EP2938768B1 - Caco3 en polyester pour non-tissé et fibres - Google Patents

Caco3 en polyester pour non-tissé et fibres Download PDF

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Publication number
EP2938768B1
EP2938768B1 EP13814950.5A EP13814950A EP2938768B1 EP 2938768 B1 EP2938768 B1 EP 2938768B1 EP 13814950 A EP13814950 A EP 13814950A EP 2938768 B1 EP2938768 B1 EP 2938768B1
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EP
European Patent Office
Prior art keywords
calcium carbonate
nonwoven fabric
meltblown
polymer
polyester
Prior art date
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EP13814950.5A
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German (de)
English (en)
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EP2938768A1 (fr
Inventor
Martin Brunner
Erik Laursen
Francesco Pullega
Tazio Fornera
Michael Tinkl
Samuel Rentsch
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Omya International AG
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Omya International AG
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Priority to EP13814950.5A priority Critical patent/EP2938768B1/fr
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Classifications

    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005—Synthetic yarns or filaments
    • D04H3/009—Condensation or reaction polymers
    • D04H3/011—Polyesters
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/435—Polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
    • Y10T442/642—Strand or fiber material is a blend of polymeric material and a filler material

Definitions

  • the invention relates to a nonwoven fabric, a process for preparing a nonwoven fabric, articles containing said nonwoven fabric, and the use of said nonwoven fabric as well as to the use of fibers for the manufacture of nonwoven fabrics and the use of calcium carbonate as fillers for nonwoven fabrics.
  • Nonwoven fabrics are sheets or web structures made by bonding together fibers or filaments. They can be flat or bulky and, depending upon the process by which they are produced and the materials used, can be tailored for a variety of applications. In contrast to other textiles such as woven fabrics or knitted fabrics, nonwoven fabrics need not to go through the preparatory stage of yarn spinning in order to be transformed into a web of a certain pattern. Depending on the strength of material needed for the specific use, it is possible to use a certain percentage of recycled fabrics in the nonwoven fabric. Conversely, some nonwoven fabrics can be recycled after use, given the proper treatment and facilities. Therefore, nonwoven fabrics may be the more ecological fabric for certain applications, especially in fields and industries where disposable or single use products are important such as hospitals, schools or nursing homes.
  • PET Polyethylene terephthalate
  • talc talc
  • these heterogeneous particles can act as stress concentrators, and thereby, may affect the mechanical properties of the polymer. Therefore, nucleated PET is often reinforced with glass fibers.
  • a talc filled PET is disclosed in the article of Sekelik et al. entitled "Oxygen barrier properties of crystallized and talc-filled poly(ethylene terephthalate)" published in Journal of Polymer Science: Part B: Polymer Physics, 1999, 37, 847 to 857 .
  • US 5,886,088 A is concerned with a PET resin composition comprising an inorganic nucleating agent.
  • a method for producing a thermoplastic polymer material, which is filled with calcium carbonate is described in WO 2009/121085 A1 .
  • WO 2012/052778 A1 relates to tearable polymer films comprising a polyester and calcium carbonate or mica fillers.
  • Extruded fibers and nonwoven webs containing titanium dioxide and at least one mineral filler are disclosed in US 6,797,377 B1 .
  • WO 2008/077156 A2 describes spunlaid fibers comprising a polymeric resin and one filler as well as nonwoven fabrics containing said fibers.
  • Nonwovens of synthetic polymers with an improved binding composition are disclosed in EP 2 465 986 A1 .
  • WO 97/30199 relates to fibers or filaments suitable for the production of a nonwoven fabric, the fibers or filaments consisting essentially of a polyolefin and inorganic particles.
  • a nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate is provided.
  • the present invention provides a process for producing a nonwoven fabric comprising the steps of
  • the present invention provides an article comprising the inventive nonwoven fabric, wherein said article is selected from construction products, consumer apparel, industrial apparel, medical products, home furnishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
  • the present invention provides the use of calcium carbonate as filler in a nonwoven fabric comprising at least one polymer comprising a polyester.
  • the present invention provides the use of fibers for the manufacture of a non-woven fabric, wherein the fibers comprise at least one polymer comprising a polyester and at least one filler comprising calcium carbonate.
  • the present invention provides the use of the inventive nonwoven fabric in construction products, waterproofing, thermal insulation, soundproofing, roofing, consumer apparel, upholstery and clothing industries, industrial apparel, medical products, home furnishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
  • the polyester is selected from the group consisting of a polyglycolic acid, a polycaprolactone, a polyethylene adipate, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyethylene terephthalate, a polytrimethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate, a polylactic acid, or a mixture thereof, or copolymers thereof, preferably the polyester is a polyethylene terephthalate.
  • the polyester has a number average molecular weight from 5000 to 100000 g/mol, preferably from 10000 to 50000 g/mol, and more preferably from 15000 to 20000 g/mol.
  • the calcium carbonate is ground calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium carbonate, or a mixture thereof, preferably surface-treated calcium carbonate.
  • the calcium carbonate has an average particle size d 50 from 1.2 to 1.8 ⁇ m and a top cut particle size d 98 from 4 to 7 ⁇ m, and most preferably from 6 to 7 ⁇ m.
  • the calcium carbonate is present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, preferably from 0. 2 to 40 wt.-%, and more preferably from 1 to 35 wt.-%, based on the total weight of the nonwoven fabric.
  • step b) the mixture is formed into fibers, preferably by an extrusion process, and more preferably by a melt blown process, a spunbond process, or a combination thereof.
  • the nonwoven fabric is formed by collecting the fibers on a surface or carrier.
  • steps b) and c) are repeated two or more times to produce a multilayer nonwoven fabric, preferably a spundbonded-meltblown-spunbonded (SMS), a meltblown-spunbonded-meltblown (MSM), a spundbonded-meltblown-spunbonded-meltblown (SMSM), a meltblown-spunbonded-meltblown-spunbonded (MSMS), a spundbonded-meltblown- meltblown-spunbonded (SMMS), or a meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric.
  • SMS spundbonded-meltblown-spunbonded
  • MSM meltblown-spunbonded-meltblown
  • SMSM spundbonded-meltblown-spunbonded-meltblown
  • MSMS meltblown-spunbonded-meltblown-spunbonded-meltblown
  • GCC GCC in the meaning of the present invention is a calcium carbonate obtained from natural sources, such as limestone, marble, calcite or chalk, and processed through a wet and/or dry treatment such as grinding, screening and/or fractionation, for example by a cyclone or classifier.
  • intrinsic viscosity is a measure of the capability of a polymer in solution to enhance the viscosity of the solution and is specified in dl/g.
  • Modified calcium carbonate in the meaning of the present invention may feature a natural ground or precipitated calcium carbonate with an internal structure modification or a surface-reaction product, i.e. "surface-reacted calcium carbonate".
  • a "surface-reacted calcium carbonate” is a material comprising calcium carbonate and insoluble, preferably at least partially crystalline, calcium salts of anions of acids on the surface.
  • the insoluble calcium salt extends from the surface of at least a part of the calcium carbonate.
  • the calcium ions forming said at least partially crystalline calcium salt of said anion originate largely from the starting calcium carbonate material.
  • MCCs are described, for example, in US 2012/0031576 A1 , WO 2009/074492 A1 , EP 2 264 109 A1 , EP 2 070 991 A1 , or 2 264 108 A1 .
  • nonwoven fabric refers to a flat, flexible, porous sheet structure that is produced by interlocking layers or networks of fibers, filaments, or film-like filamentary structures.
  • the "particle size" of a calcium carbonate filler is described by its distribution of particle sizes.
  • the value d x represents the diameter relative to which x % by weight of the particles have diameters less than d x .
  • the d 98 value is also designated as "top cut”.
  • the d 50 value is thus the weight median particle size, i.e. 50 wt.-% of all grains are bigger or smaller than this particle size.
  • the particle size is specified as weight median particle size d 50 unless indicated otherwise.
  • For determining the weight median particle size d 50 value or the top cut particle size d 98 value a Sedigraph 5100 or 5120 device from the company Micromeritics, USA, can be used.
  • polymer generally includes homopolymers and copolymers such as, for example, block, graft, random and alternating copolymers, as well as blends and modifications thereof.
  • Precipitated calcium carbonate in the meaning of the present invention is a synthesized material, generally obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment or by precipitation of a calcium- and a carbonate source in water. Additionally, precipitated calcium carbonate can also be the product of introducing calcium and carbonate salts, calcium chloride and sodium carbonate for example, in an aqueous environment.
  • PCC may be vaterite, calcite or aragonite. PCCs are described, for example, in EP 2 447 213 A1 , EP 2,524,898 A1 , EP 2 371 766 A1 , or unpublished European patent application no. 12 164 041.1 .
  • a "surface-treated calcium carbonate” is a ground, precipitated or modified calcium carbonate comprising a treatment or coating layer, e.g. a layer of fatty acids, surfactants, siloxanes, or polymers.
  • the inventive nonwoven fabric comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate.
  • the at least one polymer is the at least one polymer
  • the nonwoven fabric of the present invention comprises at least one polymer comprising a polyester.
  • Polyesters are a class of polymers which contain the ester functional group in their main chain and are generally obtained by a polycondensation reaction. Polyesters may include naturally occurring polymers such as cutin as well as synthetic polymers such as polycarbonate or poly butyrate. Depending on their structure polyesters may be biodegradable. The polyester is a polyethylene terephthalate, it may be in pure form, i.e. in form of a homopolymer, or may be modified by copolymerization and/or by adding one or more substituents to the main chain or side chains of the main chain.
  • the at least one polymer consists of a polyester.
  • the polyester may consist of only one specific type of polyester or a mixture of one or more types of polyesters.
  • the at least one polymer can be present in the nonwoven fabric in an amount of at least 40 wt.-%, preferably of at least 60 wt.-%, more preferably of at least 80 wt.-%, and most preferably of at least 90 wt.-%, based on the total weight of the nonwoven fabric.
  • the at least one polymer is present in the nonwoven fabric in an amount from 50 to 99 wt.-%, preferably from 60 to 98 wt.-%, and more preferably from 65 to 95 wt.-%, based on the total weight of the nonwoven fabric.
  • the polyester is a polyethylene terephthalate.
  • PET Polyethylene terephthalate
  • PET may be polymerized by ester interchange employing the monomers diethyl terephthalate and ethylene glycol or direct esterification by employing the monomers terephthalic acid and ethylene glycol. Both ester interchange and direct esterification processes are combined with polycondensation steps either batch-wise or continuously. Batch-wise systems require two reaction vessels; one for esterification or ester interchange and one for polymerization. Continuous systems require at least three vessels; one for esterification or ester interchange, another for reducing excess glycols, and still another for polymerization.
  • PET may be produced by solid-phase polycondensation.
  • a melt polycondensation is continued until the pre-polymer has an intrinsic viscosity of 1.0 to 1.4 dl/g, at which point the polymer is cast into a solid film.
  • the pre-crystallization is carried out by heating, e.g. above 200°C, until the desirable molecular weight of the polymer is obtained.
  • PET is obtained from a continuous polymerization process, a batch-wise polymerization process or a solid phase polymerization process.
  • polyethylene terephthalate comprises unmodified and modified polyethylene terephthalate.
  • the polyethylene terephthalate may be a linear polymer, a branched polymer, or a cross-linked polymer.
  • each glycerol will generate a branch point.
  • internal coupling occurs, for example, by reaction of a hydroxyl group and an acid function from branches at the same or a different molecule, the polymer will become crosslinked.
  • the polyethylene terephthalate can be substituted, preferably with a C 1 to C 10 alkyl group, a hydroxyl, and/or an amine group.
  • the polyethylene terephthalate is substituted with a methyl, ethyl, propyl, butyl, tert .-butyl, hydroxyl and/or amine group.
  • the polyethylene terephthalate can also be modified by copolymerization, e.g, with cyclohexane dimethanol or isophthalic acid.
  • PET may exist both as an amorphous and as a semi-crystalline polymer, i.e. as a polymer comprising crystalline and amorphous fractions.
  • the semi-crystalline material can appear transparent or opaque and white depending on its crystal structure and particle size.
  • the polyethylene terephthalate is amorphous. According to another embodiment, the polyethylene terephthalate is semi-crystalline, preferably the polyethylene terephthalate has a degree of crystallinity of at least 20%, more preferably of at least 40%, and most preferably of at least 50%. According to still another embodiment, the polyethylene terephthalate has a degree of crystallinity from 10 to 80%, more preferably from 20 to 70%, and most preferably from 30 to 60%. The degree of crystallinity may be measured with differential scanning calorimetry (DSC).
  • DSC differential scanning calorimetry
  • the polyethylene terephthalate has an intrinsic viscosity, IV, from 0.3 to 2.0 dl/g, preferably from 0.5 to 1.5 dl/g, and more preferably from 0.7 to 1.0 dl/g.
  • the polyethylene terephthalate has a glass transition temperature, Tg, from 50 to 200°C, preferably from 60 to 180°C, and more preferably from 70 to 170°C.
  • the polyethylene terephthalate has a number average molecular weight from 5000 to 100000 g/mol, preferably from 10000 to 50000 g/mol, and more preferably from 15000 to 20000 g/mol.
  • the polyethylene terephthalate may be a virgin polymer, a recycled polymer, or a mixture thereof.
  • a recycled polyethylene terephthalate may be obtained from post consumed PET bottles, preform PET scrap, regrained PET, or reclaimed PET.
  • the polyethylene terephthalate includes 10 wt.-%, preferably 25 wt.-%, more preferably 50 wt.-%, and most preferably 75 wt.-% recycled PET, based on the total amount of polyethylene terephthalate.
  • the at least one polymer consists of a polyethylene terephthalate.
  • the PET may consist of only one specific type of PET or a mixture of two or more types of PET.
  • the at least one polymer comprises further polymers, preferably polyolefines, polyamides, cellulose, polybenzimidazols, or mixtures thereof, or copolymers thereof.
  • polymers preferably polyhexamethylene diadipamide, polycaprolactam, aromatic or partially aromatic polyamides ("aramids"), nylon, polyphenylene sulfide (PPS), polyethylene, polypropylene, polybenzimidazols, or rayon.
  • the at least one polymer comprises at least 50 wt.-%, preferably at least 75 wt.-%, more preferably at least 90 wt.-%, and most preferably at least 95 wt.-% of a polyethylene terephthalate, based on the total amount of the at least one polymer.
  • the nonwoven fabric comprises at least one filler comprising a calcium carbonate.
  • the at least one filler is dispersed within the at least one polymer.
  • the use of at least one filler comprising calcium carbonate in polyester-based nonwoven fabrics has certain advantages compared to conventional nonwoven fabrics.
  • the hydrophobic or hydrophilic properties of the nonwoven web can be adapted to the intended application by using an appropriate calcium carbonate filler.
  • the use of calcium carbonate fillers allows for the reduction of polyesters in the production of nonwoven fabrics without affecting the quality of the nonwoven significantly.
  • calcium carbonate acts as nucleating agent for PET, and thus, increases the crystallization temperature of PET.
  • nonwoven webs manufactured from PET including calcium carbonate fillers have an improved soft touch and a higher stiffness compared to nonwoven webs made from PET only.
  • the calcium carbonate is ground calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium carbonate, or a mixture thereof.
  • the calcium carbonate is surface-treated calcium carbonate.
  • Ground (or natural) calcium carbonate is understood to be a naturally occurring form of calcium carbonate, mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble rocks.
  • Calcium carbonate is known to exist as three types of crystal polymorphs: calcite, aragonite and vaterite.
  • Calcite the most common crystal polymorph, is considered to be the most stable crystal form of calcium carbonate. Less common is aragonite, which has a discrete or clustered needle orthorhombic crystal structure.
  • Vaterite is the rarest calcium carbonate polymorph and is generally unstable.
  • Ground calcium carbonate is almost exclusively of the calcitic polymorph, which is said to be trigonal-rhombohedral and represents the most stable of the calcium carbonate polymorphs.
  • the term "source" of the calcium carbonate in the meaning of the present application refers to the naturally occurring mineral material from which the calcium carbonate is obtained.
  • the source of the calcium carbonate may comprise further naturally occurring components such as magnesium carbonate, a
  • the source of ground calcium carbonate is selected from marble, chalk, calcite, dolomite, limestone, or mixtures thereof.
  • the source of ground calcium carbonate is selected from marble.
  • the GCC is obtained by dry grinding.
  • the GCC is obtained by wet grinding and subsequent drying.
  • Precipitated calcium carbonate in the meaning of the present invention is a synthesized material, generally obtained by precipitation following reaction of carbon dioxide and lime in an aqueous environment or by precipitation of a calcium and carbonate ion source in water or by precipitation of calcium and carbonate ions, for example CaCl 2 and Na 2 CO 3 , out of solution. Further possible ways of producing PCC are the lime soda process, or the Solvay process in which PCC is a by-product of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal habits) for each of these crystalline forms.
  • Calcite has a trigonal structure with typical crystal habits such as scalenohedral (S-PCC), rhombohedral (R-PCC), hexagonal prismatic, pinacoidal, colloidal (C-PCC), cubic, and prismatic (P-PCC).
  • Aragonite is an orthorhombic structure with typical crystal habits of twinned hexagonal prismatic crystals, as well as a diverse assortment of thin elongated prismatic, curved bladed, steep pyramidal, chisel shaped crystals, branching tree, and coral or worm-like form.
  • Vaterite belongs to the hexagonal crystal system.
  • the obtained PCC slurry can be mechanically dewatered and dried.
  • the calcium carbonate comprises one precipitated calcium carbonate.
  • the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of precipitated calcium carbonate.
  • the at least one precipitated calcium carbonate may comprise one PCC selected from S-PCC and one PCC selected from R-PCC.
  • a modified calcium carbonate may feature a GCC or PCC with an internal structure modification or a surface-reacted GCC or PCC.
  • a surface-reacted calcium carbonate may be prepared by providing a GCC or PCC in form of an aqueous suspension, and adding an acid to said suspension. Suitable acids are, for example, sulphuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or a mixture thereof.
  • the calcium carbonate is treated with gaseous carbon dioxide. If a strong acid such as sulphuric acid or hydrochloric acid is used for the acid treatment step, the carbon dioxide will form automatically in situ. Alternatively or additionally, the carbon dioxide can be supplied from an external source.
  • a surface-treated calcium carbonate may feature a GCC, PCC, or MCC comprising a treatment or coating layer on its surface.
  • the calcium carbonate may be treated or coated with a hydrophobising surface treatment agent such as, e.g., aliphatic carboxylic acids, salts or esters thereof, or a siloxane. Suitable aliphatic acids are, for example, C 5 to C 28 fatty acids such as stearic acid, palmitic acid, myristic acid, lauric acid, or a mixture thereof.
  • the calcium carbonate may also be treated or coated to become cationic or anionic with, for example, a polyacrylate or polydiallyldimethylammonium chloride (polyDADMAC).
  • PolyDADMAC polydiallyldimethylammonium chloride
  • the modified calcium carbonate is a surface-reacted calcium carbonate, preferably obtained from the reaction with sulphuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or a mixture thereof, and carbon dioxide.
  • the surface-treated calcium carbonate comprises a treatment layer or surface coating obtained from the treatment with fatty acids, their salts, their esters, or combinations thereof, preferably from the treatment with aliphatic C 5 to C 28 fatty acids, their salts, their esters, or combinations thereof, and more preferably from the treatment with ammonium stearate, calcium stearate, stearic acid, palmitic acid, myristic acid, lauric acid, or mixtures thereof.
  • the calcium carbonate has an average particle size d 50 from 0.1 to 3 ⁇ m, preferably from 0.4 to 2.5 ⁇ m, more preferably from 1.0 to 2.3 ⁇ m, and most preferably from 1.2 to 1.8 ⁇ m.
  • the calcium carbonate has an top cut particle size d 98 from 1 to 10 ⁇ m, preferably from 5 to 8 ⁇ m, more preferably from 4 to 7 ⁇ m, and most preferably from 6 to 7 ⁇ m.
  • the calcium carbonate can be present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, preferably from 0.2 to 40 wt.-%, and more preferably from 1.0 to 35 wt.-%, based on the total weight of the nonwoven fabric. According to another embodiment, the calcium carbonate is present in the nonwoven fabric in an amount from 0.5 to 20 wt.-%, from 1.0 to 10 wt.-%, from 5.0 to 40 wt.-%, from 7.5 to 30 wt.-%, or from 10 to 25 wt.-%, based on the total weight of the nonwoven fabric.
  • the calcium carbonate is dispersed within the at least one polymer and is present in an amount from 0.1 to 50 wt.-%, preferably from 0.2 to 40 wt.-%, and more preferably from 1 to 35 wt.-%, based on the total weight of the at least one polymer.
  • the calcium carbonate is dispersed within the at least one polymer and is present in an amount from 0.5 to 20 wt.-%, from 1.0 to 10 wt.-%, from 5.0 to 40 wt.-%, from 7.5 to 30 wt.-%, or from 10 to 25 wt.-%, based on the total weight of the at least one polymer.
  • the at least one filler consists of calcium carbonate.
  • the calcium carbonate may consist of only one specific type of calcium carbonate or a mixture of two or more types of calcium carbonates.
  • the at least one filler comprises further mineral pigments.
  • further pigment particles comprise silica, alumina, titanium dioxide, clay, calcined clays, talc, kaolin, calcium sulphate, wollastonite, mica, bentonite, barium sulfate, gypsum, or zinc oxide.
  • the at least one filler comprises at least 50 wt.-%, preferably at least 75 wt.-%, more preferably at least 90 wt.-%, and most preferably at least 95 wt.-% calcium carbonate, based on the total amount of the at least one filler.
  • the at least one filler is present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, preferably from 0.2 to 40 wt.-%, and more preferably from 1 to 35 wt.-%, based on the total weight of the nonwoven fabric.
  • the at least one filler is dispersed within the at least one polymer and is present in an amount from 1 to 50 wt.-%, preferably from 2 to 40 wt.-%, and more preferably from 5 to 35 wt.-%, based on the total weight of the at least one polymer.
  • the use of calcium carbonate as filler in a nonwoven fabric comprising at least one polymer comprising a polyester is provided.
  • the use of calcium carbonate as filler in a nonwoven fabric is provided, wherein the filler is dispersed within at least one polymer comprising a polyester.
  • the use of calcium carbonate as filler in a nonwoven fabric comprising a polyethylene terephthalate is provided.
  • the use of calcium carbonate as filler in a nonwoven fabric is provided, wherein the filler is dispersed within at least one polymer comprising a polyethylene terephthalate.
  • the calcium carbonate is a surface-treated calcium carbonate.
  • the use of calcium carbonate as filler in a nonwoven fabric fiber, filament and/or film-like filamentary structure comprising at least one polymer comprising a polyester, preferably a polyethylene terephthalate is provided.
  • the use of calcium carbonate as filler in a nonwoven fabric fiber, filament and/or film-like filamentary structure comprising at least one polymer comprising a polyester, preferably a polyethylene terephthalate is provided, wherein the filler is dispersed within at least one polymer.
  • a nonwoven fabric is a flat, flexible, porous sheet structure that is produced by interlocking layers or networks of fibers, filaments and/or film-like filamentary structures.
  • nonwoven fabric fiber, filament and/or film-like filamentary structure comprising at least one polymer comprising a polyester and at least one filler comprising calcium carbonate is provided.
  • the nonwoven fabric comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate, wherein the at least one filler is dispersed within the at least one polymer.
  • the nonwoven fabric comprises the at least one polymer and the at least one filler in form of fibers, filaments and/or film-like filamentary structures, wherein the at least one filler is dispersed within the at least one polymer.
  • the fibers and/or filaments may have a diameter from 0.5 to 40 ⁇ m, preferably from 5 to 35 ⁇ m. Furthermore, the fibers and/or filaments can have any cross-section shape, e.g., a circular, oval, rectangular, dumpbell-shaped, kidney-shaped, triangular, or irregular. The fibers and/or filaments can also be hollow and/or bi-component and/or tri-component fibers.
  • the nonwoven fabric may comprise further additives, for example, waxes, optical brighteners, heat stabilizers, antioxidants, anti-static agents, anti-blocking agents, dyestuffs, pigments, luster improving agents, surfactants, natural oils, or synthetic oils.
  • the nonwoven fabric may also comprise further inorganic fibers, preferably glass fibers, carbon fibers, or metal fibers. Alternatively or additionally, natural fibers such as cotton, linen, silk, or wool may be added.
  • the nonwoven fabric may also be reinforced by reinforcement threads in form of a textile surface structure, preferably in form of a fabric, laying, knitted fabric, knitwear or nonwoven fabric.
  • the nonwoven fabric consists of the at least one polymer comprising a polyester and the at least one filler comprising calcium carbonate. According to another embodiment, the nonwoven fabric comprises at least one polymer comprising a polyethylene terephthalate and at least one filler comprising calcium carbonate. According to still another embodiment, the nonwoven fabric consists of a polyethylene terephthalate and calcium carbonate.
  • the nonwoven fabric comprises the at least one polymer in an amount from 50 to 99 wt.-%, and the at least one filler in an amount from 1 to 50 wt.-%, based on the total weight of the nonwoven fabric, preferably the at least one polymer in an amount from 60 to 98 wt.-%, and the at least one filler in an amount from 2 to 40 wt.-%, and more preferably the at least one polymer in an amount from 65 to 95 wt.-%, and the at least one filler in an amount from 5 to 35 wt.-%.
  • the nonwoven fabric consists of 90 wt.-% of a polyester, preferably a polyethylene terephthalate, and 10 wt.-% calcium carbonate, preferably a ground calcium carbonate, based on the total weight of the nonwoven fabric.
  • the nonwoven fabric consists of 80 wt.-% of a polyester, preferably a polyethylene terephthalate, and 20 wt.-% calcium carbonate, preferably a ground calcium carbonate, based on the total weight of the nonwoven fabric.
  • a process for producing a nonwoven fabric comprising the steps of
  • the polyester is a polyethylene terephthalate and/or the calcium carbonate is surface-treated calcium carbonate.
  • the mixture of the at least one polymer comprising a polyethylene terephthalate and at the least one filler comprising calcium carbonate provided in process step a) can be prepared by any method known in the art.
  • the at least one polymer and the at least one filler may be dry blended, melt blended and optionally formed into granulates or pellets, or a masterbatch of the at least one polymer and the at least one filler may be premixed, optionally formed into granulates or pellets, and mixed with additional polymer or filler.
  • step b) the mixture is formed into fibers, preferably by an extrusion process, and more preferably by a melt blown process, a spunbond process, or a combination thereof.
  • any other suitable process known in the art for forming polymers into fibers may also be used.
  • melt blown fibers may be produced by melting the mixture, extruding the mixture through a die or small orifices to form fibers, and attenuating the molten polymer fibers by hot air. Surrounding cool air can then be induced into the hot air stream for cooling and solidifying the fibers.
  • the mixture can be melt-spun into fibers by pumping the molten mixture through a multitude of capillaries arranged in a uniform array of columns and rows. After extrusion, the fibers can be attenuated by high velocity air.
  • the air creates a draw force on the fibers that draws them down to a desired denier.
  • the spunbond process may have the advantage of giving nonwovens greater strength.
  • a second component may be co-extruded in the spunbond process, which may provide extra properties or bonding capabilities.
  • the Lurgi process is based on the extrusion of molten polymer through spinneret orifices followed by the newly formed extruded filaments being quenched with air and drawn by suction through Venturi tubes. Subsequent to formation, the filaments are disbursed on a conveyor belt to form a nonwoven web.
  • the Reifen Reifenberger process differs from the Lurgi process in that the quenching area for the filaments is sealed, and the quenched air stream is accelerated, thus inducing more effective entrainment of the filaments into the air stream.
  • the fibers formed in process step b) may be drawn or elongated to induce molecular orientation and affect crystallinity. This may result in a reduction in diameter and an improvement in physical properties.
  • step b) the mixture is formed into fibers by combining a melt blown process and a spunbond process.
  • a multilayer nonwoven fabric By combining a meltblown and a spunbond process, a multilayer nonwoven fabric can be produced, for example, a nonwoven fabric comprising two outer layers of spunbond fabric and an inner layer of meltblown fabric, which is known in the art as spundbonded-meltblown-spunbonded (SMS) nonwoven fabric. Additionally either or both of these processes may be combined in any arrangement with a staple fiber carding process or bonded fabrics resulting from a nonwoven staple fiber carding process. In such described laminate fabrics, the layers are generally at least partially consolidated by one of the optional bonding methods described further below.
  • SMS spundbonded-meltblown-spunbonded
  • the nonwoven fabric produced by the inventive process can be a multilayered nonwoven fabric, preferably a spundbonded-meltblown-spunbonded (SMS), a meltblown-spunbonded-meltblown (MSM), a spundbonded-meltblown-spunbonded-meltblown (SMSM), a meltblown-spunbonded-meltblown-spunbonded (MSMS), a spundbonded-meltblown-meltblown-spunbonded (SMMS), or a meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric.
  • Said nonwoven fabric may be compressed in order to ensure the cohesion of the layers, for example, by lamination.
  • steps b) and c) of the inventive process are repeated two or more times to produce a multilayer nonwoven fabric, preferably a spundbonded-meltblown-spunbonded (SMS), a meltblown-spunbonded-meltblown (MSM), a spundbonded-meltblown-spunbonded-meltblown (SMSM), a meltblown-spunbonded-meltblown-spunbonded (MSMS), a spundbonded-meltblown-meltblown-spunbonded (SMMS), or a meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric.
  • SMS spundbonded-meltblown-spunbonded
  • MSM meltblown-spunbonded-meltblown
  • SMSM spundbonded-meltblown-spunbonded-meltblown
  • MSMS meltblown-spunbonded-meltblown-spunbonded-meltblown
  • the nonwoven fabric is formed by collecting the fibers on a surface or carrier.
  • the fibers can be collected on a foraminous surface such as a moving screen or a forming wire.
  • the fibers may be randomly deposited on the foraminous surface so as to form a sheet, which may be held on the surface by a vacuum force.
  • the obtained nonwoven fabric is subjected to a bonding step.
  • bonding methods include thermal point bonding or calendering, ultrasonic bonding, hydroentanglement, needling and through-air bonding.
  • Thermal point bonding or calendering is a commonly used method and involves passing nonwoven fabric to be bonded through a heated calender roll and an anvil roll.
  • the calender roll is usually patterned in some way so that the entire fabric is not bonded across its entire surface.
  • Various patterns can be used in the process of the present invention without affecting the mechanical properties of the web.
  • the web can be bonded according to a ribbed knit pattern, a wire weave pattern, a diamond pattern, and the like. However, any other bonding method known in the art may also be used.
  • binding agents, adhesives, or other chemicals may be added during the binding step.
  • the obtained nonwoven fabric is subjected to a post-treatment step.
  • post-treatment processes are direction orientation, creping, hydroentanglement, or embossing processes.
  • the use of fibers for the manufacture of a non-woven fabric wherein the fibers comprise at least one polymer comprising a polyester and at least one filler comprising calcium carbonate.
  • the use of fibers for the manufacture of a non-woven fabric wherein the fibers comprise at least one polymer comprising a polyethylene terephthalate and at least one filler comprising calcium carbonate.
  • the use of a polymer composition for the manufacture of a non-woven fabric wherein the polymer composition comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate.
  • the use of a polymer composition for the manufacture of a non-woven fabric is provided, wherein the polymer composition comprises at least one polymer comprising a polyethylene terephthalate and at least one filler comprising calcium carbonate.
  • the nonwoven fabric of the present invention can be used in many different applications.
  • the inventive nonwoven fabric is used in construction products, waterproofing, thermal insulation, soundproofing, roofing, consumer apparel, upholstery and clothing industries, industrial apparel, medical products, home furnishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
  • an article comprising the inventive nonwoven fabric is provided, wherein said article is selected from construction products, consumer apparel, industrial apparel, medical products, home furnishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
  • Examples for construction products are house wrap, asphalt overlay, road and railroad beds, golf and tennis courts, wallcovering backings, acoustical wall coverings, roofing materials and tile underlayment, soil stabilizers and roadway underlayment, foundation stabilizers, erosion control products, canals construction, drainage systems, geomembranes protection and frost protection products, agriculture mulch, pond and canal water barriers, or sand infiltration barriers for drainage tile.
  • Other examples for construction products are fixations or reinforcements for earth fillings.
  • Examples for consumer apparel are interlinings, clothing and glove insulation, bra and shoulder paddings, handbag components, or shoe components.
  • Examples for industrial apparel are tarps, tents, or transportation (lumber, steel) wrappings.
  • Examples of medical products are protective clothing, face masks, isolation gowns, surgical gowns, surgical drapes and covers, surgical scrub suits, caps, sponges, dressings, wipes, orthopedic padding, bandages, tapes, dental bibs, oxygenators, dialyzers, filters for IV solutions or blood, or transdermal drug delivery components.
  • Examples for home furnishings are pillows, cushions, paddings in quilts or comforters, dust covers, insulators, window treatments, blankets, drapery components, carpet backings, or carpets.
  • Examples for protective products are coated fabrics, reinforced plastic, protective clothing, lab coats, sorbents, or flame barriers.
  • packaging materials are desiccant packing, sorbents packaging, gifts boxes, files boxes, various nonwoven bags, book covers, mailing envelopes, express envelopes, or courier bags.
  • Examples of filtration materials are gasoline, oil and air filters, including filtration liquid cartridge and bag filters, vacuum bags, or laminates with non woven layers.
  • the particle distribution of the calcium carbonate filler was measured using a Sedigraph 5120 from the company Micromeritics, USA. The method and the instruments are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1 wt.-% Na 4 P 2 O 7 . The samples were dispersed using a high speed stirrer and supersonics.
  • the intrinsic viscosity or IV is a measure of the molecular mass of the polymer and is measured by dilute solution viscosimetry. All IVs were measured in 60/40 ratio by weight of phenol/tetrachloroethane solution, at 25 °C according to ASTM D4603 in a Ubbelohde capillary viscometer. Typically, about 8-10 chips were dissolved to make a solution with a concentration of about 0.5%.
  • the tensile test was carried out in accordance with ISO 527-3 using a 1 BA (1:2) testing sample at a speed of 50 mm/min.
  • the properties that were determined via the tensile test are the yield stress, the break-strain, the break-stress, and the e-modulus of the polymer or polymer composition.
  • the charpy impact test was carried out in accordance with ISO 179-2:1997(E) using notched and unnotched testing samples having a size of 50 ⁇ 6 ⁇ 6 mm.
  • the inventive sample B showed a higher yield stress and e-modulus compared to the comparative sample A, while the break-strain and break-stress of the inventive sample B was reduced.
  • the inventive polymer composition (sample B) had a higher elasticity and softness compared to the pure PET polymer (sample A). This has a positive effect on the haptic properties of nonwoven fabrics produced from such a polymer composition, especially with respect to the softness of the material. For example, such a material is more pleasant to wear.
  • Sample C comparative
  • Sample D comparative
  • Sample E comparative
  • Amount polymer wt.-%) 100 90 80 Amount filler (wt.-%) - 10 20 Thickness (mm) 2.09 2.08 2.09 Yield stress (N/mm 2 ) 54.1 55.2 68.2 Break-strain (%) 830 578 242 Break-stress (N/mm 2 ) ⁇ 60 ⁇ 50 ⁇ 35
  • E-modulus (N/mm 2 ) 2280 2640 3070 Charpy (kJ/m 2 ) notched 2.9 1.6 1.0 Charpy (kJ/m 2 ) unnotched 150 72 62
  • inventive samples D and E showed a higher yield stress and e-modulus compared to the comparative sample C, while the break-strain, the break-stress, and the impact resistance of the inventive samples C and D was reduced.
  • inventive polymer compositions (samples D and E) had a higher elasticity and softness compared to the pure PET polymer (sample C). This has a positive effect on the haptic properties of nonwoven fabrics produced from such a polymer composition, especially with respect to the softness of the material. For example, such a material is more pleasant to wear.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Nonwoven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Artificial Filaments (AREA)
  • Absorbent Articles And Supports Therefor (AREA)
  • Laminated Bodies (AREA)
  • Multicomponent Fibers (AREA)

Claims (13)

  1. Tissu non tissé comprenant
    au moins un polymère comprenant un polyester, et
    au moins une charge comprenant du carbonate de calcium, le carbonate de calcium ayant une taille de particule moyenne d50 de 1,2 à 1,8 µm, et une taille de particule de coupe supérieure d98 de 4 à 7 µm, le carbonate de calcium étant présent dans le tissu non tissé en une quantité de 0,1 à 50 % en poids, et
    dans lequel le polyester est un téréphtalate de polyéthylène.
  2. Tissu non tissé selon la revendication 1, dans lequel le polyester a un poids moléculaire moyen en nombre de 5 000 à 100 000 g/mol, de préférence de 10 000 à 50 000 g/mol, et plus préférablement de 15 000 à 20 000 g/mol.
  3. Tissu non tissé selon l'une quelconque des revendications précédentes, dans lequel le carbonate de calcium est du carbonate de calcium broyé, du carbonate de calcium précipité, du carbonate de calcium modifié, du carbonate de calcium traité en surface ou un mélange de ceux-ci, de préférence du carbonate de calcium traité en surface.
  4. Tissu non tissé selon l'une quelconque des revendications précédentes, dans lequel le carbonate de calcium a une taille de particule de coupe supérieure d98 de 6 à 7 µm.
  5. Tissu non tissé selon l'une quelconque des revendications précédentes, dans lequel le carbonate de calcium est présent dans le tissu non tissé en une quantité de 0,2 à 40 % en poids, et de préférence de 1 à 35 % en poids, par rapport au poids total du tissu non tissé.
  6. Procédé de production d'un tissu non tissé comprenant les étapes de :
    a) fournir un mélange d'au moins un polymère comprenant un polyester et d'au moins une charge comprenant du carbonate de calcium, le polyester étant un téréphtalate de polyéthylène, le carbonate de calcium ayant une taille de particule moyenne d50 de 1,2 à 1,8 µm, et une taille de particule de coupe supérieure d98 de 4 à 7 µm,
    b) transformer le mélange en fibres, filaments et/ou structures filamenteuses de type film, et
    c) former un tissu non tissé à partir des fibres, filaments et/ou structures filamenteuses de type film, le carbonate de calcium étant présent dans le tissu non tissé en une quantité de 0,1 à 50 % en poids.
  7. Procédé selon la revendication 6, dans lequel dans l'étape b), le mélange est transformé en fibres, de préférence par un procédé d'extrusion, et plus préférablement par un procédé de fusion/soufflage, un procédé de filage direct, ou une combinaison de ceux-ci.
  8. Procédé selon la revendication 7, dans lequel le tissu non tissé est formé par collecte des fibres sur une surface ou un support.
  9. Procédé selon l'une quelconque des revendications 6 à 8, dans lequel les étapes b) et c) sont répétée deux fois ou plus pour produire un tissu non tissé multicouche, de préférence un tissu non tissé obtenu par filage direct-fusion/soufflage-filage direct (SMS), fusion/soufflage-filage direct-fusion/soufflage (MSM), filage direct-fusion/soufflage-filage direct-fusion/soufflage (SMSM), fusion/soufflage-filage direct-fusion/soufflage-filage direct (MSMS), filage direct-fusion/soufflage-fusion/soufflage-filage direct (SMMS) ou fusion/soufflage-filage direct filage direct-fusion/soufflage (MSSM).
  10. Utilisation de carbonate de calcium en tant que charge dans un tissu non tissé comprenant au moins un polymère comprenant un polyester, le polyester étant un téréphtalate de polyéthylène, le carbonate de calcium ayant une taille de particule moyenne d50 de 1,2 à 1,8 µm, et une taille de particule de coupe supérieure d98 de 4 à 7 µm.
  11. Utilisation de fibres pour la fabrication d'un tissu non tissé, dans laquelle les fibres comprennent au moins un polymère comprenant un polyester et au moins une charge comprenant du carbonate de calcium, le polyester étant un téréphtalate de polyéthylène, le carbonate de calcium ayant une taille de particule moyenne d50 de 1,2 à 1,8 µm, et une taille de particule de coupe supérieure d98 de 4 à 7 µm.
  12. Utilisation d'un tissu non tissé selon l'une quelconque des revendications 1 à 5, dans les produits de construction, l'étanchéité, l'isolation thermique, l'insonorisation, la toiture, les vêtements de consommation, les industries d'ameublement et d'habillement, les vêtements industriels, les articles médicaux, les accessoires pour la maison, les produits de protection, les matériaux d'emballage, les produits cosmétiques, les produits d'hygiène ou les matériaux de filtration.
  13. Article comprenant le tissu non tissé selon l'une quelconque des revendications 1 à 5, dans lequel ledit article est choisi parmi les produits de construction, les vêtements de consommation, les vêtements industriels, les produits médicaux, les accessoires pour la maison, les produits de protection, les matériaux d'emballage, les produits cosmétiques, les produits d'hygiène ou les matériaux de filtration.
EP13814950.5A 2012-12-28 2013-12-20 Caco3 en polyester pour non-tissé et fibres Active EP2938768B1 (fr)

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EP13814950.5A EP2938768B1 (fr) 2012-12-28 2013-12-20 Caco3 en polyester pour non-tissé et fibres

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EP12199746.4A EP2749679B1 (fr) 2012-12-28 2012-12-28 CaCO3 en polyester pour non-tissé et fibres
US201361748779P 2013-01-04 2013-01-04
PCT/EP2013/077742 WO2014102197A1 (fr) 2012-12-28 2013-12-20 Caco3 dans du polyester pour un non-tissé et des fibres
EP13814950.5A EP2938768B1 (fr) 2012-12-28 2013-12-20 Caco3 en polyester pour non-tissé et fibres

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ES2629257T3 (es) 2017-08-08
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JP2019065447A (ja) 2019-04-25
JP2020090771A (ja) 2020-06-11
MY171233A (en) 2019-10-04
KR20150103112A (ko) 2015-09-09
HRP20170893T1 (hr) 2017-09-08
ZA201505319B (en) 2016-10-26
RU2621660C2 (ru) 2017-06-06
PT2749679T (pt) 2017-06-27
AU2013369411B2 (en) 2016-12-22
AU2013369411A1 (en) 2015-07-02
TW201443305A (zh) 2014-11-16
EP2749679A1 (fr) 2014-07-02
EP2938768A1 (fr) 2015-11-04
JO3260B1 (ar) 2018-09-16
WO2014102197A1 (fr) 2014-07-03
BR112015015568A2 (pt) 2017-07-11
EP2749679B1 (fr) 2017-03-22
US20150322604A1 (en) 2015-11-12
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PL2749679T3 (pl) 2017-09-29
CA2894803C (fr) 2017-05-16
JP7106514B2 (ja) 2022-07-26
KR20170104675A (ko) 2017-09-15
MX2015008130A (es) 2015-09-23
SG11201505040RA (en) 2015-07-30
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JP2016508190A (ja) 2016-03-17
CA2894803A1 (fr) 2014-07-03
JP2022141779A (ja) 2022-09-29
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