CN110914489A - Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre - Google Patents

Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre Download PDF

Info

Publication number
CN110914489A
CN110914489A CN201880027044.XA CN201880027044A CN110914489A CN 110914489 A CN110914489 A CN 110914489A CN 201880027044 A CN201880027044 A CN 201880027044A CN 110914489 A CN110914489 A CN 110914489A
Authority
CN
China
Prior art keywords
filament
meth
copolymer
fibre
mass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201880027044.XA
Other languages
Chinese (zh)
Inventor
S·福廷
B·柯奇许
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Decathlon SE
Original Assignee
Decathlon SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Decathlon SE filed Critical Decathlon SE
Publication of CN110914489A publication Critical patent/CN110914489A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
    • 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
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/11—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with halogen acids or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/55—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur trioxide; with sulfuric acid or thiosulfuric acid or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/68—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
    • D06M11/70—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/188—Monocarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/192—Polycarboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/20—Polyalkenes, polymers or copolymers of compounds with alkenyl groups bonded to aromatic groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/18—Synthetic fibres consisting of macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/26—Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/32—Polyesters

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention relates to a thread or fibre which absorbs odorous molecules, in particular acidic and/or basic gases, having a defined outer surface, wherein at least one part of the surface comprises carboxyl groups-COOH and/or carboxylate groups complexed with metal salts. Advantageously, the portion consists ofThe matrix comprises: the matrix is derived from a first copolymer (A) comprising a polyester and at least one olefin and alkyl (meth) acrylate and/or (meth) acrylic acid and a copolymer comprising ethylene oxide-C2H3Reaction of a mixture of a second polymer (copolymer) (B) of O, at least some of the (meth) acrylate functions of copolymer (A) having been converted to the corresponding carboxylate and/or corresponding carboxylic acid functions.

Description

Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre
Background
The present invention relates to the technical field of fibres or filaments having an absorbing capacity for acidic and/or alkaline gases, in particular with respect to bad odours deriving from perspiration.
During exercise, physical labor elevates body temperature, producing more perspiration than at rest and producing odorous volatile compounds. The first textile layer worn by the user during exercise exercises is the preferred recipient of the sweat and, in particular, of the odorous molecules produced by the degradation of the proteins contained in the sweat by the bacteria present on the skin. This textile layer retains these odorous molecules and therefore smells very poorly after a sports competition, especially when dry, and has to be washed before the next competition. With polyester textile layers, bad odors are often released even during sports competitions.
This unpleasant odour-related property of textiles made of polyester generally occurs immediately upon contact of the textile with the wearer's perspiration, rather than being produced by the latter during physical activity.
Textile materials do not react in the same way to odors. Natural materials, especially wool-based materials, do not smell too much or even not much under bad smell, especially in connection with perspiration.
Today, existing solutions for limiting the bad smell of synthetic textiles, in particular polyesters, consist of: the odor is suppressed by absorbing and/or destroying and/or masking the odor, or by eliminating bacteria responsible for synthesizing the odoriferous molecules.
To remedy these drawbacks, use is made of textiles obtained from fibres and/or functionalized filaments with cyclodextrin cage molecules or nanoparticles of charcoal, bamboo or coconut, or even coffee-based fibres. These solutions are not long lasting, however, because the functionalizing agents are eliminated during the washing and/or also have a limited odor-absorbing efficacy and/or modify the feel characteristics of the textiles, for example by stiffening them, in particular cyclodextrins.
Another solution consists of: odour-absorbing materials, such as natural fibres, for example cotton, are incorporated in polyester-based textiles. However, this solution has the disadvantage of being costly and does not allow the textile to dry quickly and thus also accelerates the removal of perspiration. The quick drying and removal properties of perspiration are particularly preferred for technical textiles used for sports practice. In addition, cotton tends to pill.
The textile may also have antimicrobial agents such as silver, copper, zinc oxide, titanium, zirconium or platinum nanometals. But these antibacterial agents act directly on bacteria that come into contact with the skin. This solution is therefore only suitable for textiles intended to be worn very close to the body, such as socks, but is ineffective or significantly less effective, for example for T-shirts. Furthermore, regulations on biocides are becoming more and more stringent as they affect the skin bacterial flora.
EP 0.792.957B 1 describes carboxylic acid salt groups (-COO) complexed by means of carboxyl groups (-COOH) and by metal salts (e.g.sodium salts)-) To produce fibers having both acidic and basic gas absorption properties for odor removal (see [0002 ]]). The fibers are prepared by reacting hydrazine (NH)2-NH2) Modifying a base fiber comprising more than 40% by weight Polyacrylonitrile (PAN) to reticulate the fiber and increase its nitrogen content by 1% to 8% of its total weight. The nitrile groups based on the fibers are hydrolyzed with the aid of an alkaline solution of a metal salt, for example sodium hydroxide or potassium hydroxide. The fibers were then soaked in a nitric acid solution for 30 minutes, followed by washing (see embodiment 1, [0048 ]])。
The process described in EP 0.792.957B 1 is only applicable to polyacrylonitrile fibers obtained by coagulation of Polyacrylonitrile (PAN) followed by spinning thereof, by definition. The resulting fibers have a rose color and are not or very difficult to dye. In addition, these fibers are not sufficiently resilient to constitute a yarn alone, and it is therefore necessary to use them in combination with other fibers and/or filaments in order to alleviate their limited mechanical properties. Blends of acrylic and synthetic fibers (e.g. polyester fibers) are complicated by dyeing problems (acrylic fibers are often blended with wool and cannot withstand temperatures in excess of 100 ℃). In addition, yarns comprising polyacrylonitrile fibers (e.g., yarns spun from fibers) tend to pill and have poor abrasion resistance.
Finally, the technical articles of sports are mainly in synthetic materials, such as polyester or polyamide, and not based on cotton or viscose or even acrylic fibres, because of the cost and efficiency in terms of quick drying and evacuation of humidity, as well as the ease of use, in particular with regard to mechanical properties and dyeing.
There is therefore a need for a fibre or filament, in particular based on polyethylene terephthalate, which eliminates the above-mentioned problems, in particular absorbs and/or neutralizes unpleasant odours, and which, despite being durable in washing, is easy to manufacture and can be made into yarn, then into textile form and easily dyed.
Objects and summary of the invention
A first aspect of the object according to the invention is a filament or fibre which absorbs odorous molecules, in particular acidic and/or basic gases, having a defined outer surface, wherein at least a part of the surface comprises carboxyl groups-COOH and/or carboxylate groups-COO complexed with a metal salt-. Advantageously, this part consists of a matrix derived from a first copolymer (A) comprising a polyester, at least one olefin and an alkyl (meth) acrylate and/or (meth) acrylic acid and comprising an ethylene oxide group-C2H3Reaction of a mixture of a second polymer (copolymer) (B) of O, at least some of the (meth) acrylic acid or (meth) acrylate functional groups of copolymer (a) having been converted to the corresponding carboxylate and/or corresponding carboxylic acid functional groups.
Advantageously, the fiber or filament according to the invention comprises a portion of its external surface constituted by a polyester matrix combining a first polymer (A) and a second polymer (B), the first polymer (A) contributing (meth) acrylate functions, all or some of which are converted into carboxylic acid functions-COOH and/or carboxylate functions-COO-. The first copolymer (A) may also comprise acrylic functional groups with the necessary carboxylic functional groups-COOH and therefore does not need to be converted by an acid-base reaction to absorb alkaline gases. The second polymer (B) stably incorporates the first polymer (a) into the matrix and adapts the viscosity of the matrix, in particular so that it can be extrusion-spun.
Advantageously, once the (meth) acrylate group in this moiety has undergone the saponification and/or acidification and/or complexation steps described hereinafter, it forms said corresponding carboxylic group (-COOH) and/or said corresponding carboxylate group (-COO) complexed with a metal salt-)。
The main mechanisms for gas absorption are based on carboxylic acid functional groups carried by the fibers or filaments (which will react with alkaline gases) and/or on carried carboxylate 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. With respect to acid gases, the deodorization of acid gases (e.g., acetic acid) is by salinization, by capturing acid gases as nonvolatile metal carboxylates (e.g., by producing (CH)3COO-,M+) Wherein M is+Is a metal salt of acetic acid). Regeneration of the fibres or filaments may be achieved by rinsing (home washing of the textile comprising the fibres and/or filaments).
The absorption characteristics of the fibers or filaments towards acidic and/or alkaline gases are linked to the intrinsic structure of the fibers or filaments, which ensures a long-lasting action in terms of odor, contrary to the chemical treatments of the prior art.
Advantageously, the second polymer (copolymer) (B) ensures the function of a coupling agent between the polyester matrix and the first copolymer (a) through chemical bonds, in particular through covalent bonds, and/or polar bonds.
Observing a cross section of the filament according to the invention by means of a scanning electron microscope, polymers a and B form nodules in the polyester matrix, polymer a being encapsulated by polymer B, which forms the physical interface between polymer a and the polyester matrix.
In addition, the reactive oxirane groups in the second (co) polymer are reactive with the polyester matrix by means of polar and/or covalent bonds. Advantageously, the ends of the polyester chains in the polyester matrix comprising carboxylic acid functions (COOH) are reacted with the ethylene oxide groups of polymer B, in particular glycidyl (meth) acrylate. The second polymer (copolymer) (B) must advantageously have a "compatible" chemical structure, i.e. capable of being processed together with the first copolymer (a) and the polyester matrix in an extrusion-spinning reaction.
According to one embodiment, polymer B is a copolymer of at least one olefin and at least one monomer unit comprising an ethylene oxide group.
The presence of olefin monomer units in the polymer chain of the second polymer (copolymer) (B) results in a "polyolefin" backbone which very significantly improves the compatibility with the first copolymer (a) also comprising a "polyolefin" backbone.
According to one embodiment, polymer B is a copolymer of at least one monomer unit comprising an ethylene oxide group with an alkyl (meth) acrylate and optionally at least one olefin. Advantageously, polymer B also contributes acrylate functions, wherein all or some of these acrylate functions are converted into the corresponding carboxylate and/or the corresponding carboxylic acid functions.
Preferably, the ratio of the mass (g) of polyester in the matrix with respect 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%, in particular greater than or equal to 75%, more in particular greater than or equal to 80%, even more in particular greater than or equal to 85%, optionally greater than or equal to 90%.
The ratio (a)/(B) of the mass of the first copolymer (a) introduced into the matrix relative to the mass of the second polymer (copolymer) (B) is between 10/90 and 95/5, preferably between 50/50 and 95/5, even more preferably between 70/30 and 90/10, in particular between 85/15 and 90/10.
According to one embodiment, the mass proportion of alkyl (meth) acrylate in the first (a) and optionally in the second (B) polymer is greater than or equal to 20%, 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 comprising an ethylene oxide group-C2H3The second polymer (copolymer) (B) of O is thermoplastic, in particular its melting temperature (Tf) allows it to be processed by extrusion, in particular by extrusion-granulation (compounding) and extrusion-spinning.
Preferably, the first (a) and optionally the second (B) polymer have a melting temperature greater than or equal to 55 ℃, more preferably less than or equal to 180 ℃, even more preferably less than or equal to 140 ℃, in particular less than or equal to 100 ℃, even more in particular less than or equal to 80 ℃.
Preferably, the flexural modulus of the first (a) and optionally of the second (B) polymer is greater than or equal to 5MPa, more preferably greater than or equal to 7 MPa. Flexural modulus can be measured on samples molded by compression using the method described in standard SO 178:2010 or using standard astm D790D 1525.
Preferably, the vicat softening point at 10N of the first (a) and optionally of the second (B) polymer is less than or equal to 60 ℃, more preferably less than or equal to 50 ℃, even more preferably less than or equal to 40 ℃. Vicat softening points can be measured on samples molded by compression using the method described in standard ISO306:2004 or using standard ASTM D1525.
Preferably, the melt flow index (190 ℃/2.16Kg) of the first (A) and optionally of the second (B) polymer is greater than or equal to 2g/10 min.
The fineness (dtex, denier) indicated herein can be measured by means of standard NFEN ISO 2060 at 6 months 1995.
In the present invention, "polyester" refers to any polymer resulting from the condensation of a polyol, especially a diol, with an aromatic polycarboxylic acid, especially an aromatic dicarboxylic acid.
Preferably, the polyester according to the invention is selected from: polyethylene terephthalate, polytetramethylene terephthalate, polycyclohexane-dimethylene or polyethylene 2, 6-naphthalene dicarboxylate (6 naphthalene), and more preferably polyethylene terephthalate. Other polyesters may be used, such as homopolymers, copolymers, terpolymers and mixtures thereof of monomer units selected from the list comprising: ethylene terephthalate, propylene terephthalate, butylene terephthalate and 1,4-cyclohexylene-dimethylene terephthalate, especially ethylene terephthalate.
Preferably, the polyester according to the invention is in a grade configured to be spun to convert into yarn.
In the present invention, "polyol" means any compound comprising at least two hydroxyl functions (-OH), in particular any (diol) compound comprising only two hydroxyl functions (-OH).
In the present invention, "aromatic polycarboxylic acid" means any compound comprising at least two carboxylic acid functions (-COOH) and at least one aromatic ring, in particular any compound comprising only two carboxylic acid functions and at least one aromatic ring (aromatic dicarboxylic acid).
In the present invention, "acid gas" means a functional group (-COO) capable of reacting with a carboxylate in an acid-base reaction-) Any gas that reacts, and "alkaline gas" refers to any gas that is capable of reacting with an acid functionality (-COOH) 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, octanoic acid, nonanoic acid, and more preferably acetic acid.
Optionally, 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.
In the present invention, "filament" refers to any elongated textile element of indefinite length (as it is not limited in theory).
In the present invention, "fiber" means any elongated textile element of defined length (since it is limited), in particular short or long fibers.
In the present invention, "yarn" means yarn spun from fibers, monofilament yarn (monofilament), multifilament yarn, and a mixture of these.
In the present invention, the metal salt means that the metal salt contains a metal cation moiety (M)n+) (n is an integer greater than or equal to 1) and an anionic moiety (optionally a non-metal), wherein the overall negative charge neutralizes the charge of the cationic metal moiety, 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)+；Ag2+；Ag3 +)。
In the present invention, "copolymer" means any polymer comprising at least two different monomer units, which repeat at regular or irregular (random) intervals, depending on the chain of the copolymer. When the copolymer comprises three different monomer units, it is more particularly a terpolymer.
In the present invention, "olefin" means a compound of the formula- (CH)2-CR1R2)nAny repeating olefin monomer of (a), wherein R1And R2Each independently of the other represents: a hydrogen atom or an alkyl group, preferably a linear or branched and acyclic, preferably a hydrogen atom. The alkyl group may comprise one to ten carbon atoms, more preferably one to six carbon atoms, especially one to four carbon atoms. The alkyl group is preferably: methyl-CH3(ii) a ethyl-CH2-CH3Or propyl (n-propyl or isopropyl), butyl (e.g. n-, sec-, iso-or tert-butyl), pentyl, hexyl, heptyl, octyl, nonyl, decyl.
The first (a) and/or second (B) polymers according to the invention may be syndiotactic, isotactic or atactic polymers.
In the present invention, "(meth) acrylic acid alkyl ester" means a compound of the formula- (CH)2-C(CH3)COO(R1) Is- (CH) or (C-H)2-CHCOO(R1) Any of the monomer units of (a) or (b), wherein R is a hydrogen atom1The group is an alkyl chain, preferably saturated, linear or branched, more preferably acyclic, more preferably containing from 1 to 20 carbon atoms (represented by C1-C20), more preferably C1-C15, even more preferably C1-C10, more particularly C1-C8, even more particularly 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.
Herein, the expression methyl as (methyl) below means that the latter is considered optional.
In the present invention, "(meth) acrylic acid" means a compound of the formula- (CH)2-C(CH3Or H) COOH) -.
In the present invention, "thermoplastic" means any polymer (copolymer) having a melting temperature Tf and capable of being transformed by extrusion. The melting temperature Tf can be measured using the method described in the standard ISO 11357-3: 2011.
In the present invention, "ethylene oxide" means a compound of the formula-C2H3Any group of O. This group may be carried by glycidyloxy groups which in turn are carried by one or more different repeating monomer units present in the polymer chain of the second polymer (copolymer) (B). Preferably, the monomer unit is glycidyl (meth) acrylate.
Preferably, the ethylene oxide groups are contributed by monomer units selected from: glycidyl acrylate, Glycidyl Methacrylate (GMA) and glycidyl vinyl ether, preferably glycidyl acrylate and Glycidyl Methacrylate (GMA).
In one variation, the metal salt is a salt of one or more metals selected from the group consisting of: potassium (K), sodium (Na) (particularly after saponification), calcium (Ca), magnesium (Mg), aluminum (Al) and silver (Ag) (particularly after complexation) or mixtures thereof.
In one variant, the first copolymer (a) of an olefin with an alkyl (meth) acrylate or (meth) acrylic acid and optionally the second polymer (copolymer) (B) (each) are elastomeric.
In one variant, the second polymer comprising ethylene oxide groups is a terpolymer of at least one olefin, an alkyl (meth) acrylate or (meth) acrylic acid and monomer units comprising ethylene oxide groups, in particular an ethylene, alkyl (meth) acrylate or (meth) acrylic acid and glycidyl (meth) acrylate terpolymer.
In one variant, the filament or fibre according to the invention comprises a first and a second non-mixed polymeric structure, the first structure being the matrix.
Preferably, the mass of the first polymeric structure is less than or equal to 30% and greater than or equal to 0%, in particular less than or equal to 20%, more in particular less than or equal to 10%, relative to the total mass of the fibre or the filament.
Preferably, the mass of the second polymeric structure is greater than or equal to 50%, in particular greater than or equal to 70%, more in particular greater than or equal to 80%, especially greater than or equal to 90%, relative to the total mass of the fibres or the filaments.
This arrangement optimizes the mass proportion of the functional gas-absorbing matrix according to the invention and therefore the final cost.
Advantageously, the first and second polymeric structures are coextruded, followed by spinning, but two distinct structures are formed in the fiber or filament.
In one variation, 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 (especially polyethylene terephthalate), polypropylene and polyethylene or combinations thereof.
Preferably, the polymer constitutes at least 85%, more preferably at least 90%, in particular at least 95% of the mass of the second polymeric structure.
In one variant, the filaments or fibres have a heterogeneous cross-section (heterogonous cross-section) of the core-outer layer type, the outer layer being constituted by the matrix (or the first polymeric structure), preferably the core being constituted by the second polymeric structure.
The fiber or filament according to the present invention may have any arrangement as seen in its cross-section, as long as it comprises at least a portion of its surface such as defined according to the present invention. In particular, the fibers or filaments according to the invention may be of the core-outer layer type, having a multilobal or cylindrical core and an outer layer conforming to the shape of the core, or conversely independently substantially cylindrical or multilobal.
In one variation, the mass relationship of the first (a) and second (B) polymers in the matrix is between 99/1 and 85/15.
In one variant, the sum of the mass of the first copolymer (a) and of the mass of the second polymer (copolymer) (B) has a relationship to the total mass of the matrix of less than or equal to 20%, preferably less than or equal to 15%.
According to a second aspect, the present invention is directed to an extrudable-spinnable composition for making at least part of the outer surface of a filament or fibre, such as defined according to any one of the variant embodiments described with reference to the first aspect of the invention, said composition being derived from a first copolymer comprising a polyester, at least one olefin and an alkyl (meth) acrylate or (meth) acrylic acid, and comprising an ethylene oxide group-C2H3Reaction of a mixture of a second (co) polymer of O, the proportion of the mass of the polyester relative to the total mass of the mixture being greater than or equal to 50%, also preferably greater than or equal to 60%, in particular greater than or equal to 70%, more in particular greater than or equal to 80%, especially greater than or equal to 85%.
Preferably, the extrudable-spinnable composition according to the invention is in the form of granules, chips, flakes or even powder.
The extrudable-spinnable compositions according to the invention can be prepared by reactive extrusion by mixing in the molten state in a (single-screw or twin-screw) extruder, a BUSS blender, and preferably in a twin-screw co-rotating extruder.
Advantageously, the composition according to the invention is prepared in an extruder-reactor during an extrusion-granulation step (also named compounding) before the (co) extrusion-spinning step (i) defined hereinafter with reference to the third aspect. This compounding step is carried out within the scope of the present invention, preferably on an extruder comprising at least two supply screws co-rotating with different zones and capable of being heated independently of each other. These are, in particular, two co-penetrating extrusion screws rotating in the same direction in a bore of a fixed environment called sheath; the pitch of the screw may be reversed compared to another screw according to one or more determined zones for increasing shear.
Preferably, during the extrusion-pelletization step for preparing the extrudable-spinnable composition according to the invention, the extruder/die extruder comprises at least one temperature zone having a temperature higher than or equal to 200 ℃, more preferably higher than or equal to 220 ℃, even more preferably higher than or equal to 240 ℃, in particular higher than or equal to 250 ℃, notably lower than or equal to 300 ℃.
The extrusion reactive step comprises the previous step of mixing the polyester, the first copolymer (a) and the second polymer (copolymer) (B), the reaction step carried out by subjecting the mixture conveyed by the supply screw to successive shearing and pressing operations. All these steps are carried out on a continuous extrusion reactor comprising at least two supply screws. The extruder forming the continuous reactor comprises a first zone for introducing the polyester and polymers (a) and (B). The polymers (a) and (B) may be combined in the same input area or in separate input areas. Preferably, the extruder is fed with each of the starting components (polyester polymers (a) and (B)) used independently, with one or more inputs provided. The supply rates of the starting components are independently controlled. The polyester and the polymers (A) and (B) are introduced into the extruder while hot or at ambient temperature. They may be introduced in solid form, in particular in the form of granules, flakes, powder or any other solid form, or even in the molten state.
The reactive extrusion step may be carried out as described, for example, in FR 2.897.356 a 1. Preferably, the reaction between the polyester, the first (a) and the second (B) polymer may be a homogeneous reaction.
The extrudable-spinnable composition according to the invention may comprise various additives, in particular lubricants, such as silicon dioxide, N' -ethylene-bisamide, calcium stearate or magnesium stearate, which make the extrudable-spinnable composition easy to handle. The additives may also be mineral fillers, colour pigments, UV-resistant or antioxidants.
In one embodiment, the MFI (melt flow index) of the extrudable-spinnable composition according to the invention, in particular measured according to one of the standards ISO 1133-1, month 2 2012 or astm d1238, month 8 2013, at a temperature of 270 ℃ under a weight of 2.16Kg, is greater than or equal to 10cm310min, preferably greater than or equal to 20cm3A/10 min, more preferably greater than or equal to 30cm310min, even more preferably greater than or equal to 40cm310min, in particular greater than or equal to 45cm310min, notably less than or equal to 100cm3/10min。
According to a third aspect, the object of the invention is a method of manufacturing a filament or fibre according to any of the variant embodiments described with reference to the first aspect of the invention, comprising the steps of:
i) an extrusion-spinning step of a composition as defined with reference to the second aspect of the invention, or
A coextrusion-spinning step for forming a composition as defined with reference to the second aspect of the invention, for forming a first polymeric structure constituting the matrix, and at least one polymeric composition (in particular extrudable and spinnable) for forming at least one second polymeric structure,
to obtain fibers or filaments;
ii) optionally, at least one drawing step of the filaments or the fibers obtained in step (i);
iii) optionally, a shaping step in which the filaments or the fibers are used to make a textile;
iv) hydrolyzing alkyl (meth) acrylate groups to carboxylate groups (-COO) by immersing the fibers or the filaments (obtained upon completion of step (i) or (ii) or the textile in an alkaline bath for shaping-) A step of converting;
v) optionally, a drying step of the filaments or the fibers or the textile.
Preferably, the fiber, filament or textile is subjected to a dyeing step prior to the drying step.
Preferably, the first and second polymeric structures are immiscible.
Preferably, the (co) extrusion-spinning step (i) is carried out on a single screw extruder, followed by passage of the molten material through a die orifice. The filaments at the die exit are then subjected to at least one drawing step as described below. For the purposes of the present invention, the stretching step may be carried out as known to those skilled in the art.
The fibers or filaments according to the invention can be treated according to techniques known to those skilled in the art, such as a drawing step via POY-type (partially oriented yarn), or FDY (fully drawn yarn) directly during the POY-type step, after the POY-type step or by adding a drawing step to the machine performing the POY-type operation. Once the filament or fiber has undergone the POY type step, it may be followed by a texturing step of DTY type (draw textured yarn) or ATY (air textured yarn, Taslan).
Preferably, the step of shaping the filaments or fibres for manufacturing the textile may comprise a knitting step, a weaving step, a knitting step, a manufacturing step of a non-woven fabric, or a combination thereof, optionally a heat-fixing step of the textile to stabilize the dimensions of the article.
In the present invention, "alkaline bath" means any aqueous solution having a pH greater than or equal to 6, more preferably greater than or equal to 7, even more preferably greater than or equal to 8, in particular greater than or equal to 10, even more in particular greater than or equal to 12.
In particular, the aqueous solution is an aqueous solution comprising a solution of a metal salt of the invention, for example sodium hydroxide and/or potassium hydroxide. Carboxylic acid functions carried by polymer A and optionally polymer BThe group and/or the acrylate function being converted into a carboxylate function (-COO)-) Which is complexed by the metal salts present in the aqueous saponification solution.
Preferably, the hydrolysis step is carried out by immersing the fibre or filament or textile to be treated in a full bath at a temperature greater than or equal to 40 ℃, in particular greater than or equal to 60 ℃, more in particular greater than or equal to 80 ℃, in particular less than or equal to 95 ℃, for at least 1 minute, in particular at least 30 minutes and preferably at most 50 minutes.
This full bath immersion step is followed by a padding step which comprises directing the treated textile product between two rollers to remove any excess solution.
This saponification step is preferably followed by a rinsing step of the fibres, filaments or textiles with water, in particular at ambient temperature (in particular at a temperature greater than 0 ℃ and less than or equal to 40 ℃), for example in running water. This step may 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 has lost at least 1 mass%, in particular at least 2 mass%, more preferably at most 8 mass% of its total initial mass before hydrolysis.
In the present invention, "textile" refers to any article comprising a textile element produced by forming fibers and/or filaments according to the present invention.
In one variant, the method comprises an acidification step vi) after step iv), by immersing the fiber or the filament or the textile in an acid bath.
The function of this acidification step is to convert all or some of the carboxylate groups formed during saponification to carboxyl groups.
Preferably, H of the solution acid+The ion concentration is determined according to the proportion of carboxylate functional groups to be converted into acid functional groups and thus the expected absorption characteristics of the acidic or basic gas.
In the present invention, "acid bath" means any aqueous solution having a pH of less than or equal to 6, more preferably less than or equal to 5, even more preferably less than or equal to 4.
In particular, the aqueous solution is an aqueous solution comprising an acid, in particular a mono-or polycarboxylic acid, such as acetic acid, or a strong acid, such as hydrochloric acid or sulfuric acid or phosphoric acid.
Preferably, the acidification step is carried out by immersing the fibre, filament or textile to be treated in a full bath at a temperature greater than or equal to 10 ℃, in particular less than or equal to 60 ℃, more in particular less than or equal to 40 ℃, in particular at ambient temperature, for at least 1 minute, in particular at least 10 minutes, and preferably at most 30 minutes.
This full bath step immersion step (especially by padding) is followed by an extrusion step which comprises directing the treated textile product between two rollers to remove any excess solution.
This acidification step is preferably followed by a rinsing step of the fibres, filaments or textiles with water, in particular at ambient temperature, for example in running water. This step may be followed by drying, for example in hot air.
In one variant, the method comprises an application step, wherein at least one metal salt (such as defined in the present invention) is applied to said filaments or said fibers or said textile, which is carried out during the hydrolysis step iv), said alkaline bath comprising at least one metal salt; and/or in a supplementary complexing step vii), in particular by applying a solution of at least one metal salt (as defined in the present invention) to the filaments or fibres.
The metal salt (e.g. sodium or potassium) present in the alkaline bath in the hydrolysis step and thus the saponification step may then be replaced by another metal salt in the complexation step according to the expected need for the absorbed gas.
When a metal salt is present in the bath in the hydrolysis step (iv), the carboxyl groups are fully or partially hydrolysed and complexed by the metal salt depending on the concentration of the metal salt in the solution.
Preferably, the concentration of the metal salt is determined in the hydrolysis bath (iv) and optionally the complexing (vii) such that only some (preferably half) of the carboxyl groups are hydrolyzed and complexed with the metal salt, enabling the fibers and/or filaments to absorb both alkaline and acidic gases.
Advantageously, the metal salt used in the complexation step is selected from the following salts: ca. Mg, Al and Ag or mixtures thereof.
According to a fourth aspect, the present invention is directed to a textile product comprising at least 5% by mass, relative to its total mass, of filaments and/or fibers according to any of the variant embodiments described with reference to the first aspect of the invention.
In a variant, the textile also comprises synthetic fibers and/or filaments, in particular fibers and/or filaments selected from the group comprising: polyesters, polyamides and polypropylene or mixtures thereof.
According to a fifth aspect, the present invention is directed to an article for sports absorbing acidic and/or basic gases comprising a textile according to any one of the variant embodiments described with reference to the fourth aspect of the invention, in particular selected from the following articles or articles considered alone or in combination: a backpack; a sports bag; articles of clothing, such as undershirts, trousers, shorts, undergarments, gloves, socks, tights (legging); a shoe; a component of a shoe, such as an insole, a liner, or an upper.
According to another aspect, the invention is directed to a multifilament yarn comprising a plurality of filaments according to any one of the variant embodiments described in the first aspect of the invention.
According to a fourth aspect, the present invention is directed to the use of an extrudable-spinning composition according to any of the embodiments described with reference to the second aspect of the present invention for the manufacture of a fiber or filament according to any of the embodiments described with reference to the first aspect of the present invention.
Brief description of the drawings
The invention will be more clearly understood from the following description of embodiments of the invention, given by way of non-limiting example with reference to the accompanying drawings, in which:
figure 1 is a schematic representation of a first polymer a used for making filaments according to the invention in the embodiments described below, and is a copolymer of ethylene and methyl acrylate;
figure 2 is a schematic view of a second polymer (B) used in the embodiment described below for making the filaments according to the invention and which is a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate;
figure 3 schematically shows polyethylene terephthalate;
figure 4 schematically shows the grafting of a second polymer B, shown in figure 2, on the polyester shown in figure 3 during reactive extrusion;
FIG. 5 schematically shows the saponification of the methyl group of the acrylate function of the first polymer A shown in FIG. 1;
FIG. 6 schematically shows the acidification of the carboxylate functions of the first saponified polymer A.
Detailed description of the embodiments
I-preparation of the extrudable-spinnable compositions according to the invention
The extrudable-spinnable composition according to the invention in the form of granules is prepared by: the polyester (thermoplastic) in the form of granules is mixed with the first and second copolymers (A, B) according to the invention, also in the form of granules. The particulate mixture was fed according to a rate of about 50g/min into the feed hopper of an extruder comprising two co-rotating material feed screws. The components are gathered in an extruder where they are melted, mixed and dispersed. This step is a reactive extrusion step, since the carboxylic acid functions (-COOH) at the ends of the polyester chains will react with the ethylene oxide groups, especially glycidyl groups, of the second polymer (B). The material exiting the extruder was formed into rods of about 3mm in diameter, which were immediately cooled with the aid of cold water or at ambient temperature. The rods are then fed to a pelletizing apparatus which drives the formed rods at a constant speed and forms pellets by cutting the rods. The extruder contains at least five zones, which differ in their heating temperature: a first feeding zone of starting components, which is at ambient temperature, thus in solid form, in this example in the form of granules; a second melting zone during which the starting components store heat and begin to melt; a third zone corresponding to the first mixing, wherein the starting components are sheared and completely melted upon exiting the third zone; a fourth zone corresponding to the second mixing during which the starting components are dispersed; a fifth zone, corresponding to the end of the twin screw, where the mixed and dispersed starting components are extruded through an extrusion die, including in this particular example a unique orifice for forming the rod. One of the two feed screws comprises a reverse flight in at least the fifth zone, compared to the flights in the other zones, to disperse the starting components in the molten state. The extruder was heated on either side of each zone, which represents six separate and distinct heating stages. The twin screw in this particular example was a screw RheomexPTW 16/25 OS coupled to a rheostatic 7OS-3 x 400V motor, sold by ThermoScientificHaake.
Before this, the polyester granules have been heated at 90 ℃ for 16 hours, in order to limit to a minimum humidity rate, and thus optionally to carry out a subsequent hydrolysis of the polyester chains.
The initial parameters of the extruder were: the torque was 65Nm, the screw rotation speed was 450rpm, the screw feed speed in the region of the first zone was 12%, the die pressure was 5.7 bar, the material temperature was about 260 ℃ and the die temperature was about 245 ℃. In order from the first zone to the sixth zone, the six temperature phases are respectively as follows: 165 ℃, 274 ℃, 270 ℃, 260 ℃ and 255 ℃.
The first copolymer A is
Copolymers of ethylene with and with methyl acrylate,
the proportion of methyl acrylate is about 29% by mass, and the melt index (190 ℃/2.16Kg) is about 2-3.5g/10min (ASTM D1238 in ISO 1133-1/2013 month 8, 2/2012); melting point 61 ℃ (ISO 11357-3 of 3 months in 2013); the weight-average molar mass Mw was 105213 g/mol and the number-average molar mass Mn was 16322 g/mol, the Vicat softening point was at 40 ℃ (ISO 306/2017 at 1 month 2014 or ASTM D1525 at 2009), and the elongation at break was 900% (ISO 527-2/ASTM D6382014 at 4 months 2012).
The second copolymer B is a terpolymer of ethylene, methyl acrylate and glycidyl methacrylate, with a proportion of methyl acrylate of about 24% by mass, a proportion of glycidyl methacrylate of about 8% by mass, a melt index (190 ℃/2.16Kg) of about 6g/10min (astm d1238 ISO 1133-1/2013 month 8, 2012 month 2); melting point 65 deg.C (ISO 11357-3, 3 months 2013); has a weight-average molar mass Mw of 103499 g/mol, a number-average molar mass Mn of 16491 g/mol, a Vicat softening point of 40 ℃ (ISO 306/2017 at 1 month 2014 or ASMD 1525 at 2009), and an elongation at break of 1100% (ISO 527-2/ASTM D6382014 at 4 months 2012).
The polyester may be selected as an extrudable-spinnable grade, such as that sold by Invista under reference RT20 or by Dupont de Nemours. The first polymer (A) and the second polymer (B) can be found in the Dupont de Nemours product range of Elvaloy, or in the Arkema product range of Lotryl and Lotader.
Table 1 below lists the mass ratios of the different starting components relative to the total mass of the composition that has been extruded and then converted into granules.
Figure BDA0002245392000000151
Figure BDA0002245392000000161
TABLE 1
The MFI values shown in table 1 have been measured for the compositions (trials 1 to 9) as well as for the Polyester (PET) alone (trial 10) (preferably, MFI was measured independently at 270 ℃ under a weight of 2.16Kg according to standard ISO 1133-1 at month 2 2012 and ASTM1238 at month 8 at year 2013).
Figure BDA0002245392000000162
TABLE 2
Table 2 above shows the theoretical molar amounts of acrylate functions given relative to the mass of the first and second polymers (a) and (B), where the acrylate functions are carried by the first and second polymers (a) and (B) in these examples. It is clear that the more the amount of the second copolymer B is increased, the more the pressure in the extrusion die is increased than the set point of 5.7 bar and the more the temperature T5 in the extrusion die is increased. A not exhaustive explanation for this would be that the glycidyl functions of the second copolymer B react with the carboxylic acid functions of the polyester chain ends, which would increase the viscosity of the extruded material and therefore the friction and shear in the latter and correspondingly the pressure and temperature in the die area. The grafting reaction is depicted in fig. 4.
II-spinning of the composition converted into particles in I
Tests 1 to 4 in table 3 below correspond to the compositions of tests 1 to 4 defined in table 1. The compositions have been extruded and spun through a single screw extruder comprising an extrusion die having a plurality of spinning orifices and an array of filters. The drawing and spinning device is arranged at the output end of the extrusion die and comprises, in particular, a nozzle which sends a jet of air to interlace the filaments. The yarn formed was a multifilament yarn containing 48 filaments. The filaments are cooled by means of a cold air flow. As they leave the spinning and drawing step, the yarns are coated, in particular with a sizing agent (sold for example under the reference faswavin KB 88) in an amount of 10% by mass relative to the total mass of the filaments.
Figure BDA0002245392000000171
TABLE 3
Table 3 lists the fineness and resilience measured on the different yarns obtained according to the drawing technique performed.
The structure of the obtained yarn was also characterized by analyzing sections of the filament with an electron scanning microscope. This shows the formation of nodules comprising a first copolymer a placed in a pocket, wherein the "shell" is formed by a second copolymer B using a coupling agent with a polyester matrix.
III-saponification step and acidification step
A 150 denier yarn containing 48 filaments according to the DTY of test 4 defined in table 3 was knitted (jersey weave). The surface quality of the knitted fabric was 31g/m2. Samples of 6cm by 6cm were prepared and soaked for 45 minutes at 85-90 ℃ in a bath containing 5g/l of soda. The pH meter dose measured the soda consumption (by measuring the soda concentration in the bath after the saponification step) of 50+/-10meq/Kg knitwear. Texture of knitted goods after saponificationThe loss of amount was about 1.8%. The acrylate in meq and therefore saponifiable amount was 168.5mmol per Kg of knitwear tested. In this way, the measured soda consumption is inferred to be about 30% of the acrylate functions having been saponified to the form of carboxylate functions.
The saponified knit fabric then undergoes an acidification step in which the sample is acidified at 0.02mol/L (or 0.04mol/L ═ H+]) Is immersed in the bath of sulfuric acid solution for 45 minutes at ambient temperature. pH meter dosing measured an average acid consumption of 15+/-5mmol H+Per kg of knitwear. This acid consumption corresponds to about 30% of the 50meq soda consumed in the saponification step per Kg of knitted fabric.
IV-measurement of acid gas absorption
These rates are measured according to ISO 17299-3:2014 standard entitled "Textiles-Determination of depathology-Part 3: gases phase chromatography method" beginning at 3 months 2014. The calculation of the rate of reduction is shown in point 8 of the standard and corresponds to the average difference of the area (Sb) of the FID spectrum (hydrogen flame ionization detector) of the gas test without textile element minus the average area (Sm) of the FID peak of the gas test with textile element, this difference being divided by the area 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 measurements reported hereinafter is acetic acid.
It should be noted that the above-mentioned ISO 17299-3:2014 standard starting at 3 months 2014 provides a wash before taking absorption measurements of the target gas.
The acetic acid absorption value of the knitted fabric described above with reference to paragraph III and saponified only was 73% +/-4%.
By comparison, the absorption value of a standard knitted fabric comprising only polyester is below 40%.
The acetic acid uptake value of the knitted fabric having undergone the saponification step and the acidification step described above with reference to paragraph III was 88% +/-2%. Thus, the acidification step improves the acetic acid absorption characteristics.
During the "internal sniffing test", the inventors noted that starting from a gas absorption value of at least 50%, the user perceives olfactively the performance of the synthetic textile against bad smells, and the latter still increases significantly from 80%.
The mechanism of acid gas (acetic acid in this example) absorption is related to the acid-base reaction of the carboxylic acid functional group and the carboxylate salt carried by the filaments. In particular, the reaction between the carboxylate functionality and acetic acid produces a non-volatile metal Carboxylate (CH)3COONa) which may explain the reduction in perceived odor. This will result in deodorization of the gas by salination.
Due to the remarkable properties obtained in terms of perceived odor reduction, polar interactions and hydrogen bonds between carboxylic acid functional groups and acetic acid may also occur to explain this remarkable absorption phenomenon of acetic acid. Reinitializing the textile can be achieved by rinsing in running water (e.g. during home washing) or even by drying the textile, transferring the acid-base equilibrium and evaporating the acid gases. The yarns according to the invention and implemented in the knitted and test samples are entirely in the extrudable-spinnable composition according to the invention. However, for the purposes of the present invention, only the yarn surface is in contact with odorous molecules, so that, for cost savings, when producing a core-outer layer type yarn, it is possible to have a functional matrix based on a polyester comprising polymers a and B only at the yarn surface, the outer layer comprising a functional matrix absorbing a gas. In this case, the extrudable-spinnable composition according to the invention is coextruded with another polymeric composition, so as to form a first polymeric structure consisting of the matrix (for example to form an outer layer) parallel to a second polymeric structure consisting of the second coextruded polymeric composition (for example consisting of more than 95% by mass of polyester).

Claims (19)

1. A filament or fibre absorbing odorous molecules, in particular acidic and/or basic gases, having a defined outer surface, wherein at least a part of said surface comprises carboxyl-COOH and/or carboxylate groups-COO complexed with metal salts-Characterized in that said fraction consists of the following matrix: the matrix is derived from a first copolymer (A) comprising a polyester and at least one olefin and alkyl (meth) acrylate and/or (meth) acrylic acid and from a second copolymer (A) comprising ethylene oxideAlkyl radical-C2H3Reaction of a mixture of a second polymer (copolymer) (B) of O, at least some of the (meth) acrylate functions of said copolymer (A) having been converted to the corresponding carboxylate and/or corresponding carboxylic acid functions.
2. The filament or fiber according to claim 1, wherein the first copolymer (a) of at least one olefin and alkyl (meth) acrylate and/or (meth) acrylic acid and optionally the second polymer (copolymer) (B) (each) is an elastomer.
3. The filament or fiber according to claim 1 or 2, characterized in that the second polymer (B) comprising ethylene oxide groups is a terpolymer of at least one olefin, an alkyl (meth) acrylate or (meth) acrylic acid and monomer units comprising ethylene oxide groups, in particular a terpolymer of ethylene, an alkyl (meth) acrylate or (meth) acrylic acid and glycidyl (meth) acrylate.
4. A filament or fibre according to any one of claims 1 to 3 characterised in that the metal salt is a salt of one or more metals selected from the group consisting of: potassium (K), sodium (Na), calcium (Ca), magnesium (Mg), aluminum (Al), silver (Ag), or mixtures thereof.
5. A filament or fibre according to any one of claims 1 to 4 characterised in that it comprises first and second non-intermingled polymeric structures, the first polymeric structure being the matrix.
6. The filament or fiber according to any one of claims 1 to 5, wherein 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, polypropylene and polyethylene or mixtures thereof.
7. A filament or fibre according to any one of claims 1 to 6 wherein the filament or fibre has a non-uniform cross-section of the core-outer layer type, the outer layer being formed from the matrix.
8. The filament or fiber according to any one of claims 1 to 7, characterized in that the matrix comprises more than 50 mass% (g) of polyester relative to its total mass (g), preferably more than 60 mass%, more preferably more than 70 mass%, in particular more than 75 mass% of polyester relative to its total mass (g).
9. The filament or fiber according to any one of claims 1 to 8, characterized in that the mass ratio of first (A) to second (B) polymer in the matrix is between 99/1 and 85/15.
10. The filament or fiber according to any one of claims 1 to 9, characterized in that the sum of the mass of the first copolymer (a) and the mass of the second polymer (B) is less than or equal to 20% relative to the total mass of the matrix.
11. An extrudable-spinnable composition for making at least part of the determined outer surface of the filament or fibre according to any of claims 1 to 10, characterised in that the composition is derived from a first copolymer (a) comprising a polyester, an olefin and an alkyl (meth) acrylate and/or (meth) acrylic acid and comprises an ethylene oxide group-C2H3Reaction of a mixture of a second (co) polymer (B) of O, the mass of said polyester being greater than or equal to 50% with respect to the total mass of said mixture, and characterized in that said polyester is chosen from: polyethylene terephthalate, polytetramethylene terephthalate, polycyclohexane-dimethylene or polyethylene 2,6 naphthalate; or a homopolymer, copolymer, terpolymer, and mixtures thereof, selected from the following monomer units: ethylene terephthalate, propylene terephthalate, butylene terephthalate and 1,4-cyclohexylene-dimethylene terephthalate, in particular ethylene terephthalate.
12. The composition of claim 11, having a height of 10cm or more3MFI (melt flow index) at 10min, measured in particular according to Standard ASTM D1238, 8 months 2013, at a temperature of 270 ℃ and under a weight of 2.16 Kg.
13. Use of the extrudable-spinnable composition according to any one of claims 11 and 12 for manufacturing at least a part of a defined outer surface of an absorbent filament or fibre according to any one of claims 1 to 10.
14. A process for the manufacture of a filament or fibre according to any one of claims 1 to 10, characterised in that it comprises the steps of:
i) a step of extrusion-spinning the composition of claim 11, or
A coextrusion-spinning step of the composition according to claim 11 for forming a first polymeric structure constituting the matrix and of at least one polymeric composition for forming at least one second polymeric structure,
in order to obtain a fibre or a filament,
ii) optionally, at least one drawing step of the filaments or the fibers obtained in step (i);
iii) optionally, a shaping step in which the filaments or the fibers are used to make a textile;
iv) hydrolyzing alkyl (meth) acrylate groups to carboxylate groups (-COO) by immersing the fiber or the filament or the textile in an alkaline bath-) The step of converting.
15. Manufacturing process according to claim 14, characterized in that it comprises an acidification step vi) carried out after step iv) by immersing the fiber or the filament or the textile in an acid bath.
16. Manufacturing method according to any of claims 14 and 15, characterized in that at least one metal salt is applied to the filaments or the fibers or the textile or during step iv), the alkaline bath comprising at least one metal salt; or in a supplementary complexing step vii), in particular by applying a solution of at least one metal salt to the filaments or the fibers or the textile.
17. A multifilament yarn, characterized in that it comprises a plurality of filaments according to any one of claims 1 to 10.
18. A textile product, characterized in that it comprises at least 5 mass%, relative to its total mass, of filaments and/or fibers according to any one of claims 1 to 10.
19. Sports article absorbing acidic and/or basic gases, characterized in that it comprises a textile according to claim 18, in particular selected from: a backpack; a sports bag; articles of clothing, such as undershirts, trousers, shorts, undergarments, gloves, socks, tights; a shoe; a component of a shoe, such as an insole, a liner, or an upper.
CN201880027044.XA 2017-04-26 2018-04-24 Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre Pending CN110914489A (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR1753624A FR3065738B1 (en) 2017-04-26 2017-04-26 ACID AND / OR BASIC GAS ABSORBING FILAMENT OR FIBER, PROCESS FOR PRODUCING SUCH A FILAMENT OR SUCH FIBER, TEXTILE ARTICLE COMPRISING SUCH A FILAMENT OR SUCH FIBER
FR1753624 2017-04-26
PCT/EP2018/060468 WO2018197485A1 (en) 2017-04-26 2018-04-24 Filament or fibre absorbing acid and/or basic gases, method for manufacturing such a filament or such a fibre, textile item comprising such a filament or such a fibre

Publications (1)

Publication Number Publication Date
CN110914489A true CN110914489A (en) 2020-03-24

Family

ID=59974500

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201880027044.XA Pending CN110914489A (en) 2017-04-26 2018-04-24 Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre

Country Status (5)

Country Link
EP (1) EP3615717A1 (en)
CN (1) CN110914489A (en)
FR (1) FR3065738B1 (en)
TW (1) TWI705853B (en)
WO (1) WO2018197485A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117384469A (en) * 2023-10-16 2024-01-12 台州天奇鞋业股份有限公司 Breathable wear-resistant vamp material and preparation method thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020252694A1 (en) * 2019-06-19 2020-12-24 江苏国望高科纤维有限公司 Emulsion composition, polystyrene nanofiber, polystyrene nanofiber article and preparation methods therefor and use thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6385163A (en) * 1986-09-19 1988-04-15 東レ株式会社 Polyester fiber
EP0792957A2 (en) * 1996-02-26 1997-09-03 Japan Exlan Company, Ltd. Acidic or basic gas absorptive fiber and fabric
CN1745202A (en) * 2003-01-30 2006-03-08 罗姆有限及两合公司 Method for producing synthetic fibres with an improved dye receptivity, synthetic fibres with an improved dye receptivity and the use thereof
US20060173133A1 (en) * 2003-12-12 2006-08-03 Flexman Edmund A Toughened poly(lactic acid) compositions
CN1898306A (en) * 2003-10-21 2007-01-17 纳幕尔杜邦公司 Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles
FR2902434A1 (en) * 2006-06-16 2007-12-21 Arkema France Polylactic composition, useful e.g. to make molded-, extruded- and thermoformed articles, comprises polylactic acid, ethylene copolymer e.g. ethylene-methylacrylate-glycidyl methacrylate and ethylene-alkyl(meth)acrylate copolymer
US20100247826A1 (en) * 2009-03-30 2010-09-30 Cellresin Technologies, Llc Malodor Absorbent Polymer and Fiber

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4529146B2 (en) * 2004-09-07 2010-08-25 日本エクスラン工業株式会社 Advanced flame retardant hygroscopic fibers and fiber structures
CN1896306A (en) * 2005-07-11 2007-01-17 电子科技大学 Thin-film depositer
FR2897356B1 (en) 2006-02-16 2012-07-13 Arkema USE OF THERMOPLASTIC COMPOSITIONS BASED ON FUNCTIONALIZED POLYOLEFINS GRAFTED BY POLYETHER MOTIFS TO PRODUCE IMPER-BREATHING MATERIALS AND THEIR APPLICATIONS

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6385163A (en) * 1986-09-19 1988-04-15 東レ株式会社 Polyester fiber
EP0792957A2 (en) * 1996-02-26 1997-09-03 Japan Exlan Company, Ltd. Acidic or basic gas absorptive fiber and fabric
CN1745202A (en) * 2003-01-30 2006-03-08 罗姆有限及两合公司 Method for producing synthetic fibres with an improved dye receptivity, synthetic fibres with an improved dye receptivity and the use thereof
CN1898306A (en) * 2003-10-21 2007-01-17 纳幕尔杜邦公司 Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles
US20060173133A1 (en) * 2003-12-12 2006-08-03 Flexman Edmund A Toughened poly(lactic acid) compositions
FR2902434A1 (en) * 2006-06-16 2007-12-21 Arkema France Polylactic composition, useful e.g. to make molded-, extruded- and thermoformed articles, comprises polylactic acid, ethylene copolymer e.g. ethylene-methylacrylate-glycidyl methacrylate and ethylene-alkyl(meth)acrylate copolymer
US20100247826A1 (en) * 2009-03-30 2010-09-30 Cellresin Technologies, Llc Malodor Absorbent Polymer and Fiber

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117384469A (en) * 2023-10-16 2024-01-12 台州天奇鞋业股份有限公司 Breathable wear-resistant vamp material and preparation method thereof
CN117384469B (en) * 2023-10-16 2024-05-07 台州天奇鞋业股份有限公司 Breathable wear-resistant vamp material and preparation method thereof

Also Published As

Publication number Publication date
WO2018197485A1 (en) 2018-11-01
FR3065738A1 (en) 2018-11-02
FR3065738B1 (en) 2020-03-13
TW201841682A (en) 2018-12-01
EP3615717A1 (en) 2020-03-04
TWI705853B (en) 2020-10-01

Similar Documents

Publication Publication Date Title
CN104818543B (en) A kind of modified polylactic acid fiber haveing excellent performance
AU656433B2 (en) Starch fiber, process for its production and use
US5047448A (en) Antimicrobial-shaped article and a process for producing the same
EP3737782A1 (en) Biodegradation-enhanced synthetic fiber and methods of making the same
CN107502975B (en) Crimped polyester conductive filament yarn, manufacturing method and application thereof
CN101747624B (en) Hygroscopic fine denier/superfine denier nylon masterbatch, nylon and preparation method thereof
CN110914489A (en) Filament or fibre absorbing acidic and/or basic gases, method for manufacturing the filament or fibre, textile comprising the filament or fibre
WO2019099350A1 (en) Reduced density synthetic fiber utilizing hollow microcapsules
JP7130193B2 (en) Fabric and clothing using it
JP3703775B2 (en) Endothermic composite fiber
WO2018017147A1 (en) Processes for producing an antimicrobial masterbatch and products therefrom
JPWO2015182088A1 (en) Polyamide fiber, fiber structure using the same, and clothing
CN111556912B (en) Modified ethylene-vinyl alcohol copolymer fibers
CN101676450A (en) Multicomponent white conductive fiber and preparation method thereof
JP2006022451A (en) Fiber having excellent heat-storing and temperature-keeping properties
JP4797905B2 (en) Knitted fabric containing nanofiber fibers
JPH08170217A (en) Antimicrobial fibrous material
KR102182612B1 (en) Functional fabric incluing illite and manufacturing method of the same
JP2003286659A (en) Polylactic acid stereo complex fiber structure excellent in durable water repellency and method for producing the same
CN107849744B (en) Soft fiber and fabric thereof
JP2593890B2 (en) Antibacterial molded article and method for producing the same
RU2786589C2 (en) Synthetic fiber with increased biodegradability and its production methods
Gupta Manufactured textile fibers
EP1928953A2 (en) Composition for producing poyester and polyamide yarns with improved moisture management properties
JP2007217855A (en) Ethylene-vinyl alcohol-based fiber having deodorizing property and antimicrobial property and method for producing the same

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20200324