TWI705853B - Filament or fibre absorbing acid and/or basic gases, manufacturing method of such a filament or such a fibre, textile article comprising such a filament or such a fibre - Google Patents

Abstract

The aim of the present invention is a filament or fibre absorbing the odorous molecules, especially acid and/or basic gas(es), having a determined external surface whereof at least one portion of said surface comprises carboxylic groups -COOH and/or carboxylate groups -COO^- complexed with metallic salts. Advantageously, said portion is constituted by a matrix originating from the reaction of a mixture comprising a polyester as well as a first copolymer of at least one olefin and alkyl (meth)acrylate and/or (meth)acrylate acid (A), and a second (co)polymer comprising oxiran groups -C₂H₃O (B), at least some of the (meth)acrylate functions of the copolymer (A) having been transformed into corresponding carboxylate and/or corresponding carboxylic functions.

Description

Silk or fiber that absorbs acid and/or alkaline gas, the manufacturing method of this silk or this fiber, and the textile article containing this silk or this fiber

The present invention relates to a silk or fiber that absorbs acid and/or alkaline gas, a method of manufacturing the silk or the fiber, and a textile article containing the silk or the fiber

Background of the invention

The present invention relates to the technical field of fibers or silks that have the ability to absorb acid and/or alkaline gases, specifically, and wick bad odors produced by perspiration.

During exercise, physical work raises body temperature, produces more sweat and odorous volatile compounds than when at rest. The first layer of textile that the user wears during exercise exercises is a better recipient of sweat and especially the odorous molecules produced by the degradation of proteins contained in sweat by bacteria present on the skin. This textile article layer retains these odorous molecules and therefore will smell bad after a sports game, especially when it is dry, and must be washed before the next game. During sports competitions, the polyester textile article layer usually releases a bad smell.

The poor odor-generating properties of textile articles made of polyester usually occur immediately when the textile articles come into contact with the wearer's sweat, rather than being applied later during sports activities.

Textile materials do not react to odors in the same way. Natural materials, especially those based on wool, do not smell too much, or even produce bad odors, especially those related to sweat.

Nowadays, existing solutions for limiting the unpleasant odor of synthetic textiles, especially polyester, consist of: by absorbing and/or destroying and/or masking the odor, or by eliminating the bacteria responsible for the synthesis of odorous molecules to inhibit The smell.

In order to correct these shortcomings, textiles obtained from fibers and/or functionalized filaments with cyclodextrin cage molecules or nanoparticles of charcoal, bamboo or coconut are used, or even coffee-based fibers are used. However, these solutions are not durable, because the functionalizing agent is eliminated during washing, and/or also has a limited odor absorption effect and/or for example by strengthening it, especially cyclodextrin to adjust the touch characteristics of the textile article.

Another solution consists of the introduction of odor-absorbing materials, such as natural fibers, such as cotton in polyester textile articles. However, the disadvantage of this solution is that it is costly and does not allow the textile articles to dry quickly, and therefore also accelerates the discharge of sweat. For technical textiles used for sports exercises, the fast drying and drainage properties of sweat are particularly good. In addition, cotton tends to pilling.

It is also possible to have antibacterial agents on textile articles, such as nanosilver, copper, zinc oxide, titanium, zirconium or platinum. However, these antibacterial agents directly act on bacteria in contact with the skin. Therefore, this solution is only suitable for textile items that are intended to be worn very close to the body, such as socks, but for example, it is ineffective or significantly less effective for T-shirts. In addition, regulations on biocides are becoming stricter because they affect the bacterial flora of the skin.

EP 0.792.957 B1 describes the use of metal salts (e.g., sodium salt) complexed carboxyl group (-COOH) and carboxylate group (-COO-) to produce fibers that have both acidic and alkaline gas absorption characteristics to remove odors ( See [0002]). This fiber is modified with hydrazine (NH ₂ -NH ₂ ) containing more than 40% by weight of polyacrylonitrile (PAN) base fiber to make the fiber reticulated, and its nitrogen content increases by 1% to 8% of its total weight And get. The nitrile group based on the fiber is hydrolyzed by means of an alkaline solution such as a metal salt of sodium hydroxide or potassium hydroxide. Then the fibers were soaked in a nitric acid solution for 30 minutes, followed by washing (see Example 1, [0048]).

The method described in EP 0.792.957 B1 is only applicable to polyacrylonitrile fibers obtained by coagulating polyacrylonitrile (PAN) according to the definition and then spinning it. The resulting fiber has a rose color and is not dyed or extremely difficult to dye. In addition, the resilience of these fibers is not enough to form a yarn alone, so it is necessary to mix them with other fibers and/or filaments to alleviate their limited mechanical properties. The mixture of acrylic fibers and synthetic fibers (such as polyester fibers) is complicated due to dyeing problems (acrylic fibers are usually mixed with wool and cannot withstand temperatures exceeding 100°C). In addition, yarns containing polyacrylonitrile fibers (such as yarns spun from fibers) tend to pilling and have poor wear resistance.

In the end, the technical objects for movement are mainly in synthetic materials such as polyester or polyamide, rather than based on cotton or viscose or even acrylic fibers. This is because of the cost and effectiveness in terms of rapid drying and draining humidity, but easy Use, especially with regard to mechanical performance and dyeing.

Therefore, there is a need for fibers or filaments especially based on polyethylene terephthalate, which eliminates the above-mentioned problems, and especially absorbs bad odors and/or neutralizes bad odors, and is durable even without washing, is easy to manufacture and can be manufactured Yarn is then made into textile form and easy to die.

SUMMARY OF THE INVENTION The first aspect according to the object of the present invention is a silk or fiber that absorbs odorous molecules, especially acid and/or alkaline gas, which has a defined outer surface, wherein at least a part of the surface contains carboxyl-COOH and/ Or the carboxylate group -COO- complexed with the metal salt. Advantageously, this part is composed of a matrix derived from a first copolymer (A) comprising polyester, at least one olefin and alkyl (meth)acrylate and/or (meth)acrylic acid, and comprising a ring Reaction of the second (co)polymer (B) mixture of oxyethylene-C2H3O, at least some of the (meth)acrylic or (meth)acrylate functional groups of the copolymer (A) have been converted into the corresponding carboxylate Acid radical and/or corresponding carboxylic acid functional group.

Advantageously, the fiber or filament according to the present invention comprises a part of its outer surface composed of a combination of a polyester matrix and a first polymer (A) and a second polymer (B), the first copolymer (A) contributes (A yl) acrylate functional groups, converting it into all or some of the carboxylic acid functional groups -COOH and / or carboxylate functional group -COO ^-. The first copolymer (A) may also contain an acrylic functional group with an essential carboxylic acid functional group -COOH and therefore does not need to undergo acid-base reaction conversion to absorb alkaline gas. The second polymer (B) stably incorporates the first polymer (A) into the matrix and adjusts the viscosity of the matrix, in particular, it can be extruded and spun.

Advantageously, once the (meth)acrylate group in this part undergoes the saponification and/or acidification and/or complexation steps described below, it forms the corresponding carboxyl groups (-COOH) and/or the metal salts of malocclusion corresponding carboxylate (-COO ^-).

The main mechanism for gas absorption is based on carboxylic acid functional groups supported by fibers or filaments, which will react with alkaline gases and/or based on the supported carboxylic acid functional groups, which will react with acid gases. Polar interactions and hydrogen bonds can also be established between carboxylic acid functional groups and acid gases. About deodorizing acid gas, an acidic gas (e.g. acetic acid) by the salified, by an acid gas capture (e.g., by generating (CH ₃ COO to form non-volatile metal salts of carboxylic acids ^-, M ^+), wherein M ⁺ Is a metal salt of acetic acid). The regeneration of fibers or silks can be achieved by washing (home washing of textile articles containing the fibers and/or silks).

The acid and/or alkaline gas absorption characteristics of the fiber or silk are related to the inherent structure of the fiber or silk, which ensures a long-lasting odor effect contrary to the chemical treatment of the prior art.

Advantageously, the second (co)polymer (B) ensures the function of the coupling agent between the polyester matrix and the first copolymer (A) by chemical bonds (especially by covalent bonds) and/or polar bonds.

Observing the cross-section of the yarn according to the present invention with a scanning electron microscope, polymers A and B form nodules in the polyester matrix, polymer A is encapsulated by polymer B, and polymer B forms polymer A and polyester matrix The physical interface between.

In addition, the reactive oxirane group in the second (co)polymer is reactive with the polyester matrix via polar and/or covalent bonds. Advantageously, the ends of the polyester chains in the polyester matrix containing carboxylic acid functional groups (COOH) react with ethylene oxide groups, in particular the glycidyl (meth)acrylate of polymer B. The second (co)polymer (B) must advantageously have a "compatible" chemical structure, that is, be able to perform with the first copolymer (A) and the polyester matrix in the extrusion-spinning reaction.

According to one embodiment, the polymer B is a copolymer of at least one olefin and at least one monomer unit containing an ethylene oxide group.

The presence of olefin monomer units in the polymer chain of the second (co)polymer (B) produces a "polyolefin" backbone, which also significantly improves the phase with the first copolymer (A) containing the "polyolefin" backbone. Capacitive. According to one embodiment, the polymer B is a copolymer of at least one monomer unit containing an ethylene oxide group, an alkyl (meth)acrylate, and optionally at least one olefin. Advantageously, polymer B also contributes acrylate functional groups, wherein all or some of these acrylate functional groups are converted into corresponding carboxylate and/or corresponding carboxylic acid functional groups.

Preferably, the ratio of the mass (g) of the polyester in the matrix to the total mass of the matrix is greater than or equal to 50%, more preferably greater than or equal to 60%, even more preferably greater than or equal to 70%, specifically greater than or equal to 75 %, more specifically greater than or equal to 80%, even more specifically greater than or equal to 85%, as appropriate, greater than or equal to 90%.

The ratio (A)/(B) of the mass of the first copolymer (A) introduced into the matrix to the mass of the second (co)polymer (B) is between 10/90 and 95/5, preferably Between 50/50 and 95/5, even better between 70/30 and 90/10, specifically between 85/15 and 90/10.

According to one embodiment, the mass ratio of the alkyl (meth)acrylate in the first copolymer (A) and optionally the second (co)polymer (B) is greater than or equal to 20%, and even more preferably greater than or equal to 25 %. This value can be measured by Fourier transform infrared spectroscopy.

Preferably, the first copolymer (A) of polyester and/or at least one olefin and alkyl (meth)acrylate and/or (meth)acrylate, and/or contains ethylene oxide-C The second (co)polymer (B) of ₂ H ₃ O is thermoplastic, in particular its melting temperature (Tf) allows it to be extruded, in particular extrusion-granulation (compounding) and extrusion- Spinning.

Preferably, the melting temperature of the first copolymer (A) and optionally the second (co)polymer (B) is greater than or equal to 55°C, more preferably less than or equal to 180°C, even more preferably less than or equal to 140 °C, specifically less than or equal to 100 °C, even more specifically less than or equal to 80 °C.

Preferably, the flexural modulus of the first copolymer (A) and optionally the second (co)polymer (B) is greater than or equal to 5 MPa, more preferably greater than or equal to 7 MPa. The flexural modulus can be measured using the method described in the standard SO 178: 2010 or the standard ASTM D790 D1525 on a sample molded by compression.

Preferably, the Vicat softening point of the first copolymer (A) and optionally the second (co)polymer (B) at 10 N is less than or equal to 60°C, more preferably less than or equal to 50°C, even More preferably, it is less than or equal to 40°C. The Vicat softening point can be measured using the method described in the standard ISO 306:2004 or the standard ASTM D1525 on the sample by compression molding.

Preferably, the melt flow index (190°C/2.16 Kg) of the first copolymer (A) and optionally the second (co)polymer (B) is greater than or equal to 2 g/10 min.

The indicated titer (dtex, denier) in the context of the present invention can be measured with the aid of the standard NF EN ISO 2060 dated June 1995.

For the purposes of the present invention, "polyester" means any polymer produced by the condensation of polyols, especially diols, and aromatic carboxylic acid polyacids, especially aromatic carboxylic acid diacids.

Preferably, the polyester according to the present invention is selected from: polyethylene terephthalate, polytetramethylene terephthalate, polycyclohexane-dimethylene (polycyclohexane-dimethylene) or poly 2 ,6 polyethylene dicarboxylate 2,6 naphthalene, and more preferably polyethylene terephthalate. Other polyesters can be used, such as homopolymers, copolymers, terpolymers, and mixtures of monomer units selected from the following list: ethylene terephthalate, propylene terephthalate, and Butylene phthalate and 1,4-cyclohexylene-dimethylene terephthalate (1,4-cyclohexylene-dimethylene terephthalate), specifically, ethylene terephthalate.

Preferably, the polyester according to the present invention is in a grade configured to be spun into yarn for its transformation.

For the purposes of the present invention, "polyol" means any compound containing at least two hydroxyl functional groups (-OH), especially any (diol) compound containing only two hydroxyl functional groups (-OH).

For the purposes of the present invention, "aromatic carboxylic acid polyacid" means any compound containing at least two carboxylic acid functional groups (-COOH) and at least one aromatic ring, especially containing only two carboxylic acid functional groups and at least one Any compound of aromatic ring (aromatic carboxylic diacid).

For the present invention, "acid gas" means any gas that can react with the carboxylate functional group (-COO ^- ) in an acid-base reaction, and "basic gas" means any gas that can react with the acid functional group (-COOH) ) Any gas that reacts in an acid-base reaction.

Preferably, the acid gas is selected from the list comprising: propionic acid, formic acid, butyric acid, benzothiazole, acetic acid, valeric acid, dodecanoic acid, caprylic acid, nonanoic acid, and more preferably acetic acid.

Preferably, the alkaline gas is selected from the list comprising: amines such as trimethylamine, methylamine, ethylamine, triethylamine, propylamine; diethylamine, pyrazine, ammonia, aniline, and more preferably ammonia.

For the purposes of the present invention, "silk" means any elongated textile element of indefinite length (theoretically unlimited).

For the purposes of the present invention, "fiber" means any elongated textile element of a certain length (according to its limitation), specifically short or long fibers.

For the purposes of the present invention, "yarn" means yarns spun from fibers, monofilament yarns (monofilaments), multifilament yarns, and mixtures thereof.

For the purposes of the present invention, a metal salt means any salt comprising a metal cation part (M ⁿ⁺ ) (n is an integer greater than or equal to 1) and an anion part (non-metal as appropriate), wherein the total negative charge neutralizes the cation The charge of the metal part, preferably the metal salt is selected from: potassium salt (K ⁺ ), sodium salt (Na ⁺ ), calcium salt (Ca ²⁺ ), magnesium salt (Mg ²⁺ ), aluminum salt (Al ³⁺⁾ ) And silver salt (Ag ⁺ ; Ag ²⁺ ; Ag ³⁺ ).

For the purposes of the present invention, "copolymer" means any polymer containing at least two different monomer units that repeat at regular or irregular (random) intervals according to the chain of the copolymer. When the copolymer contains three different monomer units, it is more specifically a terpolymer.

For the purposes of the present invention, "olefin" means any repeating olefin monomer of the formula -(CH ₂ -CR ₁ R ₂ ) _n -, wherein R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group. It is preferably straight or branched chain and acyclic, preferably a hydrogen atom. The alkyl group may contain one to ten carbon atoms, more preferably one to six carbon atoms, especially one to four carbon atoms. The alkyl group is preferably: methyl -CH ₃ ; ethyl -CH ₂ -CH ₃ or propyl (n-propyl or isopropyl), butyl, such as n-butyl, second butyl, isobutyl or Tertiary butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl.

The first copolymer (A) and/or the second (co)polymer (B) according to the present invention can be syndiotactic, isotactic or atactic polymers.

For the purposes of the present invention, "alkyl (meth)acrylate" means a formula -(CH ₂ -C(CH ₃ )COO(R ₁ ))- or -(CH ₂ -CHCOO(R ₁ ))- Any monomer unit acrylate, where the R ₁ group is an alkyl chain, preferably saturated, linear or branched, more preferably acyclic, more preferably containing 1 to 20 carbon atoms (in C1-C20), More preferably C1-C15, even better C1-C10, more specifically C1-C8, even more specifically C1-C4, especially methyl. Preferably, the alkyl (meth)acrylate is selected from methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, ( Octyl meth)acrylate or 2-ethylhexyl (meth)acrylate.

In the context of the present invention, the methyl group represented as (methyl) as follows means that (methyl) is considered to exist as appropriate.

For the purposes of the present invention, "(meth)acrylic acid" means any monomer unit of the formula -(CH ₂ -C(CH ₃ or H)COOH)-.

For the purposes of the present invention, "thermoplastic" means any (co)polymer that has a melting temperature Tf and can be transformed by extrusion. The melting temperature Tf can be measured using the method described in the standard ISO 11357-3:2011.

For the purposes of the present invention, "ethylene oxide" means any group of formula -C ₂ H ₃ O. This group can be carried by a glycidoxy group, which in turn is carried by one or more different repeating monomer units present in the polymer chain of the second (co)polymer (B). Preferably, the monomer unit is glycidyl (meth)acrylate.

Preferably, the ethylene oxide group is contributed by monomer units selected from the group consisting of glycidyl acrylate, glycidyl methacrylate (GMA) and glycidyl vinyl ether, preferably glycidyl acrylate and methacrylic acid Glycidyl esters (GMA).

In a variant, the metal salt is a salt of one or more metals selected from the group consisting of the following metals: potassium (K), sodium (Na) (specifically after saponification), calcium (Ca), magnesium (Mg) , Aluminum (Al) and Silver (Ag) (specially after complexing) or their mixtures.

In a variant, the first copolymer (A) of olefin and alkyl (meth)acrylate or (meth)acrylic acid and optionally the second (co)polymer (B) (each) is Elastomer. In a variant, the second polymer containing ethylene oxide groups is a ternary of at least one olefin, alkyl (meth)acrylate or (meth)acrylic acid, and monomer units containing ethylene oxide groups. Copolymers, specifically ethylene, alkyl (meth)acrylate or terpolymer of (meth)acrylic acid and glycidyl (meth)acrylate.

In a variant, the filaments or fibers according to the invention comprise first and second non-mixed polymeric structures, the first structure being the matrix.

Preferably, the mass of the first polymer structure relative to the total mass of the fiber or the filament is less than or equal to 30% and greater than or equal to 0%, specifically less than or equal to 20%, more specifically less than or equal to 10% .

Preferably, the mass of the second polymeric structure relative to the total mass of the fiber or the filament is greater than or equal to 50%, specifically greater than or equal to 70%, more specifically greater than or equal to 80%, especially greater than or equal to 90 %.

This arrangement optimizes the mass ratio of the gas-absorbing functional matrix according to the present invention, and therefore the final cost.

Advantageously, the first and second polymeric structures are co-extruded and then spun, but two unique structures are formed in the fiber or filament.

In a variant, the second polymeric structure comprises at least one polymer selected from the list comprising: polyamide 6, polyamide 6-6, polyamide 12, polyamide 11, polyamide 4- 6. Polyester (specifically polyethylene terephthalate), polypropylene and polyethylene or a combination thereof.

Preferably, the polymers are at least 85% based on the second polymer structure, more preferably at least 90%, in particular at least 95%.

In a variant, the filament or the fiber has a heterogeneous transversal cross-section of the core-outer layer type, and the outer layer is composed of the matrix (or the first polymeric structure). Preferably, the core is composed of the The second polymer structure is composed.

The fiber or filament according to the present invention may have any configuration according to its cross-section when it contains at least a part of its surface such as defined according to the present invention. In particular, the fiber or filament according to the present invention may be of the core-outer layer type, which has a multilobal or cylindrical core and an outer layer having the shape of the core, or on the contrary, is independently substantially cylindrical or multilobal.

In a variant, the mass ratio of the first copolymer (A) to the second (co)polymer (B) in the matrix is between 99/1 and 85/15.

In a variant, the ratio of the sum of the mass of the first copolymer (A) and the mass of the second (co)polymer (B) to the total mass of the matrix is less than or equal to 20%, preferably less than or equal to 15%.

According to the second aspect, the object of the present invention is an extrudable-spinnable composition for the production of at least a part of the outer surface of a filament or fiber, such as implemented according to the variant described with reference to the first aspect of the present invention As defined by any of the examples, the composition is derived from a first copolymer containing polyester, at least one olefin, and alkyl (meth)acrylate or (meth)acrylic acid, and containing ethylene oxide-C The reaction of the second (co)polymer mixture of ₂ H ₃ O, the ratio of the mass of the polyester to the total mass of the mixture is greater than or equal to 50%, still preferably greater than or equal to 60%, specifically greater than Or equal to 70%, more specifically greater than or equal to 80%, especially greater than or equal to 85%.

Preferably, the extrudable-spinnable composition according to the present invention is in the form of granules, chips, flakes or even powder.

The extrudable-spinnable composition according to the present invention can be used in a (single-screw or two-screw) extruder, BUSS blender, and preferably in a twin-screw co-rotating extruder in the molten state. Mixed, prepared by reactive extrusion.

Advantageously, the composition according to the invention is extruded during the extrusion-granulation step (also named compounding) before the (co)extrusion-spinning step (i) defined in the following with reference to the third aspect Machine-reactor preparation. This compounding step is within the scope of the present invention, and is preferably carried out on an extruder comprising at least two supply screws co-rotating with different regions, which can be heated independently of each other. These especially two co-penetrating extrusion screws rotate in the same direction in a hole in a fixed environment called a sheath; compared to another screw based on one or more defined areas for increasing shear, The screw pitch can be exchanged.

Preferably, during the extrusion-granulation step for preparing the extrudable-spinnable composition according to the present invention, the extruder/die extruder contains a temperature higher than or equal to 200°C, more preferably It is higher than or equal to 220°C, even more preferably higher than or equal to 240°C, specifically higher than or equal to 250°C, notably at least one temperature region lower than or equal to 300°C.

The extrusion reactive step includes the previous step of mixing polyester, the first copolymer (A) and the second (co)polymer (B), which is performed by sequentially shearing and pressing the mixture conveyed by the supply screw The reaction steps. All these steps are performed on a continuous extrusion reactor containing at least two supply screws. The extruder forming the continuous reactor contains a first zone for introducing polyester and polymers (A) and (B). The polymers (A) and (B) can be combined in the area of the same input terminal or the area of separate input terminals. Preferably, when one or more input ports are provided, each of the starting components used (polyester polymers (A) and (B)) is fed independently to the extruder. Independently control the supply rate of starting components. The polyester and polymers (A) and (B) are introduced into the extruder while hot or at ambient temperature. It can be introduced in solid form, especially granules, flakes, powder or any other solid form, or even in the molten state.

The reactive extrusion step can be carried out such as described in FR 2.897.356 A1. Preferably, the reaction between the polyester, the first copolymer (A) and the second (co)polymer (B) may be a homogeneous reaction.

The extrudable-spinnable composition according to the present invention may contain various additives to facilitate the implementation of the extrudable-spinnable composition, in particular slip agents, such as silica, N,N'-ethylene Base-bisamide, calcium stearate or magnesium stearate. These additives can also be mineral fillers, color pigments, anti-UV or antioxidants.

In one embodiment, the melt flow index (MFI, Melt Flow Index) of the extrudable-spinnable composition according to the present invention is specifically based on the standard ISO 1133-1 February 2012 or ASTM D 1238-2013 8. One of the months, measured at a temperature of 270°C under a weight of 2,16 Kg, which is greater than or equal to 10 cm ³ /10 min, preferably greater than or equal to 20 cm ³ /10 min, more preferably greater than or equal to 30 cm ³ /10 min, even more preferably greater than or equal to 40 cm ³ /10 min, especially greater than or equal to 45 cm ³ /10 min, notably less than or equal to 100 cm ³ /10 min.

According to the third aspect, the object of the present invention is a method of manufacturing silk or fiber according to any one of the modified embodiments described with reference to the first aspect of the present invention, which includes the following steps: i) Refer to the first aspect of the present invention The extrusion-spinning step of the composition defined in the two aspects, or the composition defined with reference to the second aspect of the present invention for forming the first polymeric structure constituting the matrix, and for forming at least one second polymeric structure Co-extrusion-spinning step of at least one polymeric composition (specifically extrudable and spinnable) to obtain fibers or filaments; ii) the filaments or the filaments obtained in step (i) as appropriate At least one drawing step of the fiber; iii) the forming step of the filament or the fiber used in the manufacture of textile articles as appropriate; iv) by the fiber or the filament (when step (i) or (ii) is completed) ) or for the textile article immersed in an alkaline bath in the shaping of the (meth) acrylic acid alkyl ester group is hydrolyzed to a carboxylate (-COO ^-) of the converting step; present in the filament v) optionally the fibers or Or the drying step of the textile article.

Preferably, the fiber, silk or textile article undergoes a dyeing step before the drying step.

Preferably, the first and second polymer structures are not mixed.

Preferably, the (co)extrusion-spinning step (i) is performed on a single screw extruder, and then the molten material passes through the die hole. The filament at the exit of the die then undergoes at least one drawing step such as described below. With regard to the present invention, the stretching step can be performed as known to those skilled in the art.

The fiber or filament according to the present invention can be carried out according to techniques known to those skilled in the art, such as the POY type (semi-drawn yarn) or FDY (full-drawn yarn) drawing step after the POY type step or directly During the POY type step, by adding a stretching step to the machine performing the POY type operation. Once the silk or fiber undergoes the POY type step, it can be followed by a DTY type (painted textured yarn) or ATY (air textured yarn, Taslan) texturing step.

Preferably, the forming step of the filament or the fiber used to manufacture the textile article may include a knitting step, a knitting step, a knitting step, a non-woven fabric manufacturing step or a combination thereof, and the thermal fixing of the textile article as the case may be Steps to stabilize the size of the product.

For the purposes of the present invention, "alkaline bath" means pH greater than or equal to 6, more preferably greater than or equal to 7, even more preferably greater than or equal to 8, specifically greater than or equal to 10, or even more specifically greater than or equal to Any aqueous solution of 12.

Specifically, the aqueous solution is an aqueous solution containing a solution of the metal salt of the present invention, such as sodium hydroxide and/or potassium hydroxide. Carboxylic acid functional groups and / or acrylate functional groups of the polymer is present A, polymer B and optionally converted into a metal salt carried dislocation in the presence of an aqueous solution of saponified bonded carboxylate functional group (-COO ^-).

Preferably, the hydrolysis step is performed by immersing the fiber or silk or textile article to be treated in a full bath for at least 1 minute, especially at least 30 minutes and preferably at most 50 minutes, and the temperature of the bath is greater than or equal to 40 °C, specifically 60 °C or higher, more specifically 80 °C or higher, especially 95 °C or lower.

This full bath immersion step is followed by a filling step, which consists of guiding the treated textile product between two rollers to remove any excess solution.

This saponification step is preferably followed by water for fibers, silk or textile articles, specifically at ambient temperature (especially at a temperature greater than 0°C and less than or equal to 40°C), such as a washing step in running water. This step can be followed by drying, for example by hot air or even microwaves.

Preferably, after the hydrolysis step (by saponification) and the drying step, the fiber, silk or textile article loses at least 1% of its mass, especially at least 2% of its mass, and more preferably at most 8% of its total initial mass before hydrolysis .

For the purposes of the present invention, "textile article" means any article that includes textile elements produced by forming fibers and/or silks according to the present invention.

In a variant, the method comprises an acidification step vi) after step iv) by immersing the fiber or the silk or the textile article in an acid bath.

The function of this acidification step is to convert all or some of the carboxylate groups formed during saponification into carboxyl groups.

Preferably, the H ⁺ ion concentration of the acid in the solution is determined based on the ratio of carboxylate functional groups to be converted into acid functional groups and therefore the absorption characteristics of acidic or alkaline gases are expected.

For the purposes of the present invention, "acid bath" means any aqueous solution with a pH less than or equal to 6, more preferably less than or equal to 5, and even more preferably less than or equal to 4.

In particular, the aqueous solution is an aqueous solution containing an acid, especially a mono- or polycarboxylic acid, for example acetic acid, or a strong acid such as hydrochloric acid or sulfuric acid or phosphoric acid.

Preferably, the acidification step is performed by immersing the fiber, silk or textile article to be treated in a full bath for at least 1 minute, especially at least 10 minutes, and preferably at most 30 minutes, and the temperature of the bath is greater than or equal to 10°C, specifically less than or equal to 60°C, more specifically less than or equal to 40°C, especially at ambient temperature.

This full bath step immersion step, especially by filling, is followed by an expression step consisting of guiding the treated textile product between two rollers to remove any excess solution.

This acidification step is preferably followed by a specific step of washing fibers, silks or textile articles with water, such as running water, at ambient temperature. This step can be followed by drying, for example in hot air.

In a variant, the method comprises an application step of applying at least one metal salt (such as defined in the present invention) to the silk or the fiber or the textile article during the hydrolysis step iv), the alkaline bath comprising at least one The metal salt and/or in the supplemental complexation step vii), especially by applying a solution of at least one metal salt (as defined in the present invention) to the filament or the fiber.

A metal salt (such as sodium or potassium) is present in the alkaline bath in the hydrolysis step, and therefore the saponification step can be subsequently replaced by another metal salt in the complexation step according to the expected need for gas absorption.

When a metal salt is present in the bath in the hydrolysis step (iv), all or parts of the carboxyl groups are hydrolyzed and complexed by the metal salt according to the concentration of the metal salt in the solution.

Preferably, the concentration of the metal salt is measured in the hydrolysis bath (iv), and if the case is complexed (vii), only some, preferably half of the carboxyl groups are hydrolyzed and complexed with the metal salt, so that the fiber and/or silk can absorb at the same time Alkaline and acid gases.

Advantageously, the metal salt used in the complexing step is selected from the following salts: Ca, Mg, Al and Ag or mixtures thereof.

According to the fourth aspect, the object of the present invention is a textile article comprising at least 5% by mass relative to its total mass of silk according to any of the variant embodiments described with reference to the first aspect of the present invention and /Or fiber.

In a variant, the textile article also contains synthetic fibers and/or silks, specifically selected from fibers and/or silks comprising the following group: polyester, polyamide and polypropylene or mixtures thereof.

According to the fifth aspect, the object of the present invention is a sports article that absorbs acid and/or alkaline gas, which includes a textile article according to any one of the variant embodiments described in the fourth aspect of the present invention, especially From the following items or items considered individually or in combination: backpacks; sports bags; clothing items such as undershirts, pants, shorts, underwear, gloves, socks, leggings; shoes; shoe components, such as insoles, linings, or uppers.

According to another aspect, the object of the present invention is a multifilament yarn comprising a plurality of filaments according to any of the variant embodiments described in the first aspect of the present invention.

According to the fourth aspect, the object of the present invention is the use of an extrudable-spinning composition according to any of the embodiments described with reference to the second aspect of the present invention, which is used to manufacture The first aspect describes the fiber or silk of any embodiment.

I-Preparation of the extrudable-spinnable composition according to the invention

The extrudable-spinnable composition according to the invention in the form of particles is obtained by mixing polyester (thermoplastic) in the form of particles with the first and second copolymers (A, B ) To prepare. The pellet mixture was fed at a rate of about 50 g/min to the hopper of the extruder containing two material feeding screws co-rotating. The components are assembled in an extruder, where they are melted, mixed and dispersed. This step is a reactive extrusion step, because the carboxylic acid functional group (-COOH) at the end of the polyester chain will react with the ethylene oxide group of the second polymer (B), especially the glycidyl group. The material leaving the extruder forms a stem with a diameter of about 3 mm, which is immediately cooled by means of cold water or at ambient temperature. The stalks are then fed to a granulation device, which drives the formed stalks at a constant speed and forms particles by cutting the stalks. The extruder contains at least five zones with different heating temperatures: the first feeding zone of the starting components at ambient temperature, therefore in solid form, in the form of pellets in this example; the second melting zone, where During this period, the starting component stores heat and begins to melt, corresponding to the third zone of the first mixing, where the starting component is cut off and completely melts when leaving the third zone; corresponding to the fourth zone of the second mixing, During this period, the starting components are dispersed, corresponding to the fifth zone at the end of the twin screw, where the mixed and dispersed starting components are extruded through an extrusion die, which in this example contains the only hole for forming the stem mouth. One of the two feeding screws includes at least a reverse step in the fifth zone, keeping synchronization with the other zones to disperse the starting components in the molten state. The extruder is heated on either side of each zone, which represents six independent and separate heating stages. The twin screw in this example is a screw Rheomex PTW 16/25 OS coupled to a Rheodrive 7 OS-3*400V motor, sold by ThermoScientificHaake.

Prior to this, the polyester particles had been heated at 90°C for 16 hours to limit the minimum humidity rate, and therefore the subsequent hydrolysis of the polyester chain was carried out as appropriate.

The initial parameters of the extruder are: the torque is 65 Nm, the screw rotation speed is 450 rpm, the screw supply speed in the first zone is 12%, the mold pressure is 5.7 bar, the material temperature is about 260°C and the mold temperature It is about 245°C. The six temperature stages from the first zone to the sixth zone are respectively 165°C, 274°C, 274°C, 270°C, 260°C and 255°C.

The first copolymer A is a copolymer of ethylene and methyl acrylate; it has a ratio of about 29% by mass of methyl acrylate and a melt index of about 2-3.5 g/10 min (190°C/2.16 Kg) (February 2012) ISO 1133-1/ASTMD1238 in August 2013); melting point is 61℃ (ISO 11357-3 in March 2013); the average molar mass Mw by mass is 105 213 g/mol and the average molar mass is average Mn is 16 322 g/mol, the Vicat softening point is at 40℃ (ISO 306/ASTMD 1525 2017 or 2009 in January 2014), and the elongation at break is 900% (ISO 527-2/ASTM D638 in April 2012) 2014).

The second copolymer B is a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate, which has a ratio of about 24% by mass of methyl acrylate and a ratio of about 8% by mass of glycidyl methacrylate. Melt index of about 6 g/10 min (190℃/2.16 Kg) (ISO 1133-1 in February 2012/ASTMD1238 in August 2013); melting point is 65℃ (ISO 11357-3 in March 2013); by mass The calculated average molar mass Mw is 103 499 g/mol, and the average average molar mass Mn is 16 491 g/mol, and the Vicat softening point is 40℃ (ISO 306/ASMD 1525 2017 or 2009 in January 2014 ), and 1100% elongation at break (ISO 527-2/ASTM D638 2014 in April 2012).

The polyester is selected according to the extrudable-spinnable grade, such as the polyester sold by Invista or Dupont de Nemours with reference to RT20. The first polymer (A) and the second polymer (B) can be found in Dupont de Nemours in the Elvaloy product range, or again in the Lotryl and Lotader product range in Arkema.

表1

表2Table 1 below lists the mass ratios of different starting components to the total mass of the composition that has been extruded and then converted into pellets.

Table 1

Table 2

Table 2 above shows the theoretical molar amount of the acrylate functional group proposed relative to the mass of the first and second polymers (A) and (B). In these examples, the acrylate functional group here consists of the first The first and second polymers (A) and (B) are supported. Obviously, the more the amount of the second copolymer B increases, the more the pressure in the extrusion die increases from the set point of 5.7 bar, and the temperature T5 in the extrusion die also increases. The inexhaustible explanation of this phenomenon will lie in the reaction of the glycidyl functional group of the second copolymer B with the carboxylic acid functional group at the end of the polyester chain, which will increase the viscosity of the extruded material and therefore increase the Friction and shear, and correspondingly increase the pressure and temperature in the mold area. This grafting reaction is shown in Figure 4. II- Spinning the composition of I converted into particles

表3The analysis methods 1 to 4 in Table 3 below correspond to the composition of the analysis methods 1 to 4 defined in Table 1. These compositions have been extruded and spun by a single screw extruder, which includes an extrusion die with multiple spinning holes and a filter array. The stretching and spinning means are arranged at the output end of the extrusion die and especially include nozzles that send air jets to interweave the filaments. The formed yarn is a multifilament yarn containing 48 filaments. The wire is cooled by means of a flow of cold air. As it leaves the spinning and drawing steps, the yarn is especially coated with a sizing agent (such as sold under reference Fasavin KB 88) of about 10% by mass relative to the total mass of the monofilament.

table 3

Table 3 lists the measured denier and resilience of different yarns obtained according to the stretching technology performed.

The structure of the obtained yarn was also characterized by analyzing the silk segment with a scanning electron microscope. This shows the formation of a nodule comprising a first copolymer A placed in a bag, where the "shell" is formed by a second copolymer B that uses a coupling agent with a polyester matrix. III- Saponification step and acidification step

Knitting (jersey weave) was performed according to DTY 150 denier yarn containing 48 filaments according to the analysis method 4 defined in Table 3. The surface quality of knitwear is 31 g/m². Prepare a 6 cm × 6 cm sample and soak in a bath containing 5 g/l of soda at 85-90°C for 45 minutes. The non-pH indicator dosage measures the soda consumption of 50+/-10 meq/Kg knitwear (by measuring the soda concentration in the bath after the saponification step). The loss of knit quality after saponification is about 1.8%. The amount of acrylate in meq and therefore saponifiable is 168.5 mmol per kilogram of the knitted fabric tested. In this way, the measured soda consumption infers that about 30% of the acrylate functional groups have been saponified into the form of carboxylate functional groups.

The saponified knitwear is then subjected to an acidification step, in which the sample is immersed in a 0.02 mol/L (or 0.04 mol/L = [H ⁺ ]) sulfuric acid solution bath for 45 minutes, and the bath is at ambient temperature. The pH indicator dose measures the average acid consumption of 15 +/- 5 mmol H ⁺ /kg knitwear. This acid consumption corresponds to about 30% of the 50 meq of soda consumed in the saponification step per kilogram of knitwear. IV- Measure the absorption of acid gas

These rates are measured in accordance with the ISO 17299-3:2014 standard and "Textiles-Determination of deodorant property-Part 3: gaseous phase chromatography method" that began in March 2014. The reduction rate calculation is indicated in point 8 of the standard, and corresponds to the FID spectrum (Hydrogen Flame Ionization Detector) surface (Sb) of the gas test without textile components is less than the FID peak value of the gas test with textile components The average difference of the average surface (Sm), which is applied to the surface Sb and then multiplied by 100. In this way, a negative or zero value indicates that there is no reduction in the gas target. The gas target used in the measurement reported below is acetic acid.

It should be noted that the ISO 17299-3:2014 standard of March 2014 mentioned above provides scrubbing before obtaining the absorption measurement of the target gas.

The acetic acid absorption value of the knitted fabric described in paragraph III and only saponification above is 73% +/- 4%.

By comparison, the absorption value of standard knitwear containing only polyester is lower than 40%.

The acetic acid absorption value of the knitted fabric that has been subjected to the saponification step and the acidification step described in paragraph III above is 88% +/- 2%. The acidification step thus improves the acetic acid absorption characteristics.

During the "internal sampling test", the inventor noticed that the effectiveness of synthetic textiles on bad odors was sensed by users from at least 50% of the gas absorption value, and the value increased significantly from 80%.

The absorption mechanism of acid gas (acetic acid in this example) is related to the acid-base reaction, and the carboxylic acid functional group and the carboxylic acid radical are carried by the silk. In particular, the reaction between the carboxylate functional group and acetic acid produces a non-volatile metal carboxylate (CH ₃ COONa), which can explain the reduction in perceived odor. This will lead to the deodorization of the gas by salinization.

Due to the significant effect obtained in the reduction of the perceived odor, the polar interaction and hydrogen bonding between the carboxylic acid functional group and the acetic acid may also occur to explain this remarkable phenomenon of acetic acid absorption. Reinitialization of the textile article can be achieved by rinsing the textile article in running water (for example during household washing) or even by drying the textile article, transferring the acid-base balance and vaporizing acid gas. The yarns according to the invention and implemented in knitted and test samples are entirely in the extrudable-spinable composition according to the invention. However, as far as the present invention is concerned, only the surface of the yarn is in contact with odorous molecules, so that in order to save energy, when the core-outer type yarn is prepared, it can only have a polyester based on the polymer A and B on the surface of the yarn. The outer layer contains a functional matrix that absorbs gas. In this case, the extrudable-spinnable composition according to the present invention is co-extruded with another polymeric composition, thereby forming a first polymeric structure composed of the matrix (for example, forming an outer layer), which is parallel to the second A polymer structure, the second polymer structure being composed of a second co-extrusion polymer composition (for example, more than 95% by mass of polyester).

The present invention will be more clearly understood from the following description of the embodiments of the present invention given by non-limiting examples with reference to the accompanying drawings, in which:-Figure 1 is used in the embodiments described below for manufacturing according to the present invention The schematic diagram of the first polymer A of the silk, which is a copolymer of ethylene and methyl acrylate;-Figure 2 is the second polymer (B) used to manufacture the silk of the present invention in the examples described below Schematic diagram, and it is a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate;-Figure 3 schematically shows polyethylene terephthalate;-Figure 4 schematically shows the reactive extrusion During pressing, the second polymer B shown in Figure 2 is grafted onto the polyester shown in Figure 3;-Figure 5 schematically shows the methacrylate of the first polymer A shown in Figure 1 Saponification of functional groups;-Figure 6 schematically shows the acidification of the carboxylate functional groups of the first saponified polymer A.

Claims (28)

A silk or fiber that absorbs odorous molecules, which has a definite outer surface, wherein at least a part of the surface contains carboxyl -COOH and/or carboxylate -COO ^- complexed with a metal salt, characterized in that the part is composed of The following matrix composition, the matrix derived from the first copolymer (A) containing a polyester and at least one olefin and alkyl (meth)acrylate and/or (meth)acrylic acid, and containing ethylene oxide group- Reaction of a mixture of the second (co)polymer (B) of C ₂ H ₃ O in which at least some of the (meth)acrylate functional groups of the copolymer (A) have been converted into corresponding carboxylate and/or corresponding Carboxylic acid functional group. Such as the silk or fiber of claim 1 , wherein the odorous molecule is acid and/or alkaline gas. The silk or fiber of claim 1 or 2 , characterized in that the first copolymer (A) of at least one olefin and alkyl (meth)acrylate and/or (meth)acrylic acid is an elastomer. The yarn or fiber of claim 3 , characterized in that the second (co)polymer (B) is an elastomer. The silk or fiber of claim 1 or 2 , characterized in that the second (co)polymer (B) containing ethylene oxide group is at least one olefin, alkyl (meth)acrylate or (meth) A terpolymer of acrylic acid and monomer units containing ethylene oxide groups. The silk or fiber of claim 1 or 2 , characterized in that the second (co)polymer (B) containing an oxirane group is an ethylene, an alkyl (meth)acrylate or (methyl) A terpolymer of acrylic acid and glycidyl (meth)acrylate. Such as the silk or fiber of claim 1 or 2 , characterized in that the metal salts are one or more metal salts selected from the group consisting of the following metals: potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), aluminum (Al), silver (Ag) or mixtures thereof. The silk or fiber of claim 1 or 2 , characterized in that it comprises first and second non-mixed polymeric structures, and the first polymeric structure is the matrix. The silk or fiber according to claim 8 , characterized in that the second polymeric structure comprises at least one polymer selected from the group consisting of: polyamide 6, polyamide 6-6, polyamide 12, polyamide 11, Polyamide 4-6, polyester, polypropylene and polyethylene or their mixtures. The silk or fiber of claim 1 or 2 , characterized in that the silk or the fiber has a heterogeneous transversal cross-section of the core-outer layer type, and the outer layer is formed by the matrix. The silk or fiber of claim 1 or 2 , characterized in that the matrix contains more than 50% by mass (g) of polyester relative to its total mass (g). The silk or fiber of claim 1 or 2 , characterized in that the matrix contains more than 60% by mass (g) of polyester relative to its total mass (g). The silk or fiber of claim 1 or 2 , characterized in that the matrix contains more than 70% by mass (g) of polyester relative to its total mass (g). The silk or fiber of claim 1 or 2 , characterized in that the matrix contains more than 75% by mass (g) of polyester relative to its total mass (g). The silk or fiber of claim 1 or 2 , characterized in that the mass ratio of the first copolymer (A) to the second (co)polymer (B) in the matrix is between 99/1 and 85/15 between. The silk or fiber of claim 1 or 2 , characterized in that the sum of the mass of the first copolymer (A) and the mass of the second (co)polymer (B), relative to the total mass of the matrix, is Less than or equal to 20% and greater than 0%. An extrudable-spinnable composition for producing at least a part of the defined outer surface of the filament or fiber of claim 1 or 2 , characterized in that the composition is derived from the reaction of a mixture comprising: The first copolymer (A) of polyester, olefin, and alkyl (meth)acrylate and/or (meth)acrylic acid, and the second (co)polymer containing ethylene oxide-C ₂ H ₃ O (B), the mass of the polyester relative to the total mass of the mixture is greater than or equal to 50%, and is characterized in that the polyester is selected from: polyethylene terephthalate, polyethylene terephthalate Methyl ester, polycyclohexane-dimethylene or polyethylene dicarboxylate 2,6 naphthalene; or selected from any of the monomer units listed below Polymers, copolymers, terpolymers, and mixtures thereof: ethylene terephthalate, propylene terephthalate, butylene terephthalate, and 1,4-cyclohexylene-dimethylene Terephthalate (1,4-cyclohexylene-dimethylene terephthalate). The composition of claim 17 , characterized in that the polyester is ethylene terephthalate The composition of claim 17 , characterized in that it has a melt flow index (MFI MFI) greater than or equal to 10cm ³ /10min, which is based on ASTM D 1238-August 2013, at a temperature of 270°C, and a weight of 2.16Kg Measured below. A use of the extrudable-spinnable composition according to claim 17 for the manufacture of at least a part of the defined outer surface of the absorbent yarn or fiber according to claim 1. A method for manufacturing silk or fiber as claimed in claim 1 or 2 , characterized in that it comprises the following steps: i) an extrusion-spinning step of the composition as claimed in claim 17 , or a first polymerization for forming a matrix The co-extrusion-spinning step of the composition of claim 17 and the at least one polymeric composition used to form at least one second polymeric structure to obtain fibers or filaments, iv) by the wire or textile article immersed in an alkaline bath, (meth) acrylic acid alkyl ester group is hydrolyzed to a carboxylate (-COO ^-) conversion step. The manufacturing method of claim 21 , which is characterized by further comprising ii) at least one drawing step of the filament or the fiber obtained in step (i). The manufacturing method of claim 21 , which is characterized by further comprising iii) a forming step of the silk or the fiber for manufacturing the textile article. The manufacturing method according to any one of claims 21 to 23 , characterized in that it comprises an acidification step vi) performed by immersing the fiber or the silk or the textile article in an acid bath after step iv). The manufacturing method according to any one of claims 21 to 23 , characterized in that during step iv) at least one metal salt is applied to the silk or the fiber or the textile article, and the alkaline bath contains at least one metal salt; or In a supplementary complex step vii), by applying a solution of at least one metal salt to the silk or the fiber or the textile article. A multifilament yarn characterized in that it contains a plurality of filaments as claimed in any one of claims 1 to 16 . A textile article characterized in that it contains at least 5% by mass relative to its total mass of silk and/or fiber as claimed in claim 1 or 2 . A sports article that absorbs acid and/or alkaline gas, characterized in that it comprises a textile article as in claim 27 , the textile article is selected from: backpack; sports bag; clothing article, such as undershirt, pants, shorts, Underwear, gloves, socks, leggings; shoes; shoe components such as insoles, linings, or uppers.

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