AU2013369411B2 - CaCO3 in polyester for nonwoven and fibers - Google Patents
CaCO3 in polyester for nonwoven and fibers Download PDFInfo
- Publication number
- AU2013369411B2 AU2013369411B2 AU2013369411A AU2013369411A AU2013369411B2 AU 2013369411 B2 AU2013369411 B2 AU 2013369411B2 AU 2013369411 A AU2013369411 A AU 2013369411A AU 2013369411 A AU2013369411 A AU 2013369411A AU 2013369411 B2 AU2013369411 B2 AU 2013369411B2
- Authority
- AU
- Australia
- Prior art keywords
- nonwoven fabric
- calcium carbonate
- polymer
- meltblown
- fibers
- 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.)
- Ceased
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 245
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 106
- 229920000728 polyester Polymers 0.000 title claims abstract description 51
- 239000000835 fiber Substances 0.000 title claims description 58
- 235000010216 calcium carbonate Nutrition 0.000 title description 97
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 121
- 229920000642 polymer Polymers 0.000 claims abstract description 105
- 239000000945 filler Substances 0.000 claims abstract description 67
- 238000000034 method Methods 0.000 claims abstract description 59
- 230000008569 process Effects 0.000 claims abstract description 51
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 69
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 69
- -1 polyethylene adipate Polymers 0.000 claims description 64
- 239000000203 mixture Substances 0.000 claims description 51
- 239000000047 product Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 229940088417 precipitated calcium carbonate Drugs 0.000 claims description 11
- 238000010276 construction Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 229940127554 medical product Drugs 0.000 claims description 7
- 239000005022 packaging material Substances 0.000 claims description 7
- 239000002537 cosmetic Substances 0.000 claims description 6
- 239000000155 melt Substances 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- 238000001125 extrusion Methods 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 4
- 229920000954 Polyglycolide Polymers 0.000 claims description 3
- 229920000331 Polyhydroxybutyrate Polymers 0.000 claims description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 claims description 3
- 239000005014 poly(hydroxyalkanoate) Substances 0.000 claims description 3
- 239000005015 poly(hydroxybutyrate) Substances 0.000 claims description 3
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 3
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 0.000 claims description 3
- 229920000921 polyethylene adipate Polymers 0.000 claims description 3
- 239000011112 polyethylene naphthalate Substances 0.000 claims description 3
- 239000004633 polyglycolic acid Substances 0.000 claims description 3
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- 239000004626 polylactic acid Substances 0.000 claims description 3
- 229920002215 polytrimethylene terephthalate Polymers 0.000 claims description 3
- 238000004078 waterproofing Methods 0.000 claims description 3
- 239000004744 fabric Substances 0.000 description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 238000011282 treatment Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
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- 150000002148 esters Chemical group 0.000 description 8
- 229910021532 Calcite Inorganic materials 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000009864 tensile test Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
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- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
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- 238000005886 esterification reaction Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 4
- 239000004579 marble Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 235000019738 Limestone Nutrition 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
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- 239000002667 nucleating agent Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 235000011149 sulphuric acid Nutrition 0.000 description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical group [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 235000021314 Palmitic acid Nutrition 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004734 Polyphenylene sulfide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 235000011116 calcium hydroxide Nutrition 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
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- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
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- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
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- 239000001993 wax Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
Landscapes
- 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)
- Multicomponent Fibers (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention concerns a nonwoven fabric comprising at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. The present invention further relates to a process of producing such a nonwoven fabric as well as to the use of calcium carbonate as filler in a nonwoven fabric comprising at least one polymer comprising a polyester.
Description
PCT/EP2013/077742 WO 2014/102197
CaC03 in polyester for nonwoven and fibers
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 5 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 10 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 yam 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 15 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. 20
Today, nonwoven fabrics are mainly produced from thermoplastic polymers such as polypropylene, polyethylene, polyamides, or polyesters. The advantage of polyester fibers or filaments is their high crystallinity, high strength and high tenacity. Polyethylene terephthalate (PET) is the most widely used polyester class and is 25 characterized by high modulus, low shrinkage, heat set stability, light fastness and chemical resistance account for the great versatility of PET. One major drawback of PET is its slow crystallization rate, which does not allow reasonable cycle times for manufacturing processes such as injection molding. Therefore nucleating agents such as talc are often added. However, these heterogeneous particles can act as stress 30 concentrators, and thereby, may affect the mechanical properties of the polymer. Therefore, nucleated PET is often reinforced with glass fibers. WO 2014/102197 PCT/EP2013/077742 -2- 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. 5 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 Al. WO 2012/052778 Al relates to tearable polymer films comprising a polyester and calcium carbonate or mica fillers. The spinning of PET fibers containing modified 10 calcium carbonate was studied by Boonsri Kusktham and is described in the article entitled “Spinning of PET fibres mixed with calcium carbonate”, which was published in the Asian Journal of Textile, 2011, 1(2), 106 to 113.
Extruded fibers and nonwoven webs containing titanium dioxide and at least one 15 mineral filler are disclosed in US 6,797,377 Bl. 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 Al. WO 97/30199 relates to fibers or filaments suitable for the production of a nonwoven fabric, the fibers or 20 filaments consisting essentially of a polyolefin and inorganic particles.
In view of the foregoing, improving the properties of polyester based nonwoven fabrics remains of interest to the skilled man. 25 It is an object of the present invention to provide a nonwoven fabric having an improved soft touch and a higher stiffness. It would also be desirable to provide a nonwoven fabric which can be tailored with respect to its hydrophobic or hydrophilic properties. It would also be desirable to provide a nonwoven fabric containing a WO 2014/102197 PCT/EP2013/077742 -3- reduced amount of polymer without affecting the quality of the nonwoven fabric significantly.
It also an object of the present invention to provide a process for producing a 5 nonwoven fabric from a polyester based polymer composition, especially a PET composition, which allows short cycle times during melt processing. It is also desirable to provide a process for producing a nonwoven fabric which allows the use of recycled polyester, especially recycled PET. 10 The foregoing objects and other objects are solved by the subject-matter as defined herein in the independent claims.
According to one aspect of the present invention, a nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium 15 carbonate is provided.
According to another aspect, the present invention provides a process for producing a nonwoven fabric comprising the steps of a) providing a mixture of at least one polymer comprising a polyester and at 20 least one filler comprising calcium carbonate, b) forming the mixture into fibers, filaments and/or film-like filamentary structures, and c) forming a nonwoven fabric from the fibers, filaments and/or film-like filamentary structures. 25
According to still another aspect, 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 WO 2014/102197 PCT/EP2013/077742 -4- fumishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
According to still another aspect, the present invention provides the use of calcium 5 carbonate as filler in a nonwoven fabric comprising at least one polymer comprising a polyester.
According to still another aspect, the present invention provides the use of fibers for the manufacture of a non-woven fabric, wherein the fibers comprise at least one 10 polymer comprising a polyester and at least one filler comprising calcium carbonate.
According to still another aspect, the present invention provides the use of the inventive nonwoven fabric in construction products, waterproofing, thermal insulation, soundproofing, roofing, consumer apparel, upholstery and clothing 15 industries, industrial apparel, medical products, home furnishings, protective products, packaging materials, cosmetic products, hygiene products, or filtration materials.
Advantageous embodiments of the present invention are defined in the 20 corresponding sub-claims.
According to one embodiment the polyester is selected from the group consisting of a polyglycolic acid, a polycapro lactone, a polyethylene adipate, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polyethylene terephthalate, a 25 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. According to another embodiment the polyester has a number average molecular weight from 5000 to 100000 g/mol, WO 2014/102197 PCT/EP2013/077742 -5- preferably from 10000 to 50000 g/mol, and more preferably from 15000 to 20000 g/mol.
According to one embodiment the calcium carbonate is ground calcium carbonate, 5 precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium carbonate, or a mixture thereof, preferably surface-treated calcium carbonate. According to another embodiment the calcium carbonate has an average particle size dso from 0.1 to 3 pm, preferably from 0.4 to 2.5 pm, more preferably from 1.0 to 2.3 pm, and most preferably from 1.2 to 1.8 pm. According to still another 10 embodiment the calcium carbonate has an top cut particle size elm from 1 to 10 pm, preferably from 5 to 8 pm, more preferably from 4 to 7 pm, and most preferably from 6 to 7 pm. According to still another embodiment 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 15 o f the nonwoven fabric.
According to one embodiment of the inventive process, in 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. According to another 20 embodiment of the inventive process, the nonwoven fabric is formed by collecting the fibers on a surface or carrier. According to still another embodiment of the inventive process, 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-25 spunbonded-meltblown (SMSM), a meltblown-spunbonded-meltblown-spunbonded (MSMS), a spundbonded-meltblown- meltblown-spunbonded (SMMS), or a meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric. WO 2014/102197 PCT/EP2013/077742 -6-
It should be understood that for the purpose of the present invention, the following terms have the following meaning:
The term “degree of crystallinity” as used in the context of the present invention 5 refers to the fraction of the ordered molecules in a polymer. The remaining fraction is designated as “amorphous”. Polymers may crystallize upon cooling from the melt, mechanical stretching or solvent evaporation. Crystalline areas are generally more densely packed than amorphous areas and crystallization may affect optical, mechanical, thermal and chemical properties of the polymer. The degree of 10 crystallinity is specified in percent and can be determined by differential scanning calorimetry (DSC). “Ground calcium carbonate” (GCC) in the meaning of the present invention is a calcium carbonate obtained from natural sources, such as limestone, marble, calcite 15 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.
The term “intrinsic viscosity” as used in the context of the present invention is a measure of the capability of a polymer in solution to enhance the viscosity of the 20 solution and is specified in dl/g. “Modified calcium carbonate” (MCC) 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”. 25 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. Preferably, 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 WO 2014/102197 PCT/EP2013/077742 -7- crystalline calcium salt of said anion originate largely from the starting calcium carbonate material. MCCs are described, for example, in US 2012/0031576 Al, WO 2009/074492 Al, EP 2 264 109 Al, EP 2 070 991 Al, or 2 264 108 Al. 5 For the purpose of the present invention, the term “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.
Throughout the present document, the “particle size” of a calcium carbonate filler is 10 described by its distribution of particle sizes. The value dx represents the diameter relative to which x % by weight of the particles have diameters less than dx. This means that the djo value is the particle size at which 20 wt.-% of all particles are smaller, and the dg8 value is the particle size at which 98 wt.-% of all particles are smaller. The dg% value is also designated as “top cut”. The dso value is thus the 15 weight median particle size, i.e. 50 wt.-% of all grains are bigger or smaller than this particle size. For the purpose of the present invention the particle size is specified as weight median particle size dso unless indicated otherwise. For determining the weight median particle size dso value or the top cut particle size dg% value a Sedigraph 5100 or 5120 device from the company Micromeritics, USA, can be used. 20
As used herein the term “polymer” generally includes homopolymers and copolymers such as, for example, block, graft, random and alternating copolymers, as well as blends and modifications thereof. 25 “Precipitated calcium carbonate” (PCC) 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, WO 2014/102197 PCT/EP2013/077742 -8- 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 Al, EP 2,524,898 Al, EP 2 371 766 Al, or unpublished 5 European patent application no. 12 164 041.1.
In the meaning of the present invention, 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. 10
Where the term “comprising” is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term “consisting of’ is considered to be a preferred embodiment of the term “comprising of’. If hereinafter a group is defined to comprise at least a certain number of 15 embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.
Where an indefinite or definite article is used when referring to a singular noun, e.g. “a”, “an” or “the”, this includes a plural of that noun unless something else is 20 specifically stated.
Terms like “obtainable” or “definable” and “obtained” or “defined” are used interchangeably. This e.g. means that, unless the context clearly dictates otherwise, the term “obtained” does not mean to indicate that e.g. an embodiment must be 25 obtained by e.g. the sequence of steps following the term “obtained” even though such a limited understanding is always included by the terms “obtained” or “defined” as a preferred embodiment. WO 2014/102197 PCT/EP2013/077742 -9-
The inventive nonwoven fabric comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. In the following details and preferred embodiments of the inventive product will be set out in more detail. It is to be understood that these technical details and embodiments also apply 5 to the inventive process for producing said nonwoven fabric and the inventive use of the nonwoven fabric, fibers, compositions, and calcium carbonate.
The at least one polymer 10
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 15 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. 20 According to one embodiment, the polyester is selected form 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. Any of 25 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. WO 2014/102197 PCT/EP2013/077742 - 10-
According to one embodiment of the present invention, 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. 5 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. According to one embodiment, 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.-%, 10 and more preferably from 65 to 95 wt.-%, based on the total weight of the nonwoven fabric.
According to a preferred embodiment of the present invention, the polyester is a polyethylene terephthalate. 15
Polyethylene terephthalate (PET) is a condensation polymer and may be industrially produced by condensating either terephthalic acid or dimethyl terephthalate with ethylene glycol. 20 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 25 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. WO 2014/102197 PCT/EP2013/077742 - 11 -
Alternatively, PET may be produced by solid-phase polycondensation. For example, in such a process a melt poly condensation 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 5 desirable molecular weight of the polymer is obtained.
According to one embodiment, PET is obtained from a continuous polymerization process, a batch-wise polymerization process or a solid phase polymerization process. 10
According to the present invention, the term “polyethylene terephthalate” comprises unmodified and modified polyethylene terephthalate. The polyethylene terephthalate may be a linear polymer, a branched polymer, or a cross-linked polymer. For example, if glycerol is allowed to react with a diacid or its anhydride each glycerol 15 will generate a branch point. If 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. Optionally, the polyethylene terephthalate can be substituted, preferably with a Ci to Cio alkyl group, a hydroxyl, and/or an amine group. According to one embodiment, the polyethylene 20 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.
Depending on its processing and thermal history, PET may exist both as an 25 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. WO 2014/102197 PCT/EP2013/077742 - 12-
According to one embodiment, 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 5 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). 10 According to one embodiment of the present invention, 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.
According to another embodiment of the present invention, the polyethylene 15 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.
According to one embodiment of the present invention, the polyethylene terephthalate has a number average molecular weight from 5000 to 100000 g/mol, 20 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 25 consumed PET bottles, preform PET scrap, regrained PET, or reclaimed PET. WO 2014/102197 PCT/EP2013/077742 - 13-
According to one embodiment, 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. 5 According to one embodiment, 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.
According to one embodiment, the at least one polymer comprises further polymers, 10 preferably polyolefines, polyamides, cellulose, polybenzimidazols, or mixtures thereof, or copolymers thereof. Examples for such polymers are polyhexamethylene diadipamide, polycaprolactam, aromatic or partially aromatic polyamides (“aramids”), nylon, polyphenylene sulfide (PPS), polyethylene, polypropylene, polybenzimidazols, or rayon. 15
According to one embodiment, 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. 20
The at least one filler
According to the present invention, the nonwoven fabric comprises at least one filler 25 comprising a calcium carbonate. The at least one filler is dispersed within the at least one polymer. WO 2014/102197 PCT/EP2013/077742 - 14-
The use of at least one filler comprising calcium carbonate in polyester-based nonwoven fabrics has certain advantages compared to conventional nonwoven fabrics. For example, the hydrophobic or hydrophilic properties of the nonwoven web can be adapted to the intended application by using an appropriate calcium 5 carbonate filler. Furthermore, 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. Moreover, the inventors surprisingly found that if calcium carbonate is added as filler to PET, the polymer exhibits a higher thermal conductivity, which leads to a faster cooling rate of the polymer. 10 Furthermore, without being bound to any theory it is believed that calcium carbonate acts as nucleating agent for PET, and thus, increases the crystallization temperature of PET. As a result the crystallization rate is increased, which, for example, allows shorter cycling times during melt processing. The inventors also found that nonwoven webs manufactured from PET including calcium carbonate fillers have an 15 improved soft touch and a higher stiffness compared to nonwoven webs made from PET only.
According to one embodiment, the calcium carbonate is ground calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface-treated calcium 20 carbonate, or a mixture thereof. Preferably the calcium carbonate is surface-treated calcium carbonate.
Ground (or natural) calcium carbonate (GCC) is understood to be a naturally occurring form of calcium carbonate, mined from sedimentary rocks such as 25 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 WO 2014/102197 PCT/EP2013/077742 - 15- 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” 5 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, alumino silicate etc. 10 According to one embodiment of the present invention the source of ground calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone, or mixtures thereof. Preferably, the source of ground calcium carbonate is selected from marble. According to one embodiment of the present invention the GCC is obtained by dry grinding. According to another embodiment of the present invention the GCC 15 is obtained by wet grinding and subsequent drying. “Precipitated calcium carbonate” (PCC) 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 20 and carbonate ion source in water or by precipitation of calcium and carbonate ions, for example CaCl2 and Na2CC>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 25 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 WO 2014/102197 PCT/EP2013/077742 - 16- 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. 5
According to one embodiment of the present invention, the calcium carbonate comprises one precipitated calcium carbonate. According to another embodiment of the present invention, the calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and 10 different polymorphs of precipitated calcium carbonate. For example, 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 15 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. In a next step, the calcium carbonate is treated with gaseous carbon dioxide. If a strong 20 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. Surface-reacted calcium carbonates are described, for example, in US 2012/0031576 Al, WO 2009/074492 Al, EP 2 264 109A1,EP2 070 991 Al,or EP 2 264 108 Al. 25 A surface-treated calcium carbonate may feature a GCC, PCC, or MCC comprising a treatment or coating layer on its surface. For example, the calcium carbonate may be treated or coated with a hydrophobising surface treatment agent such as, e.g., WO 2014/102197 PCT/EP2013/077742 - 17- aliphatic carboxylic acids, salts or esters thereof, or a siloxane. Suitable aliphatic acids are, for example, C5 to C28 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 5 polydiallyldimethylammonium chloride (polyDADMAC). Surface-treated calcium carbonates are, for example, described in EP 2 159 258 Al.
According to one embodiment, the modified calcium carbonate is a surface-reacted calcium carbonate, preferably obtained from the reaction with sulphuric acid, 10 hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or a mixture thereof, and carbon dioxide.
According to another embodiment, the surface-treated calcium carbonate comprises a treatment layer or surface coating obtained from the treatment with fatty acids, their 15 salts, their esters, or combinations thereof, preferably from the treatment with aliphatic C5 to C28 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. 20 According to one embodiment, the calcium carbonate has an average particle size dso from 0.1 to 3 pm, preferably from 0.4 to 2.5 pm, more preferably from 1.0 to 2.3 pm, and most preferably from 1.2 to 1.8 pm. In addition or alternatively, the calcium carbonate has an top cut particle size d<m from 1 to 10 pm, preferably from 5 to 8 pm, more preferably from 4 to 7 pm, and most preferably from 6 to 7 pm. 25
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 WO 2014/102197 PCT/EP2013/077742 - 18- 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. 5 According to one embodiment, 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. According to another embodiment, the calcium carbonate is dispersed within the at least one polymer and is present in an amount from 0.5 to 10 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.
According to one embodiment, the at least one filler consists of calcium carbonate. The calcium carbonate may consist of only one specific type of calcium carbonate or 15 a mixture of two or more types of calcium carbonates.
According to another embodiment, the at least one filler comprises further mineral pigments. Examples for further pigment particles comprise silica, alumina, titanium dioxide, clay, calcined clays, talc, kaolin, calcium sulphate, wollastonite, mica, 20 bentonite, barium sulfate, gypsum, or zinc oxide.
According to one embodiment, 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 25 filler. WO 2014/102197 PCT/EP2013/077742 - 19-
According to one embodiment, 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. According to another embodiment, the at least one filler is dispersed within the at 5 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.
According to one aspect of the present invention, the use of calcium carbonate as 10 filler in a nonwoven fabric comprising at least one polymer comprising a polyester is provided. According to another aspect of the present invention, 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. 15 According to one preferred embodiment of the present invention, the use of calcium carbonate as filler in a nonwoven fabric comprising a polyethylene terephthalate is provided. According to another preferred embodiment of the present invention, 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. 20 Preferably, the calcium carbonate is a surface-treated calcium carbonate.
According to a further aspect of the present invention, 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 25 terephthalate, is provided. According to a further aspect of the present invention, the use of calcium carbonate as filler in a nonwoven fabric fiber, filament and/or filmlike filamentary structure comprising at least one polymer comprising a polyester, WO 2014/102197 PCT/EP2013/077742 -20- preferably a polyethylene terephthalate, is provided, wherein the filler is dispersed within at least one polymer. 5 The nonwoven fabric 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. 10
According one aspect of the present invention a 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. 15 According to one embodiment, 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. According to another embodiment 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, 20 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 pm, preferably from 5 to 35 pm. Furthermore, the fibers and/or filaments can have any cross-section shape, e.g., a circular, oval, rectangular, dumpbell-shaped, kidney-shaped, triangular, 25 or irregular. The fibers and/or filaments can also be hollow and/or bi-component and/or tri-component fibers. WO 2014/102197 PCT/EP2013/077742 -21 -
In addition to the at least one polymer and the at least one filler, 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 5 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. 10
According to one embodiment, 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 15 comprising calcium carbonate. According to still another embodiment, the nonwoven fabric consists of a polyethylene terephthalate and calcium carbonate.
According to an exemplary embodiment, 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 20 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.-%. According to another exemplary embodiment, the nonwoven 25 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. According to still another exemplary embodiment, the nonwoven fabric consists of 80 wt.-% of a polyester, preferably a WO 2014/102197 PCT/EP2013/077742 -22- polyethylene terephthalate, and 20 wt.-% calcium carbonate, preferably a ground calcium carbonate, based on the total weight of the nonwoven fabric.
According to one aspect of the present invention, a process for producing a 5 nonwoven fabric is provided comprising the steps of a) providing a mixture of at least one polymer comprising a polyester and at least one filler comprising calcium carbonate, b) forming the mixture into fibers, filaments and/or film-like filamentary structures, and 10 c) forming a nonwoven fabric from the fibers, filaments and/or film-like filamentary structures.
According to a preferred embodiment, the polyester is a polyethylene terephthalate and/or the calcium carbonate is surface-treated calcium carbonate. 15
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. For example, the at least one polymer and the at least one filler may be dry blended, melt blended and optionally formed 20 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.
According to one embodiment, in step b) the mixture is formed into fibers, preferably 25 by an extrusion process, and more preferably by a melt blown process, a spunbond process, or a combination thereof. However, any other suitable process known in the art for forming polymers into fibers may also be used. WO 2014/102197 PCT/EP2013/077742 -23-
Any melt blown process, spunbond process, or a combination thereof, known in the art may be employed to form the mixture of at least one polymer and at least one filler into fibers. For example, melt blown fibers may be produced by melting the mixture, extruding the mixture through a die or small orifices to form fibers, and 5 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. In a spundbond process, 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 10 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. 15 Two typical spunbond processes are known in the art as the Lurgi process and the Reifenhauser process. 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. 20 The Reifenhauser 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 25 orientation and affect crystallinity. This may result in a reduction in diameter and an improvement in physical properties. WO 2014/102197 PCT/EP2013/077742 -24-
According to one embodiment of the present invention, in step b) the mixture is formed into fibers by combining a melt blown process and a spunbond process.
By combining a meltblown and a spunbond process, a multilayer nonwoven fabric 5 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 10 process. In such described laminate fabrics, the layers are generally at least partially consolidated by one of the optional bonding methods described further below.
The nonwoven fabric produced by the inventive process can be a multilayered nonwoven fabric, preferably a spundbonded-meltblown-spunbonded (SMS), a 15 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, 20 by lamination.
According to one embodiment, 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 25 (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. WO 2014/102197 PCT/EP2013/077742 -25-
According to one embodiment, in step c) the nonwoven fabric is formed by collecting the fibers on a surface or carrier. For example, the fibers can be collected on a foraminous surface such as a moving screen or a forming wire. The fibers may 5 be randomly deposited on the foraminous surface so as to form a sheet, which may be held on the surface by a vacuum force.
According to an optional embodiment of the inventive process, the obtained nonwoven fabric is subjected to a bonding step. Examples of bonding methods 10 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. 15 Various patterns can be used in the process of the present invention without affecting the mechanical properties of the web. For instance, 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. Optionally, binding agents, adhesives, or other chemicals may be added during the binding step. 20
According to another optional embodiment of the inventive process, the obtained nonwoven fabric is subjected to a post-treatment step. Examples for post-treatment processes are direction orientation, creping, hydroentanglement, or embossing processes. 25
According to one aspect of the present invention the use of fibers for the manufacture of a non-woven fabric is provided, wherein the fibers comprise at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. WO 2014/102197 PCT/EP2013/077742 -26-
According to one preferred embodiment of the present invention the use of fibers for the manufacture of a non-woven fabric is provided, wherein the fibers comprise at least one polymer comprising a polyethylene terephthalate and at least one filler comprising calcium carbonate. 5
According to another aspect of the present invention 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 polyester and at least one filler comprising calcium carbonate. According to another preferred 10 embodiment of the present invention 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. 15 The nonwoven fabric of the present invention can be used in many different applications. According to one aspect of the present invention, 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, 20 packaging materials, cosmetic products, hygiene products, or filtration materials. According to another aspect of the present invention, 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 25 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 WO 2014/102197 PCT/EP2013/077742 -27- 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 5 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 10 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. 15 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 20 clothing, lab coats, sorbents, or flame barriers. Examples of 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. 25
The scope and interest of the invention will be better understood based on the following examples which are intended to illustrate certain embodiments of the present invention and are non-limitative. WO 2014/102197 PCT/EP2013/077742 -28-
Examples 5 1. Measurement methods and materials
In the following, measurement methods and materials implemented in the examples are described. 10 Particle Size
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 15 grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1 wt.-% Na4P2C>7. The samples were dispersed using a high speed stirrer and supersonics.
Intrinsic viscosity 20
The intrinsic viscosity or IV is a measure of the molecular mass of the polymer and is measured by dilute solution viscosimetry. All I Vs were measured in 60/40 ratio by weight ofphenol/tetrachloroethane solution, at 25 C according to ASTM D4603 in a Ubbelohde capillary viscometer. Typically, about 8-10 chips were dissolved to make 25 a solution with a concentration of about 0.5%. WO 2014/102197 PCT/EP2013/077742 -29-
Tensile test
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 5 tensile test are the yield stress, the break-strain, the break-stress, and the e-modulus of the polymer or polymer composition.
Charpy impact test 10 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 x 6 x 6 mm.
Materials 15 Polymer 1: Lighter S98 PET, commercially available from Equipolymers GmbH, Germany.
Intrinsic viscosity: 0.85 ± 0.02; Tg: 78°C; Tm: 247°C; crystallinity: min. 50. 20 Polymer 2: Lighter C93 PET, commercially available from Equipolymers GmbH, Germany.
Intrinsic viscosity: 0.80 ± 0.02; Tg: 78°C; Tm: 247°C; crystallinity: min. 50. 25 Filler: Omyafilm 707-OG (ground calcium carbonate), commercially available from Omya AG, Switzerland.
Particle size dso- 1.6 pm; top cut dgs’. 6 pm. WO 2014/102197 PCT/EP2013/077742 -30- 2. Examples
Example 1 5
Testing samples containing polymer 1 only as well as a composition of 90 wt.-% polymer 1 and 10 wt.-% filler, based on the total weight of the composition, were prepared. 10 The mechanical properties of the testing samples were determined using the tensile test described above at a tension of 5 N with a 500 N tester. The results of the tensile test are shown in Table 1 below.
Sample A (comparative) Sample B (inventive) Amount polymer (wt.-%) 100 90 Amount filler (wt.-%) - 10 Thickness (μπι) 206 205 Yield stress (N/mm2) 55.9 58.8 Break-strain (%) 600 500 Break-stress (N/mm2) 58.2 46.2 E-modulus (N/mm2) 10 064 11 125 15 Table 1: Mechanical properties of samples A and B.
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. Thus, the inventive polymer composition (sample B) had a 20 higher elasticity and softness compared to the pure PET polymer (sample A). This WO 2014/102197 PCT/EP2013/077742 -31 - 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. 5
Example 2
Testing samples containing polymer 2 only as well as compositions of 90 wt.-% polymer 2 and 10 wt.-% filler, and 80 wt.-% polymer 2 and 20 wt.-% filler, based on 10 the total weight of the composition, were prepared.
The mechanical properties of the testing samples were determined using the tensile test described above at a tension of 4 N with a 20 kN tester and the Charpy impact test. The results of the tensile test are shown in Table 2 below.
Sample C (comparative) Sample D (inventive) Sample E (inventive) Amount polymer (wt.-%) 100 90 80 Amount filler (wt.-%) - 10 20 Thickness (mm) 2.09 2.08 2.09 Yield stress (N/mm2) 54.1 55.2 68.2 Break-strain (%) 830 578 242 Break-stress (N/mm2) ~60 ~50 ~35 E-modulus (N/mm2) 2280 2640 3070 Charpy (kJ/m ) notched 2.9 1.6 1.0 r\ Charpy (kJ/m ) unnotched 150 72 62
Table 2: Mechanical properties of samples C, D, and E. WO 2014/102197 PCT/EP2013/077742 -32-
The 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. Thus, the inventive polymer compositions (samples D and E) had a higher elasticity and 5 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. 10
Claims (15)
- Claims1. A nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate.
- 2. The nonwoven fabric of claim 1, wherein 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.
- 3. The nonwoven fabric of claim 1 or 2, wherein 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.
- 4. The nonwoven fabric of any one of the foregoing claims, wherein 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.
- 5. The nonwoven fabric of any one of the foregoing claims, wherein the calcium carbonate has an average particle size dso from 0.1 to 3 pm, preferably from 0.4 to 2.5 pm, more preferably from 1.0 to 2.3 pm, and most preferably from 1.2 to 1.8 pm.
- 6. The nonwoven fabric of any one of the foregoing claims, wherein the calcium carbonate has an top cut particle size dgs from 1 to 10 pm, preferably from 5 to 8 pm, more preferably from 4 to 7 pm, and most preferably from 6 to 7 pm.
- 7. The nonwoven fabric of any one of the foregoing claims, wherein 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.
- 8. A process for producing a nonwoven fabric comprising the steps of a) providing a mixture of at least one polymer comprising a polyester and at least one filler comprising calcium carbonate, b) forming the mixture into fibers, filaments and/or film-like filamentary structures, and c) forming a nonwoven fabric from the fibers, filaments and/or film-like filamentary structures.
- 9. The process of claim 8, wherein in 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.
- 10. The process of claim 9, wherein the nonwoven fabric is formed by collecting the fibers on a surface or carrier.
- 11. The process of any one of claims 8 to 10, wherein 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.
- 12. Use of calcium carbonate as filler in a nonwoven fabric comprising at least one polymer comprising a polyester.
- 13. 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.
- 14. Use of a nonwoven fabric according to any one of claims 1 to 7 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.
- 15. An article comprising the nonwoven fabric according to any one of claims 1 to 7, 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.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
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| EP12199746.4A EP2749679B1 (en) | 2012-12-28 | 2012-12-28 | CaCO3 in polyester for nonwoven and fibers |
| EP12199746.4 | 2012-12-28 | ||
| US201361748779P | 2013-01-04 | 2013-01-04 | |
| US61/748,779 | 2013-01-04 | ||
| PCT/EP2013/077742 WO2014102197A1 (en) | 2012-12-28 | 2013-12-20 | Caco3 in polyester for nonwoven and fibers |
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| AU2013369411B2 true AU2013369411B2 (en) | 2016-12-22 |
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| US10717674B2 (en) | 2010-04-27 | 2020-07-21 | Biomason, Inc. | Methods for the manufacture of colorfast masonry |
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