EP2749679B1 - CaCO3 in polyester for nonwoven and fibers - Google Patents

CaCO3 in polyester for nonwoven and fibers Download PDF

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Publication number
EP2749679B1
EP2749679B1 EP12199746.4A EP12199746A EP2749679B1 EP 2749679 B1 EP2749679 B1 EP 2749679B1 EP 12199746 A EP12199746 A EP 12199746A EP 2749679 B1 EP2749679 B1 EP 2749679B1
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EP
European Patent Office
Prior art keywords
nonwoven fabric
calcium carbonate
polymer
meltblown
polyester
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.)
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EP12199746.4A
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German (de)
English (en)
French (fr)
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EP2749679A1 (en
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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Publication date
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Priority to HUE12199746A priority Critical patent/HUE034765T2/hu
Priority to PL12199746T priority patent/PL2749679T3/pl
Priority to ES12199746.4T priority patent/ES2629257T3/es
Priority to PT121997464T priority patent/PT2749679T/pt
Priority to SI201230971A priority patent/SI2749679T1/sl
Priority to EP12199746.4A priority patent/EP2749679B1/en
Priority to DK12199746.4T priority patent/DK2749679T3/da
Priority to JOP/2013/0379A priority patent/JO3260B1/ar
Priority to TW102147182A priority patent/TWI570294B/zh
Priority to KR1020157020187A priority patent/KR20150103112A/ko
Priority to MX2015008130A priority patent/MX2015008130A/es
Priority to MYPI2015001641A priority patent/MY171233A/en
Priority to KR1020177025103A priority patent/KR101846139B1/ko
Priority to SG11201505040RA priority patent/SG11201505040RA/en
Priority to JP2015550049A priority patent/JP2016508190A/ja
Priority to RU2015131156A priority patent/RU2621660C2/ru
Priority to CN202010293030.1A priority patent/CN111379073A/zh
Priority to AU2013369411A priority patent/AU2013369411B2/en
Priority to CA2894803A priority patent/CA2894803C/en
Priority to PCT/EP2013/077742 priority patent/WO2014102197A1/en
Priority to BR112015015568-5A priority patent/BR112015015568B1/pt
Priority to EP13814950.5A priority patent/EP2938768B1/en
Priority to CN201380068217.XA priority patent/CN104955995A/zh
Priority to US14/651,335 priority patent/US20150322604A1/en
Priority to UY0001035248A priority patent/UY35248A/es
Publication of EP2749679A1 publication Critical patent/EP2749679A1/en
Priority to CL2015001838A priority patent/CL2015001838A1/es
Priority to ZA2015/05319A priority patent/ZA201505319B/en
Application granted granted Critical
Publication of EP2749679B1 publication Critical patent/EP2749679B1/en
Priority to HRP20170893TT priority patent/HRP20170893T1/hr
Priority to JP2018168734A priority patent/JP2019065447A/ja
Priority to JP2019232746A priority patent/JP7106514B2/ja
Priority to JP2022112229A priority patent/JP2022141779A/ja
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Classifications

    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H3/00Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/005Synthetic yarns or filaments
    • D04H3/009Condensation or reaction polymers
    • D04H3/011Polyesters
    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING 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
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-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
    • D04H1/42Non-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
    • D04H1/4326Condensation or reaction polymers
    • D04H1/435Polyesters
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/637Including 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
    • Y10T442/642Strand 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. Further prior art can be found in WO2008/077156 . In view of the foregoing, improving the properties of polyester based nonwoven fabrics remains of interest to the skilled man.
  • a nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate, wherein the calcium carbonate is present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, based on the total weight of the nonwoven fabric, and wherein the nonwoven fabric comprises the at least one polymer and the at least one filler in form of fibers and/or filaments having a diameter from 0.5 to 40 ⁇ m, and wherein the polyester is a polyethylene terephthalate, and 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.
  • 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, wherein the calcium carbonate is present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, based on the total weight of the nonwoven fabric, and wherein the nonwoven fabric comprises the at least one polymer and the at least one filler in form of fibers and/or filaments having a diameter from 0.5 to 40 ⁇ m, and wherein the polyester is a polyethylene terephthalate, and 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.
  • 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, and wherein the polyester is a polyethylene terephthalate, and 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.
  • 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 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 top cut particle size d 98 from 6 to 7 ⁇ m.
  • the calcium carbonate is present in the nonwoven fabric in an amount from 0.2 to 40 wt.-%, and 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, wherein the polyester is a polyethylene terephthalate.
  • 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.
  • polyesters examples include a polyglycolic acid, a polycaprolactone, a polyethylene adipate, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polytrimethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate, a polylactic acid, or a mixture thereof, or copolymers thereof. Any of these polymers 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, wherein the calcium carbonate is present in the nonwoven fabric in an amount from 0.1 to 50 wt.-%, based on the total weight of the nonwoven fabric, and 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.
  • 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 top cut particle size d 98 from 6 to 7 ⁇ m.
  • the calcium carbonate can be present in the nonwoven fabric in an amount from 0.2 to 40 wt.-%, and 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 defined in the claims, as filler in a nonwoven fabric comprising at least one polymer comprising a polyester, wherein the polyester is a polyethylene terephthalate is provided.
  • the use of calcium carbonate, as defined in the claims, as filler in a nonwoven fabric is provided, wherein the filler is dispersed within at least one polymer comprising a polyester, wherein the polyester is a polyethylene terephthalate.
  • 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 defined in the claims, as filler in a nonwoven fabric fiber, filament and/or film-like filamentary structure comprising at least one polymer comprising a polyester, wherein the polyester is a polyethylene terephthalate, is provided.
  • the use of calcium carbonate, as defined in the claims, as filler in a nonwoven fabric fiber, filament and/or film-like filamentary structure comprising at least one polymer comprising a polyester, wherein the polyester is 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, wherein the polyester is a polyethylene terephthalate and at least one filler comprising calcium carbonate, as defined in the claims, is provided.
  • the nonwoven fabric comprises at least one polymer comprising a polyester, wherein the polyester is a polyethylene terephthalate and at least one filler comprising calcium carbonate, as defined in the claims, 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 have a diameter from 0.5 to 40 ⁇ m, preferably from 5 to 35 ⁇ m.
  • 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, wherein the polyester is polyethylene terephthalate and the at least one filler comprising calcium carbonate, as defined in claim 1.
  • the nonwoven fabric consists of a polyethylene terephthalate and calcium carbonate, as defined in the claims.
  • 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 polyethylene terephthalate, and 10 wt.-% calcium carbonate as defined in the claims, preferably a ground calcium carbonate, based on the total weight of the nonwoven fabric.
  • the nonwoven fabric consists of 80 wt.-% of a polyethylene terephthalate, and 20 wt.-% calcium carbonate as defined in the claims, 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 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, wherein the polyester is a polyethylene terephthalate and at least one filler comprising calcium carbonate as defined in the claims.
  • the use of a polymer composition for the manufacture of a non-woven fabric comprises at least one polymer comprising a polyester, wherein the polyester is a polyethylene terephthalate and at least one filler comprising calcium carbonate as defined in the claims.
  • 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 was determined by a Schott AVS 370 system.
  • the samples were dissolved in a 0.2 M NaCl solution, and subsequently, the pH was adjusted to 10 with NaOH. Measurements were performed at 25°C with a capillary type 0a and corrected using the Hagenbach correction.
  • 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)
EP12199746.4A 2012-12-28 2012-12-28 CaCO3 in polyester for nonwoven and fibers Active EP2749679B1 (en)

Priority Applications (31)

Application Number Priority Date Filing Date Title
HUE12199746A HUE034765T2 (hu) 2012-12-28 2012-12-28 CaCO3, nem szövött anyagok és szálak számára szolgáló poliészterben
PL12199746T PL2749679T3 (pl) 2012-12-28 2012-12-28 CaCO3 w poliestrze dla włókniny i włókien
ES12199746.4T ES2629257T3 (es) 2012-12-28 2012-12-28 CaCO3 en poliéster para textiles no tejidos y fibras
PT121997464T PT2749679T (pt) 2012-12-28 2012-12-28 Caco3 em poliéster para não-tecidos e fibras
SI201230971A SI2749679T1 (sl) 2012-12-28 2012-12-28 CaCO3 V POLIESTRU ZA NETKANINE IN VLAKNA
EP12199746.4A EP2749679B1 (en) 2012-12-28 2012-12-28 CaCO3 in polyester for nonwoven and fibers
DK12199746.4T DK2749679T3 (da) 2012-12-28 2012-12-28 CaCO3 i polyester til ikke-vævet stof og fibre
TW102147182A TWI570294B (zh) 2012-12-28 2013-12-19 用於不織布及纖維之聚酯中的碳酸鈣
JOP/2013/0379A JO3260B1 (ar) 2012-12-28 2013-12-19 كربونات الكالسيوم في بولي إستر من قماش غير منسوج أو ألياف
CN201380068217.XA CN104955995A (zh) 2012-12-28 2013-12-20 用于非织造物和纤维的聚酯中的caco3
MYPI2015001641A MY171233A (en) 2012-12-28 2013-12-20 Caco3 in polyester for nonwoven and fibers
KR1020177025103A KR101846139B1 (ko) 2012-12-28 2013-12-20 부직포 및 섬유용 폴리에스테르에서 CaCO3
SG11201505040RA SG11201505040RA (en) 2012-12-28 2013-12-20 Caco3 in polyester for nonwoven and fibers
JP2015550049A JP2016508190A (ja) 2012-12-28 2013-12-20 不織布および繊維のためのポリエステル中のCaCO3
RU2015131156A RU2621660C2 (ru) 2012-12-28 2013-12-20 СаСО3 В СЛОЖНОМ ПОЛИЭФИРЕ ДЛЯ НЕТКАНЫХ МАТЕРИАЛОВ И ВОЛОКОН
CN202010293030.1A CN111379073A (zh) 2012-12-28 2013-12-20 用于非织造物和纤维的聚酯中的CaCO3
KR1020157020187A KR20150103112A (ko) 2012-12-28 2013-12-20 부직포 및 섬유용 폴리에스테르에서 caco3
CA2894803A CA2894803C (en) 2012-12-28 2013-12-20 Caco3 in polyester for nonwoven and fibers
PCT/EP2013/077742 WO2014102197A1 (en) 2012-12-28 2013-12-20 Caco3 in polyester for nonwoven and fibers
BR112015015568-5A BR112015015568B1 (pt) 2012-12-28 2013-12-20 Material não tecido compreendendo poliéster e carbonato de cálcio, processo de produção do referido material, usos do carbonato de cálcio, fibras e do material não tecido e artigo compreendendo tal material
EP13814950.5A EP2938768B1 (en) 2012-12-28 2013-12-20 Caco3 in polyester for nonwoven and fibers
MX2015008130A MX2015008130A (es) 2012-12-28 2013-12-20 Caco3 en poliester para telas no tejidas y fibras.
US14/651,335 US20150322604A1 (en) 2012-12-28 2013-12-20 CaCO3 IN POLYESTER FOR NONWOVEN AND FIBERS
AU2013369411A AU2013369411B2 (en) 2012-12-28 2013-12-20 CaCO3 in polyester for nonwoven and fibers
UY0001035248A UY35248A (es) 2012-12-28 2013-12-27 ?caco3 en poliéster para telas no tejidas y fibras?.
CL2015001838A CL2015001838A1 (es) 2012-12-28 2015-06-25 Caco3 en poliéster para telas no tejidas y fibras
ZA2015/05319A ZA201505319B (en) 2012-12-28 2015-07-23 Caco3 in polyester for nonwoven and fibers
HRP20170893TT HRP20170893T1 (hr) 2012-12-28 2017-06-12 CaCO3 U POLIESTERU ZA NETKANE MATERIJALE I VLAKNA
JP2018168734A JP2019065447A (ja) 2012-12-28 2018-09-10 不織布および繊維のためのポリエステル中のCaCO3
JP2019232746A JP7106514B2 (ja) 2012-12-28 2019-12-24 不織布および繊維のためのポリエステル中のCaCO3
JP2022112229A JP2022141779A (ja) 2012-12-28 2022-07-13 不織布および繊維のためのポリエステル中のCaCO3

Applications Claiming Priority (1)

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EP12199746.4A EP2749679B1 (en) 2012-12-28 2012-12-28 CaCO3 in polyester for nonwoven and fibers

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EP2749679B1 true EP2749679B1 (en) 2017-03-22

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US (1) US20150322604A1 (hu)
EP (2) EP2749679B1 (hu)
JP (4) JP2016508190A (hu)
KR (2) KR101846139B1 (hu)
CN (2) CN104955995A (hu)
AU (1) AU2013369411B2 (hu)
BR (1) BR112015015568B1 (hu)
CA (1) CA2894803C (hu)
CL (1) CL2015001838A1 (hu)
DK (1) DK2749679T3 (hu)
ES (1) ES2629257T3 (hu)
HR (1) HRP20170893T1 (hu)
HU (1) HUE034765T2 (hu)
JO (1) JO3260B1 (hu)
MX (1) MX2015008130A (hu)
MY (1) MY171233A (hu)
PL (1) PL2749679T3 (hu)
PT (1) PT2749679T (hu)
RU (1) RU2621660C2 (hu)
SG (1) SG11201505040RA (hu)
SI (1) SI2749679T1 (hu)
TW (1) TWI570294B (hu)
UY (1) UY35248A (hu)
WO (1) WO2014102197A1 (hu)
ZA (1) ZA201505319B (hu)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020005400A1 (en) * 2018-06-26 2020-01-02 Intrinsic Advanced Materials, LLC Biodegradable textiles, masterbatches, and method of making biodegradable fibers

Families Citing this family (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10717674B2 (en) 2010-04-27 2020-07-21 Biomason, Inc. Methods for the manufacture of colorfast masonry
CN105431285B (zh) * 2013-03-14 2018-04-17 伊梅里斯矿物有限公司 复合结构体
US9476204B2 (en) 2014-02-03 2016-10-25 Owens Corning Intellectual Capital, Llc Boxed netting insulation system for roof deck
US9920516B2 (en) 2014-02-03 2018-03-20 Owens Corning Intellectual Capital, Llc Roof insulation systems
US9926702B2 (en) 2014-02-03 2018-03-27 Owens Corning Intellectual Property, LLC Roof insulation systems
EP3070057A1 (en) * 2015-03-16 2016-09-21 Omya International AG Process for the purification of water
ITUB20155124A1 (it) * 2015-10-21 2017-04-21 Imbotex Srl Imbottitura termica particolarmente per indumenti tecnici per attivita' outdoor
DK3325703T3 (da) 2016-08-02 2019-10-28 Fitesa Germany Gmbh System og fremgangsmåde til fremstilling af ikke-vævede polymælkesyrestoffer
US11441251B2 (en) 2016-08-16 2022-09-13 Fitesa Germany Gmbh Nonwoven fabrics comprising polylactic acid having improved strength and toughness
CN109789247B (zh) * 2016-09-08 2022-03-01 卡尔莱布宁医疗技术有限公司 含有抑制碳酸钙的植入物
SE540458C2 (en) * 2016-10-18 2018-09-18 Perstorp Ab Use of calcium carbonate to increase the melt flow rate in a polycaprolactone thermoplastic composition
WO2018081542A1 (en) 2016-10-31 2018-05-03 Biomason, Inc. Microorganism loaded aggregate and manufacturing methods
EP3318599A1 (en) 2016-11-07 2018-05-09 Omya International AG Use of mono-substituted succinic anhydride
WO2018095515A1 (en) 2016-11-22 2018-05-31 Omya International Ag Surface-treated fillers for biaxially oriented polyester films
EP3615490B1 (en) 2017-04-25 2023-06-07 Biomason Inc. Fabric and method of manufacture for biologically cemented structures for marine applications
WO2018234838A1 (en) * 2017-06-20 2018-12-27 Rhodia Poliamida E Especialidades S.A. FILTRATION MEDIUM, METHODS OF PRODUCTION AND USES THEREOF
WO2019071175A1 (en) 2017-10-05 2019-04-11 Biomason, Inc. METHOD AND SYSTEM FOR BIOCIMENTATION
US11166853B2 (en) 2017-10-13 2021-11-09 The Procter & Gamble Company Absorbent articles comprising nonwoven materials having improved thermal conductivity
CN109468752B (zh) * 2019-01-09 2020-11-10 江阴健发特种纺织品有限公司 一种多层纺熔复合厨房擦拭材料及制备方法
EP3693407A1 (en) 2019-02-11 2020-08-12 Omya International AG A surface-treated filler material product providing improved uv stability for polymeric articles
EP3997265B1 (en) * 2019-07-11 2024-03-13 Omya International AG Nonwoven fabric and process for the production thereof
US20230047798A1 (en) * 2020-01-29 2023-02-16 Omya International Ag Nonwoven fabrics comprising polylactic acid and surface-treated calcium carbonate
CN114311888A (zh) * 2021-12-30 2022-04-12 苏州赛伍应用技术股份有限公司 一种防草垫及其制备方法和应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008077156A2 (en) * 2006-12-20 2008-06-26 Imerys Pigments, Inc. Spunlaid fibers comprising coated calcium carbonate, processes for their production, and nonwoven products

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3544525A (en) * 1968-03-26 1970-12-01 Allied Chem Process for crystallization,drying and solid-state polymerization of polyesters
JPS57128217A (en) * 1981-01-28 1982-08-09 Kuraray Co Ltd Fiber from polyester copolymer composition
JP3317456B2 (ja) * 1993-03-03 2002-08-26 株式会社クラレ 生分解性繊維
JPH06305090A (ja) * 1993-04-22 1994-11-01 New Oji Paper Co Ltd 印刷用シートの製造方法
CA2116081C (en) * 1993-12-17 2005-07-26 Ann Louise Mccormack Breathable, cloth-like film/nonwoven composite
JPH08127993A (ja) * 1994-10-26 1996-05-21 Unitika Ltd 湿式不織布及びその製造方法
CA2188538A1 (en) 1995-02-23 1996-08-29 Kazuaki Matsumoto Polyethylene terephthalate resin composition
TW293049B (hu) * 1995-03-08 1996-12-11 Unitika Ltd
ES2166061T3 (es) 1996-02-12 2002-04-01 Fibervisions As Fibras que contienen particulas.
JPH1088459A (ja) * 1996-09-11 1998-04-07 Chisso Corp 長繊維不織布
JPH10158909A (ja) * 1996-11-21 1998-06-16 Shinwa Kk 使い捨て保護衣料用生地及びその製造方法
FI105840B (fi) * 1997-09-16 2000-10-13 Metsae Serla Oyj Menetelmä materiaalirainan päällystämiseksi
US6797377B1 (en) 1998-06-30 2004-09-28 Kimberly-Clark Worldwide, Inc. Cloth-like nonwoven webs made from thermoplastic polymers
JP2000178865A (ja) * 1998-12-14 2000-06-27 Unitika Ltd 衛生材用不織布
US6484107B1 (en) 1999-09-28 2002-11-19 Rosemount Inc. Selectable on-off logic modes for a sensor module
KR100623838B1 (ko) * 2000-05-25 2006-09-12 에스케이케미칼주식회사 견면의 제조방법 및 그 제조장치
TW570953B (en) * 2002-04-29 2004-01-11 Nanya Plastics Corp Polyester composition and hot-fill bottle manufactured therefrom
US6863976B2 (en) * 2002-11-16 2005-03-08 Milliken & Company Polypropylene monofilament and tape fibers exhibiting certain creep-strain characteristics and corresponding crystalline configurations
DE10330944A1 (de) * 2003-07-08 2005-02-03 Oberschelp, Axel Mischfaservlies oder-gewebe
EP1685188A1 (en) * 2003-10-21 2006-08-02 E.I. Dupont De Nemours And Company Ethylene copolymer modified oriented polyester films, tapes, fibers and nonwoven textiles
US20050260913A1 (en) * 2004-05-21 2005-11-24 Doesburg Van I Floor covering product including recycled material and method of making same
KR100595594B1 (ko) * 2004-06-17 2006-07-03 주식회사 효성 복합섬유 및 이의 제조방법
WO2006054475A1 (ja) * 2004-11-16 2006-05-26 Mitsubishi Plastics, Inc. 脂肪族ポリエステル系樹脂反射フィルム及び反射板
EP1811071A1 (en) * 2006-01-18 2007-07-25 Celanese Emulsions GmbH Latex bonded airlaid fabric and its use
DE102006020488B4 (de) * 2006-04-28 2017-03-23 Fitesa Germany Gmbh Vliesstoff, Verfahren zu dessen Herstellung und dessen Verwendung
US20100184348A1 (en) * 2006-12-20 2010-07-22 Imerys Pigments, Inc. Spunlaid Fibers Comprising Coated Calcium Carbonate, Processes For Their Production, and Nonwoven Products
DK2116367T3 (en) * 2007-03-02 2018-05-14 Mitsui Chemicals Inc LAYERED NON-WOVEN FABRICS
SI2093261T1 (sl) 2007-11-02 2013-12-31 Omya International Ag Uporaba površinsko reagiranega kalcijevega karbonata pri vpojnem papirju, postopek za pripravo izdelkov iz vpojnega papirja z izboljšano mehkobo in odgovarjajoči izdelki iz vpojnega papirja z izboljšano mehkobo
DK2070991T3 (da) 2007-12-12 2010-12-20 Omya Development Ag Fremgangsmåde til frembringelse af overflademodificeret, udfældet calciumcarbonat
US20100035045A1 (en) * 2008-01-21 2010-02-11 Imerys Pigments, Inc. Fibers comprising at least one filler and processes for their production
WO2009094321A1 (en) * 2008-01-21 2009-07-30 Imerys Pigments, Inc. Monofilament fibers comprising at least one filler, and processes for their production
AT506658B1 (de) 2008-03-31 2015-02-15 Erema Verfahren zur herstellung eines gefüllten polymermaterials
US8470222B2 (en) * 2008-06-06 2013-06-25 Kimberly-Clark Worldwide, Inc. Fibers formed from a blend of a modified aliphatic-aromatic copolyester and thermoplastic starch
JP5470532B2 (ja) * 2008-07-04 2014-04-16 株式会社高木化学研究所 難燃性原着ポリエステル繊維、これを用いた難燃材および難燃性原着ポリエステル繊維の製造方法
EP2159258B1 (en) 2008-08-26 2011-07-27 Omya Development AG Treated mineral filler products, process for the preparation thereof and uses of same
EP2264109B1 (en) 2009-06-15 2012-01-25 Omya Development AG Process for preparing surface-reacted calcium carbonate and its use
PL2264108T3 (pl) 2009-06-15 2012-07-31 Omya Int Ag Sposób wytwarzania przereagowanego powierzchniowo węglanu wapnia, z wykorzystaniem słabego kwasu
US9080258B2 (en) * 2009-07-10 2015-07-14 North Carolina State University Process of making highly oriented and crystalline thermoplastic filaments
US9394630B2 (en) * 2009-09-03 2016-07-19 Toray Industries, Inc. Pilling-resistant artificial leather
US8721943B2 (en) * 2009-12-17 2014-05-13 3M Innovative Properties Company Process of making dimensionally stable nonwoven fibrous webs
FR2957610B1 (fr) * 2010-03-17 2012-03-23 Freudenberg Politex Sa Produit non-tisse contenant des particules organiques et/ou minerales et son procede de fabrication
SI2371766T1 (sl) 2010-04-01 2013-07-31 Omya Development Ag Postopek za pridobivanje oborine kalcijevega karbonata
US20110311759A1 (en) * 2010-06-17 2011-12-22 E.I. Du Pont De Nemours And Company Flame retardant performance in poly (trimethylene) terephthalate
GB201017888D0 (en) 2010-10-22 2010-12-01 Imerys Minerals Ltd Film compositions
SI2447213T1 (sl) 2010-10-26 2015-07-31 Omya International Ag Proizvodnja visoko čistega oborjenega kalcijevega karbonata
US8651286B2 (en) 2010-12-15 2014-02-18 Johns Manville Spunbond polyester mat with binder comprising salt of inorganic acid
US20120238982A1 (en) * 2011-03-15 2012-09-20 Paul Thomas Weisman Structured Fibrous Web
PT2524898E (pt) 2011-05-16 2015-11-03 Omya Int Ag Método para a produção de carbonato de cálcio precipitado a partir de refugos de fábricas de pasta de papel

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008077156A2 (en) * 2006-12-20 2008-06-26 Imerys Pigments, Inc. Spunlaid fibers comprising coated calcium carbonate, processes for their production, and nonwoven products

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020005400A1 (en) * 2018-06-26 2020-01-02 Intrinsic Advanced Materials, LLC Biodegradable textiles, masterbatches, and method of making biodegradable fibers
WO2020005399A1 (en) * 2018-06-26 2020-01-02 Intrinsic Advanced Materials, LLC Biodegradable textiles, masterbatches, and method of making biodegradable fibers
WO2020005401A1 (en) * 2018-06-26 2020-01-02 Intrinsic Advanced Materials, LLC Biodegradable textiles, masterbatches, and method of making biodegradable fibers

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