarn), FEI (integrated spinning-draw), HOY (higly oriented yarn with a speed greater than 5500 m / min). These son can be textured, according to the use for which they are intended.
• the yarns obtained by these processes are particularly suitable for producing textile, woven or knitted surfaces.
• the PEBA thermoplastic polymer matrix may be used for the production of monofilament or monofilament yarns, multifilament or multifilament yarns, continuous fibers (in coils) and / or staple fibers (cut).
• PEBA staple fibers are particularly suitable for mixing with natural fibers.
• a process particularly well suited to the manufacture of PEBA monofilaments and multifilaments is that described in patent application US2010 / 0119804.
• the titers can range from 1.5dtex to 100dtex / filament, high titers being particularly well suited for industrial applications.
• the multifilament yarns preferably have a titre of less than or equal to 6 dtex / filament, more preferably less than or equal to 1.5 dtex / filament.
• the filaments may for example be combined in the form of wick or sheet, directly after spinning or in recovery, stretched, textured or curled and cut. The resulting fibers can be used for the manufacture of nonwovens or fiber yarns.
• the compositions can also be used for the manufacture of flock.
• the yarns, fibers and / or filaments of the invention may undergo various treatments, such as, for example, stretching in a continuous or reworked step, sizing, oiling, interlacing, texturing, crimping, stretching, thermal fixing or relaxation treatment, grinding, twisting, and / or dyeing.
• treatments such as, for example, stretching in a continuous or reworked step, sizing, oiling, interlacing, texturing, crimping, stretching, thermal fixing or relaxation treatment, grinding, twisting, and / or dyeing.
• dyeing mention is made in particular of bath or jet dyeing processes.
• the preferred dyes are acid, metalliferous or nonmetallic dyes.
• the present invention also relates to textile articles obtained by shaping a PEBA matrix or a thermoplastic composition comprising PEBA according to the invention by a process chosen from the group comprising an extrusion process, such as extrusion of sheets and films; molding, such as compression molding; and injection, such as injection molding.
• Films can thus be obtained by the aforementioned methods using a flat die.
• the films obtained may undergo one or more treatment steps, such as a one-dimensional or two-dimensional stretching, a stabilizing heat treatment, an antistatic treatment or a sizing.
• Textiles comprising hydrophobic PEB A according to the invention have a cold or cooling effect under certain conditions: the cooling effect is caused after contacting (either by simple contact, or by impregnation, spraying, or soaking) hydrophobic PEBA-based textile material with an aqueous medium, irrespective of the method of addition of the aqueous medium to the textile material.
• aqueous medium within the meaning of the invention is meant a liquid or a gas, steam, or even a solid, said medium comprising at least 85% by weight of water relative to the weight of medium, preferably at least 90% water, preferably at least 95% water; and the temperature of the aqueous medium is preferably in the range of from 1 ° C to 20 ° C, preferably from 15 ° C to 20 ° C, where Tf is the melting temperature of a textile material according to 'invention.
• the aqueous medium can naturally impregnate the textile or naturally come into contact with the textile material. This is the case for example of sweat on a garment.
• the aqueous medium may also be voluntarily added to the textile by any means such as impregnation, dipping, spraying by the aqueous medium in the form of gas, vapor or liquid, or by any other method of adding liquid, gas or steam to a textile material. This is the case of a medical, pharmaceutical, cosmetic, or perfume, which can be added respectively to a dressing or a refreshing wipe, for example.
• ambient temperature within the meaning of the invention is meant the temperature of the air or the medium surrounding the textile, whether it is controlled (air conditioning, cold room), programmed (operating temperature of a process or of a device) or uncontrolled (related to weather and external geographical conditions). More precisely, ambient temperature is understood to mean a temperature comprised in the range from -60 ° C to 150 ° C, preferably from -40 ° C to 140 ° C.
• the textile materials according to the invention comprising at least 50% hydrophobic PEBA are able to withstand these temperatures, the PEBA retaining all their properties (including flexibility and their dimensions) at these temperatures.
• the textile material according to the invention is such that it cools to a temperature below room temperature for at least 15 minutes after said contacting, preferably for at least 30 minutes, preferably for at least one hour, preferably for at least two hours, the ambient temperature being in the range of 10 to 80 ° C, preferably 10 to 50 ° C, preferably 15 to 40 ° C.
• said material is such that it has accelerated and prolonged desorption and evaporation properties of said aqueous medium in the form of cold gas with a temperature below room temperature, preferably below 20 ° C.
• the present invention also relates to a textile or textile article obtained at least partially from hydrophobic PEBA, in the form of yarns, fibers and / or filaments as defined above.
• These articles may be fabrics or textile surfaces, such as woven, knitted, nonwoven or carpet surfaces.
• Said textile is advantageously used in the medical, cosmetic, pharmaceutical, hygiene, luggage, garment, clothing, household equipment or home, furniture, carpets, automotive, industry, including industrial filtration, agriculture and / or building.
• the textile according to the invention is advantageously a felt, a filter, a film, a gauze, a web, a web ("web"), a net, a dressing, in particular a dressing to relieve pain or pain. burns, a diaper, a fabric, a knit, an article of clothing, a garment, a pantyhose, stockings, including stockings, a bedding article, a home furnishing article, a napkin, a wrapping, a curtain, a cockpit liner, a functional technical textile, a geotextile and / or an agrotextile.
• the cold effect is particularly surprising on a web (web), a net (net), a fabric knitted using monofilaments or multifilament or on a perforated film.
• a web web
• net net
• a fabric knitted using monofilaments or multifilament or on a perforated film For example, after soaking these structures in hot water at 40 ° C and then briefly spinning, they produce a cold effect in a few seconds, the temperature of the textile surface having fallen to 16 ° C in less than one hour. ten seconds. Soaking in water at room temperature (for example at 20 ° C) gives the same results. Hot water, especially above 30 ° C, brings an additional surprise effect.
• said textile comprising fibers, filaments and / or films based on PEBA has a large specific surface area. It has been demonstrated that this further increases the rate of evaporation of an aqueous liquid on the surface of the textile material comprising these fibers and / or filaments according to the invention.
• the surface of the fibers or filaments may have a particular structure such as grooves, including straight, ellipsoidal, etc., to increase the evaporation rate and therefore the cold effect of textile materials according to the invention.
• These textiles according to the invention manufactured from hydrophobic PEBA preferably predominantly (comprising at least 50% by mass of PEBA), have, in addition, other advantageous properties. They are light, Soft, soft-touch, they resist tearing, cutting, abrasion, and pilling.
• said textile further comprises natural fibers, such as cotton, wool and / or silk, artificial fibers made from natural raw materials, mineral fibers, such as carbon fibers, glass fibers. , silica and / or magnesium, metal fibers and / or synthetic fibers other than PEBA fibers.
• the synthetic fibers may in particular comprise polyester, polyether, polyetherester, polyamide, acrylic or any other synthetic material generally used in the textile field.
• the textiles according to the invention may in particular comprise combinations of hydrophobic PEBA with hydrophilic synthetic fibers (for example hydrophilic PEBA).
• hydrophilic PEBA for example hydrophilic PEBA
• the latter act as a transfer of moisture.
• the hydrophilic synthetic fibers absorb moisture and, in contact with the PEBA, it is responsible for evaporation and the production of cold on the textile.
• the hydrophilic fibers are mainly in contact with the skin (inner side of a T-shirt for example) to absorb moisture and pass it to the PEBA hydrophobic fibers which are predominantly to the outer fabric of the garment, on the environmental side
• the textiles according to the invention may comprise sandwich structures comprising a layer of predominantly hydrophilic fibers taken between two predominantly hydrophobic fiber layers, comprising at least 10% hydrophobic PEBA or, conversely, comprising a layer of predominantly hydrophobic fibers, comprising at least 10% of hydrophobic PEBA, taken between two predominantly hydrophilic fiber layers. oritally "means that the layer contains more than 50% by weight of hydrophobic or hydrophilic fibers as appropriate.
• hydrophobic PEBA-based textiles of the invention Unlike a purely hydrophilic textile that accumulates water and causes a cold effect only due to the presence of water, resulting in a sensation of "wet" cold, hydrophobic PEBA-based textiles of the invention cause a cold effect and dry surprising.
• the hydrophobic PEBA evaporates the water more quickly, causes a sensation of intense cold on the surface of the textile and makes the wet effect of the textile disappear almost instantly.
• said textile comprises synthetic fibers obtained from bio-resourced raw materials.
• the textile according to the invention is manufactured solely from bio-resourced raw materials.
• Raw materials of renewable origin or bio-resourced raw materials are materials that include biofouled carbon or carbon of renewable origin. In fact, unlike materials made from fossil materials, materials made from renewable raw materials contain 14 C.
• the "carbon content of renewable origin” or “bio-resourced carbon content” is determined according to the standards ASTM D 6866 (ASTM D 6866-06) and ASTM D 7026 (ASTM D 7026-04).
• the first standard describes a 14 C / 12 C ratio measurement of a sample and compares it with the 14 C / 12 C ratio of a 100% bioressourced original reference sample to give a relative percentage of organic C -stored in the sample.
• the standard is based on the same concepts as 14 C dating, but without applying the dating equations.
• the calculated ratio is referred to as the "pMC" (Percent Modem Carbon). If the material to be analyzed is a mixture of biomaterial and fossil material (without radioactive isotope), then the value of pMC obtained is directly correlated to the amount of biomaterial present in the sample.
• ASTM D 6866 provides several techniques for measuring the 1 C isotope content, based on either liquid scintillation counting (LSC) or AMS / IRMS (Accelerated Mass). Spectrometry coupled with Isotope Radio Mass Spectrometry). The measurement method preferably used in the case of the present invention is the mass spectrometry described in standard ASTM D6866-06 ("accelerator mass spectroscopy").
• the textiles of the invention containing PEBA based on polyamide 11 come at least partly from bioprocessed raw materials and have a bio-resourced carbon content of at least 1%, which corresponds to at an isotopic ratio of 12 C / 14 C of at least 1.2 x 10 14 .
• the textiles according to the invention comprise at least 50% by weight of bio-resourced carbon on the total mass of carbon, which corresponds to a 12 C / 14 C isotope ratio of at least 0.6 ⁇ 10 12 .
• This content is advantageously higher, especially up to 100%, which corresponds to a 12 C / 14 C isotope ratio of 1.2 ⁇ 10 -12 , in the case of PEBAs with PA 11 blocks and PE blocks comprising P03G, PTMG and / or PPG from renewable raw materials.
• the textiles according to the invention may therefore comprise 100% bio-resourced carbon or on the contrary result from a mixture with a fossil origin.
• Textiles made from PEBA of the invention are compared with textiles based on other materials commonly used in textiles: PES (polyester), PA (or polyamide), cotton.
• the PEBA is PA12-PTMG, that is to say that it comprises PA12 blocks and PTMG blocks.
• the PEBA is PA11-PTMG.
• the PEBA is respectively PA6-PTMG, PA12-PEG and PA6-PEG.
• the comparative Cpl is polyester, Cp6 is PAU, Cp7 is cotton, Cp8 is a copolyamide PA 6 / 6.6 / 12 brand Platamid® H005.
• the contents (percent by weight) of the PA and PE blocks are shown in Table 1.
• the temperature measurements are performed on the textile by infrared gun (Cole Parmer brand).
• the aqueous medium used in the examples is liquid water.
• the textile material is in the form of a light web of 80 g / m 2 for all the tests, except for example 2.
• Example 2 is a nonwoven of fibers which are narrower than those of the web and of higher grammage, which makes it more difficult to come into contact with the aqueous medium, and the smaller contact area.
• the textile is less impregnated with aqueous medium.
• PROTOCOL At room temperature of 23 ° C:
• OBSERVATIONS Apart from the textiles according to the invention, the other textiles do not have a cold effect.
• the textiles of the comparative Cpl to Cp6 swell, deform, have a soggy and heavy appearance, and one does not observe (Cpl) or very little (Cp2 to Cp6) of temperature drop of the textile after contact with the liquid.
• the hydrophobic PEBA-based fabrics of the examples according to the "Ex” invention are cooled and have a lasting cooling effect for at least 2 hours, have a dry, pleasant and supple feel, while remaining very light .
• Their temperature decreases from 5 ° C to 7 ° C for at least 1h30 relative to the initial temperature of 23 ° C, corresponding to the ambient temperature, even after impregnation with water temperature 30 ° C.
• By slightly shaking a hydrophobic PEBA-based fabric according to the invention, for example at TO + 1h30 it is noted that its temperature drops to 16 ° C., thanks to the additional evaporation produced.
• PEBA textile (Exl) according to the invention has accelerated properties of evaporation of water, in the form of cold gas with a temperature below 20 ° C; while the evaporation of water from a polyamide textile or a cotton textile is much slower.
• the PEBA used in the composition of a textile according to the invention has a surprising dry and lasting dry effect lasting for several hours, and capable of intensifying and prolonging under the effect of the movement (for example if it is shaken slightly at TO + 1 hour) or under the effect of a new contact with an aqueous medium, such as liquid water, or the sweat of an athlete for example.
• the cooling effect of the textile according to the invention is intensified and prolonged by setting the textile in motion, which has been previously brought into contact with an aqueous medium.
• the behavior of the textiles according to the invention is therefore the ideal behavior sought for technical textiles, especially in the field of sports, in particular sportswear.

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• Chemical & Material Sciences (AREA)
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• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
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• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
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• 2010
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