ES2629257T3 - CaCO3 in polyester for nonwovens and fibers - Google Patents

Abstract

A nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight , based on the total weight of the nonwoven fabric, and wherein the nonwoven fabric comprises at least one polymer and at least one filler in the form of fibers and / or filaments having a diameter of 0.5 to 40 µm, and in Polyester is a polyethylene terephthalate and calcium carbonate has an average particle size d50 of 1.2 to 1.8 µm and a higher cut particle size d98 of 4 to 7 µm.

Description

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DESCRIPTION

CaCO3 in polyester for nonwovens and fibers

The invention relates to a nonwoven fabric, a method 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 net structures made by bonding fibers or filaments. They can be flat or bulky and, depending on the procedure by which they are produced and the materials used, can be adapted for a variety of applications. In contrast to other textiles such as fabrics or knits, nonwoven fabrics do not need to go through the preparatory stage of yarn spinning in order to be transformed into a net of a certain pattern. Depending on the strength of the material necessary for specific use, it is possible to use a certain percentage of recycled fabrics on the nonwoven fabric. On the contrary, some non-woven fabrics can be recycled after use, given the proper treatment and facilities. Therefore, nonwoven fabrics can be the most 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.

Today, nonwoven fabrics are mainly produced from thermoplastic polymers such as polypropylene, polyethylene, polyamides or polyester. The advantage of polyester fibers or filaments is their high crystallinity, high strength and high toughness. Polyethylene terephthalate (PET) is the most used polyester class and is characterized by its high modulus, low shrinkage, thermal stability, light resistance and chemical resistance, which explains the great versatility of PET. A 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 concentrators and, therefore, can affect the mechanical properties of the polymer. Consequently, nucleated PET is often reinforced with glass fibers.

A talc-filled PET was reported in the article by Sekelik et al. entitled "Oxygen barrier properties of crystallized and talc-filled poly (ethylene terephthalate)" published in the Journal of Polymer Science: Part B: Polymer Physics, 1999, 37, 847-857.

US 5,886,088 A refers to a composition of PET resin comprising an inorganic nucleating agent. In WO 2009/121085 A1 a method for producing a thermoplastic polymeric material, which is filled with calcium carbonate, is disclosed. WO 2012/052778 A1 relates to tear-off polymer films comprising polyester or calcium carbonate or mica fillers. PET fiber spinning containing modified calcium carbonate was studied by Boonsri Kusktham and was described in the article entitled "Spinning of PET fibers 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 mineral filler are disclosed in US 6,797,377 B1. WO 2008/077156 A2 describes spun fibers comprising a polymeric resin and a 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. The prior art can also be found in WO2008 / 077156. In view of the above, the improvement of the properties of nonwoven fabrics based on polyester remains of interest to the expert.

An objective of the present invention is to provide a non-woven fabric that has an improved soft touch and a higher stiffness. It would also be desirable to provide a nonwoven fabric that can be adapted with respect to its hydrophobic or hydrophilic properties. It would also be desirable to provide a nonwoven fabric containing a reduced amount of polymer without significantly affecting the quality of the nonwoven fabric.

It is also an object of the present invention to provide a process for producing a nonwoven fabric from a polymer 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 that allows the use of recycled polyester, especially recycled PET.

The above and other objectives are resolved by the object as defined herein in the independent claims.

In accordance with one aspect of the present invention, a nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based on the total weight of the nonwoven fabric, and in which the nonwoven fabric comprises at least one polymer and at least one filling in the form of fibers and / or filaments that they have a diameter of 0.5 to 40 pm, and in which the polyester is a polyethylene terephthalate, and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and a particle size of superior cut dgs of 4 to 7 pm

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According to another aspect, the present invention provides a method 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) form the mixture in fibers and / or filaments having a diameter of 0.5 to 40 pm, and

c) forming a nonwoven fabric from the fibers and / or filaments, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based on the total weight of the fabric non-woven, in which the polyester is a polyethylene terephthalate and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and an upper cut particle size d98 of 4 to 7 pm.

In accordance with yet another aspect, the present invention provides an article comprising the inventive nonwoven textile, wherein said article is selected from construction products, consumer clothing, industrial clothing, medical products, articles for the household, protection products, packaging materials, cosmetic products, hygiene products, or filtration materials.

In accordance with yet another aspect, the present invention provides the use of calcium carbonate as a filler in a nonwoven fabric comprising at least one polymer comprising a polyester, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based on the total weight of the nonwoven fabric, and in which the nonwoven fabric comprises at least one polymer and at least one filling in the form of fibers and / or filaments having a diameter of 0.5 to 40 pm, and in which the polyester is a polyethylene terephthalate, and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and a larger cut particle size d98 of 4 to 7 p.m.

In accordance with yet another aspect, the present invention provides the use of fibers for the manufacture of a nonwoven fabric, in which the fibers comprise at least one polymer comprising a polyester and at least one filler material comprising calcium carbonate , and in which the polyester is a polyethylene terephthalate, and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm, and an upper cut particle size d98 of 4 to 7 pm.

In accordance with yet another aspect, the present invention provides the use of inventive nonwoven fabric in construction products, waterproofing, thermal insulation, soundproofing, roofing, consumer clothing, upholstery and confection, industrial garments, medical products , household items, protective products, packaging materials, cosmetic products, hygiene products or filtration materials.

Advantageous embodiments of the present invention are defined in the corresponding subclaims.

According to one embodiment, the polyester has a nominal average molecular weight of 5,000 to 100,000 g / mol, preferably 10,000 to 50,000 g / mol, and more preferably 15,000 to 20,000 g / mol.

According to one embodiment, the calcium carbonate is crushed calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or a mixture thereof, preferably surface treated calcium carbonate. According to another embodiment, calcium carbonate has a d98 upper cut particle size from 6 to 7 pm. According to yet another embodiment, calcium carbonate is present in the nonwoven fabric in an amount of 0.2 to 40% by weight, and preferably 1 to 35% by weight, based on the total weight of the nonwoven fabric.

According to an embodiment of the inventive process, in step b) the mixture is formed in fibers, preferably by an extrusion process, and more preferably by a blow-melt process, a spin-join process or a combination of the same. According to another embodiment of the inventive process, the nonwoven fabric is formed by collecting the fibers on a surface or support. According to yet another embodiment of the inventive process, steps b) and c) are repeated two or more times to produce a multilayer nonwoven fabric, preferably a spunblown-meltblown spunbond (SMS) , a meltblown-spunblow-meltblown joint (MSM), a spunblown-meltblown-meltblown-meltblown (SMSM), a meltblown-spunblownblown by melt-spunbond (MSMs), one spunblow-meltblown-meltblown-spunblown (SMMS), or one meltblown-spunbond-meltblown-meltblown MSSM).

It should be understood that for the purposes 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, relates to the fraction of the molecules ordered in a polymer. The remaining fraction is designated as "amorphous." The polymers can crystallize after cooling the melt, mechanical stretching or evaporation of the solvent. Crystalline areas are generally more densely packed than amorphous areas, and crystallization can affect the optical, mechanical, thermal and chemical properties of the polymer. The degree of crystallinity is specified in percentage and can be determined by differential scanning calorimeter (DSC).

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"Ground calcium carbonate" (GCC) within 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 wet treatment. dry such as crushing, and / or fractionation, for example by a cyclone or sorter.

The term "intrinsic viscosity" as used in the context of the present invention is a measure of the ability of a polymer in solution to improve the viscosity of the solution and is specified in dl / g.

"Modified calcium carbonate" (MCC) within the meaning of the present invention may have a crushed or precipitated natural calcium carbonate with a modification of internal structure or a surface reaction product, that is, "surface reacted calcium carbonate ". A "surface reaction calcium carbonate" is a material comprising calcium carbonate and insoluble calcium salts, preferably at least partially crystalline, of surface acid anions. Preferably, the insoluble calcium salt extends from the surface of at least a portion of the calcium carbonate. The calcium ions that form 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.

For the purpose of the present invention, the term "non-woven fabric" relates to a flat, flexible and porous sheet structure that is produced by interconnection layers or networks of fibers, filaments or filamentary structures similar to films.

Throughout this document, the "particle size" of a calcium carbonate filler is described by its distribution of particle sizes. The value dx represents the diameter with respect to which x% by weight of the particles have diameters smaller than dx. This means that the value of d20 is the particle size in which 20% by weight of all particles is smaller and the value of d98 is the size of particle at which 98% by weight of all particles is smaller. The value d98 is also designated as "upper cut". The value of d50 is, therefore, the weighted average particle size, that is, 50% by weight of all grains are larger or smaller than this particle size. For the purpose of the present invention, the particle size is specified as the weighted medium particle size d50 unless otherwise indicated. To determine the d50 value of the weighted average particle size or the d98 value of the upper cut particle size, a Sedigraph 5100 or 5120 device from Micromeritics, USA can be used.

As used herein, the term "polymer" generally includes homopolymers and copolymers such as, for example, block copolymers, grafts, random and alternating, as! as mixtures and modifications thereof

The "precipitated calcium carbonate" (PCC) within the meaning of the present invention is a synthesized material, generally obtained by precipitation after a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous medium or by precipitation of a calcium and a source of carbonate in water. Additionally, precipitated calcium carbonate can also be the product of the introduction of calcium and carbonate salts, calcium chloride and sodium carbonate, for example, in an aqueous medium. The PCC can 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 the unpublished European patent application no. 12 164 041.1.

Within 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, for example a layer of fatty acids, surfactants, siloxanes or polymers.

When 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 "compound of". If a group is defined below to comprise at least a certain number of embodiments, this should also be understood to disclose a group, which preferably consists solely of these embodiments.

When an indefinite or defined article is used when referring to a singular name, for example "a / a", "a / a" or "he / she", this includes a plural of that noun unless another is indicated thing specifically.

Terms such as "obtainable" or "definable" and "obtained" or "defined" are used interchangeably. This, for example, indicates that, unless the context clearly indicates otherwise, the term "obtained" does not mean that, for example, an embodiment must be obtained by for example the sequence of steps following the term "obtained", although such an understanding Limited is always included by the terms "obtained" or "defined" as a preferred embodiment.

The nonwoven fabric of the invention 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 established in more detail. It should be understood that these technical details and embodiments also apply to the inventive process for producing said nonwoven fabric and to the inventive use of the nonwoven fabric, fibers, compositions and calcium carbonate.

The at least one polymer

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The nonwoven fabric of the present invention comprises at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate.

Polyesters are a class of polymers that contain the ester functional group in their main chain and are generally obtained by a polycondensation reaction. Polyesters can include naturally occurring polymers such as cutin, as! as synthetic polymers such as polycarbonate or polybutyrate. Depending on their structure, polyester can be biodegradable.

Examples of a polyester are a polyglycolic acid, a polycaprolactone, a polyethylene adipate, a polyhydroxyalkanoate, a polyhydroxybutyrate, a polytrimethylene terephthalate, a polybutylene terephthalate, a polyethylene naphthalate, a polymethyl acid or a copolytic acid or a mixture thereof thereof. Any of these polymers may be in pure form, that is to say in the form of a homopolymer, or it may be modified by copolymerization and / or by adding one or more substituents to the main chain or side chains of the main chain.

According to an 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 polyester.

The at least one polymer may be present in the nonwoven fabric in an amount of at least 40% by weight, preferably at least 60% by weight, more preferably at least 80% by weight, and most preferably at least 90% by weight, 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 of 50 to 99% by weight, preferably 60 to 98% by weight, and more preferably 65 to 95% by weight, in based on the total weight of the nonwoven fabric.

In accordance with the present invention, the polyester is a polyethylene terephthalate.

Polyethylene terephthalate (PET) is a condensation polymer and can be produced industrially by condensing either terephthalic acid or dimethyl terephthalate with ethylene glycol.

PET can be polymerized by ester exchange using diethyl terephthalate monomers and ethylene glycol or direct esterification using terephthalic acid and ethylene glycol monomers. Both the ester exchange and direct esterification procedures are combined with polycondensation steps either discontinuously or continuously. Discontinuous systems require two reaction vessels; one for esterification or ester exchange and another for polymerization. Continuous systems require at least three vessels; one for esterification or exchange of esters, another to reduce excess glycols and yet another for polymerization.

Alternatively, PET can be produced by solid phase polycondensation. For example, in such a procedure a polycondensation in the molten state is continued until the prepolymer has an intrinsic viscosity of 1.0 to 1.4 dl / g, at which time the polymer is poured into a solid film. The pre-crystallization is carried out by heating, for example above 200 ° C, until the desirable molecular weight of the polymer is obtained.

According to one embodiment, the PET is obtained from a continuous polymerization process, a batch polymerization process or a solid phase polymerization process.

In accordance with the present invention, the term "polyethylene terephthalate" comprises unmodified and modified polyethylene terephthalate. The polyethylene terephthalate can be a linear polymer, a branched polymer or a crosslinked polymer. For example, if glycerol is allowed to react with a diacid or anhydride, each glycerol will generate a ramification point. If the internal coupling occurs, for example, by reaction of a hydroxyl group and an acid function of branches in the same or different molecule, the polymer will be crosslinked. Optionally, the polyethylene terephthalate can be substituted, preferably with a Ci to C10 alkyl group, a hydroxyl and / or amine group. According to one embodiment, the polyethylene terephthalate is substituted with a methyl, ethyl, propyl, butyl, tert-butyl, hydroxyl and / or amine group. Polyethylene terephthalate can also be modified by copolymerization, for example, with cyclohexane dimethanol or isophthalic acid.

Depending on its treatment and thermal history, PET can exist as both an amorphous and semi-crystalline polymer, that is, as a polymer comprising crystalline and amorphous fractions. The semi-crystalline material may appear transparent or opaque and white depending on its crystalline structure and particle size.

According to one embodiment, 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 yet another embodiment, polyethylene terephthalate has a degree of crystallinity of 10 to 80%, more preferably 20 to 70% and more preferably 30 to 60%. The degree of crystallinity can be measured with differential scanning calorimeter (DSC).

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According to an embodiment of the present invention, polyethylene terephthalate has an intrinsic viscosity, IV, of 0.3 to 2.0 dl / g, preferably 0.5 to 1.5 dl / g, and more preferably 0.7 to 1.0 dl / g.

According to another embodiment of the present invention, the polyethylene terephthalate has a glass transition temperature, Tg, of 50 to 200 ° C, preferably 60 to 180 ° C, and more preferably 70 to 170 ° C.

According to an embodiment of the present invention, polyethylene terephthalate has a nominal average molecular weight of 5000 to 100,000 g / mol, preferably 10,000 to 50,000 g / mol, and more preferably 15,000 to 20,000 g / mol.

The polyethylene terephthalate can be a virgin polymer, a recycled polymer, or a mixture thereof. A recycled polyethylene terephthalate can be obtained from subsequently consumed PET bottles, pieces of preform PET, twisted PET or recovered PET.

According to one embodiment, polyethylene terephthalate includes 10% by weight, preferably 25% by weight, more preferably 50% by weight, and most preferably 75% by weight of recycled PET, based on the total amount of terephthalate of polyethylene.

According to one embodiment, the at least one polymer consists of a polyethylene terephthalate. The PET may consist of a single specific type of PET or a mixture of two or more types of PET.

According to one embodiment, the at least one polymer comprises other polymers, preferably polyolefins, polyamides, cellulose, polybenzimidazoles or mixtures thereof, or copolymers thereof. Examples of such polymers are polyhexamethylene diadipamide, polycaprolactam, aromatic or partially aromatic polyamides ("aramides"), nylon, polyphenylene sulfide (PPS), polyethylene, polypropylene, polybenzimidazoles or rayon.

According to one embodiment, the at least one polymer comprises at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of a terephthalate of polyethylene, based on the total amount of the at least one polymer.

The at least one fill

In accordance with the present invention, the nonwoven fabric comprises at least one padding comprising a calcium carbonate, in which the calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based to the total weight of the nonwoven fabric, and has an average particle size d50 of 1.2 to 1.8 pm, and a larger cut particle size d98 of 4 to 7 pm. 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. For example, the hydrophobic or hydrophilic properties of the nonwoven web can be adapted to the intended application by using an appropriate calcium carbonate filler. Additionally, the use of calcium carbonate fillers allows the reduction of polyester in the production of nonwoven fabrics without significantly affecting the quality of the nonwoven material. In addition, the inventors surprisingly found that if calcium carbonate is added as a filler to PET, the polymer exhibits a higher thermal conductivity, which leads to a faster cooling rate of the polymer. In addition, without being bound to any theory, it is believed that calcium carbonate acts as a nucleating agent for PET, and therefore, increases the crystallization temperature of PET. As a result, the crystallization rate is increased, which, for example, allows shorter cycling times during fusion processing. The inventors also found that non-woven nets made from PET that include calcium carbonate fillers have an improved soft touch and higher stiffness compared to non-woven bands made of PET only.

According to one embodiment, the calcium carbonate is ground calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or a mixture thereof. Preferably, the calcium carbonate is surface treated calcium carbonate.

It is understood that ground (or natural) carbonate (GCC) is a naturally occurring form of calcium carbonate, extracted from sedimentary rocks such as limestone or chalk, or metamorphic marble rocks. It is known that calcium carbonate exists as three types of crystalline polymorphs: calcite, aragonite and vaterite. Calcite, the most common crystalline polymorph, is considered to be the most stable crystalline form of calcium carbonate. Less common is aragonite, which has a discrete or agglomerated orthromromic crystal structure. Vaterite is the rarest polymorphic calcium carbonate and is generally unstable. The ground calcium carbonate is almost exclusively from the calcium polymorph, which is said to be trigonalrhomboedrico and represents the most stable of the calcium carbonate polymorphs. The term "source" of calcium carbonate within the meaning of the present application refers to the naturally occurring mineral material from which calcium carbonate is obtained. The calcium carbonate source may comprise other naturally occurring components such as magnesium carbonate, aluminum silicate, etc.

According to an 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

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Ground calcium carbonate is selected from marble. According to an embodiment of the present invention, the GCC is obtained by dry grinding. In accordance with another embodiment of the present invention, the GCC is obtained by wet milling and subsequent drying.

"Precipitated calcium carbonate" (PCC) within the meaning of the present invention is a synthesized material, generally obtained by precipitation after reaction of carbon dioxide and lime in an aqueous medium or by precipitation from a source of calcium and carbonate ions in water or by precipitation of calcium and carbonate ions, for example CaCl2 and Na2CO3, from the solution. Other possible ways to produce PCC are the lime soda procedure, or the Solvay procedure in which PCC is a byproduct 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 scalding (S-PCC), rhombohedral (R-PCC), hexagonal prism, pinacoidal, colloidal (C-PCC), cubic and prismatic (P-PCC). Aragonite is an orthromromic structure with typical crystal habits of twin hexagonal prismatic crystals, as! as a diverse variety of fine elongated, curved prisms, sheer pyramids, chisel-shaped crystals, branched tree and coral or worm-shaped. The vaterite belongs to the hexagonal crystal system. The PCC suspension obtained can be dried and mechanically dried.

According to an embodiment of the present invention, calcium carbonate comprises a precipitated calcium carbonate. According to another embodiment of the present invention, calcium carbonate comprises a mixture of two or more precipitated calcium carbonates selected from different crystalline forms and different polymorphs of the precipitated calcium carbonate. For example, the at least one precipitated calcium carbonate may comprise a PCC selected from S-PCC and a PCC selected from R-PCC.

A modified calcium carbonate may have a GCC or PCC with an internal structure modification or a GCC or PCC with superficial reaction. A surface reaction calcium carbonate can be prepared by providing a GCC or PCC in the form of an aqueous suspension, and adding an acid to said suspension. Suitable acids are, for example, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or a mixture thereof. In a next step, calcium carbonate is treated with gaseous carbon dioxide. If a strong acid such as sulfuric acid or hydrochloric acid is used for the acid treatment step, the carbon dioxide will automatically form in situ. Alternatively or additionally, carbon dioxide can be supplied from an external source. Calcium carbonates reacted on the surface are described, for example, in US 2012/0031576 A1, WO 2009/074492 A1, EP 2 264 109 A1, EP 2 070 991 A1 or EP 2 264 108 A1.

A surface treated calcium carbonate may have a GCC, PCC or MCC comprising a treatment layer or coating on its surface. For example, calcium carbonate can be treated or coated with a hydrophobic surface treatment agent such as, for example, 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, palmetic acid, mirlstic acid, lauric acid or a mixture thereof. Calcium carbonate can also be treated or coated to become cationic or anionic with, for example, a polyacrylate or polydiallyldimethylammonium chloride (polyDADMAC). Surface treated calcium carbonates are described, for example, in EP 2 159 258 A1.

According to one embodiment, the modified calcium carbonate is a surface reaction calcium carbonate, preferably obtained from the reaction with sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid or a mixture thereof and carbon dioxide. carbon.

According to another embodiment, 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 C5 to C28 aliphatic fatty acids, its salts, esters or combinations thereof and more preferably from the treatment with ammonium stearate, calcium stearate, stearic acid, palmetic acid, mirlstic acid, lauric acid or mixtures thereof.

In addition or alternatively, calcium carbonate has a d98 upper cut-off particle size from 6 to 7 pm.

The calcium carbonate may be present in the nonwoven fabric in an amount of 0.2 to 40% by weight, and preferably 1.0 to 35% by weight, based on the total weight of the nonwoven fabric. According to another embodiment, calcium carbonate is present in the nonwoven fabric in an amount of 0.5 to 20% by weight, 1.0 to 10% by weight, 5.0 to 40% by weight, 7.5 to 30% by weight. weight, or 10 to 25% by weight, based on the total weight of the nonwoven fabric.

According to one embodiment, calcium carbonate is dispersed within the at least one polymer and is present in an amount of 0.1 to 50% by weight, preferably 0.2 to 40% by weight, and more preferably 1 to 35% by weight. weight, based on the total weight of the at least one polymer. According to another embodiment, calcium carbonate is dispersed within the at least one polymer and is present in an amount of 0.5 to 20% by weight, 1.0 to 10% by weight, 5.0 to 40% by weight, 7.5 at 30% by weight, or 10 to 25% by weight, based on the total weight of the at least one polymer.

According to one embodiment, the at least one filler consists of calcium carbonate. Calcium carbonate may consist of a single specific type of calcium carbonate or a mixture of two or more types of calcium carbonates.

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According to another embodiment, the at least one filler comprises additional mineral pigments. Examples of other pigment particles include silica, alumina, titanium dioxide, clay, calcined clays, talcum powder, caolln, calcium sulfate, wollastonite, mica, bentonite, barium sulfate, gypsum or zinc oxide.

According to one embodiment, at least one filler material comprises at least 50% by weight, preferably at least 75% by weight, more preferably at least 90% by weight, and most preferably at least 95% by weight of calcium, based on the total amount of at least one filler.

According to one embodiment, at least one filler is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, preferably 0.2 to 40% by weight, and more preferably 1 to 35% by weight, based to the total weight of the nonwoven fabric. According to another embodiment, the at least one filler is dispersed within the at least one polymer and is present in an amount of 1 to 50% by weight, preferably 2 to 40% by weight, and more preferably 5 to 35% by weight, based on the total weight of the at least one polymer.

In accordance with one aspect of the present invention, the use of calcium carbonate, as defined in the claims, is provided as filler in a non-woven fabric comprising at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate. In accordance with another aspect of the present invention, the use of calcium carbonate, as defined in the claims, is provided as a filler in a non-woven fabric, wherein the filler is dispersed within at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate.

According to a preferred embodiment of the present invention, the use of calcium carbonate is provided as a filler in a nonwoven fabric, wherein the filler is dispersed within at least one polymer comprising a polyethylene terephthalate. Preferably, calcium carbonate is a surface treated calcium carbonate.

In accordance with a further aspect of the present invention, the use of calcium carbonate, as defined in the claims, is provided as filler in a filamentous structure of nonwoven fiber, filament and / or film comprising at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate. In accordance with a further aspect of the present invention, the use of calcium carbonate, as defined in the claims, is provided as filler in a filamentous structure of nonwoven fiber, filament and / or film comprising at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate, in which the filler is dispersed within at least one polymer.

Non-woven fabric

A non-woven fabric is a flat, flexible and porous sheet structure that is produced by interconnecting layers or networks of fibers, filaments and / or filamentary structures similar to films.

In accordance with one aspect of the present invention, a filamentary structure of nonwoven fabric fiber, filament and / or film is provided, 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.

According to one embodiment, the nonwoven fabric comprises at least one polymer comprising a polyester, in which the polyester is a polyethylene terephthalate and at least one filler comprising calcium carbonate, as defined in the claims, in the that the at least one filler is dispersed within at least one polymer. According to another embodiment, the non-woven fabric comprises at least one polymer and at least one filler in the form of fibers, filaments and / or filamentary structures similar to films, in which at least one filler is dispersed within the at least one polymer .

In accordance with the present invention, the fibers and / or filaments have a diameter of 0.5 to 40 pm, preferably 5 to 35 pm. In addition, the fibers and / or filaments can have any cross-sectional shape, for example, a circular, oval, rectangular, dumbbell, kidney, triangular or irregular shape. The fibers and / or filaments may also be hollow and / or bicomponent fibers and / or tri-components.

In addition to at least one polymer and at least one filler, the nonwoven fabric may comprise additional additives, for example, waxes, optical brighteners, thermal stabilizers, antioxidants, antistatic agents, anti-blocking agents, colorants, pigments, gloss enhancing agents, surfactants , natural oils or synthetic oils. The nonwoven fabric may also comprise additional 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 non-woven fabric can also be reinforced by reinforcing threads in the form of a textile surface structure, preferably in the form of fabric, laying, knitting, knitting or non-woven fabric.

According to one embodiment, 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 In accordance with yet another embodiment of the present invention, the nonwoven fabric consists of a polyethylene terephthalate and calcium carbonate, as defined in the claims.

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According to an exemplary embodiment, the nonwoven fabric comprises at least one polymer in an amount of 50 to 99% by weight, and the at least one filler in an amount of 1 to 50% by weight, based on the total weight of the nonwoven fabric, preferably the at least one polymer in an amount of 60 to 98% by weight, and the at least one filler in an amount of 2 to 40% by weight, and more preferably the at least one polymer in an amount of 65 to 95% by weight, and the at least one filler in an amount of 5 to 35% by weight. According to another exemplary embodiment, the nonwoven fabric consists of 90% by weight of a polyethylene terephthalate and 10% by weight of calcium carbonate as defined in the claims, preferably a ground calcium carbonate, based to the total weight of the nonwoven fabric. According to another exemplary embodiment, the nonwoven fabric consists of 80% by weight of a polyethylene terephthalate and 20% by weight of calcium carbonate as defined in the claims, preferably a ground calcium carbonate, based to the total weight of the nonwoven fabric.

In accordance with one aspect of the present invention, there is provided 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) form the mixture in fibers and / or filaments having a diameter of 0.5 to 40 pm, and

c) forming a nonwoven fabric from the fibers and / or filaments, in which calcium carbonate is present in the nonwoven fabric in an amount of 01 to 50% by weight, based on the total weight of the fabric non-woven, in which the polyester is a polyethylene terephthalate, and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and an upper cut particle size d98 of 4 to 7 pm.

According to a preferred embodiment, the calcium carbonate is surface treated calcium carbonate.

The mixture of the at least one polymer comprising a polyethylene terephthalate and at least one filler comprising calcium carbonate provided in the 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 can be dry mixed, melt mixed and optionally formed into granules or granules, or a stock mixture of the at least one polymer and the at least one filler can be premixed, optionally formed in granules or pellets, and mixed with additional polymer or filler.

According to one embodiment, in step b) the mixture is formed into fibers, preferably by an extrusion process, and more preferably by a meltblown process, a spinneck process or a combination thereof. However, any other suitable method known in the art can also be used to form fiber polymers.

Any meltblown process, a spin bonding process or a combination thereof, known in the art, can be used to form the mixture of at least one polymer and at least one fiberfill. For example, meltblown fibers can be produced by melting the mixture, extrusion of the mixture through a die or small holes to form fibers and attenuation of polymer fibers melted by hot air. Then the surrounding fresh air can be induced in the hot air stream to cool and solidify the fibers. In a spin bonding process, the mixture can be spun by fusion into fibers by pumping the molten mixture through a multitude of capillaries arranged in a uniform set of columns and rows. After extrusion, the fibers can be attenuated by high speed air. The air creates a stretching force on the fibers that takes them to a desired denier. Spinning process can have the advantage of giving nonwovens greater strength. A second component can be co-extruded in the spin bonding process, which can provide additional properties or bonding capabilities.

Two typical spinning joint procedures are known in the art such as the Lurgi procedure and the Reifenhauser procedure. The Lurgi procedure is based on the extrusion of molten polymer through row holes followed by the newly formed extruded filaments that are cooled with air and suction extracted through Venturi tubes. After formation, the filaments are disbursed on a conveyor belt to form a nonwoven web. The Reifenhauser procedure differs from the Lurgi procedure in that the cooling area for the filaments is sealed, and the cooled air stream accelerates, thus inducing! a more effective drag of the filaments in the air stream.

The fibers formed in the process step b) can be stretched or elongated to induce molecular orientation and affect crystallinity. This can result in a reduction in diameter and an improvement in physical properties.

According to an embodiment of the present invention, in step b) the mixture is formed in fibers combining a meltblown process and a spinneck bonding process.

By combining a meltblowing process and a spunbonding process, for example, a multilayer nonwoven fabric comprising two outer layers of spunbond and an inner layer of meltblown can be produced, which is known in the technique as a nonwoven fabric for spinning-blown bonding

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melt-spun union (SMS). Additionally, either one or both of these procedures can be combined in any arrangement with a carding process of cut fibers or joined fabrics resulting from a carding process of nonwoven cut fibers. In such laminated fabrics described, the layers are generally consolidated at least partially by one of the optional joining methods described below.

The nonwoven fabric produced by the inventive process may be a multilayer nonwoven fabric, preferably a spunbond-meltblown spunbond (SMS), a meltblownbill -blownblownblown. cast (MSM), a spunblow-meltblown-meltblown (SMSM), a meltblown-spunblown-meltblown (MSMS), a bondblown by spin-blow-by-melt-blow-by-melt-join by spinning (SMMS), or one by melt-blow-by-spin-joint by spin-blow-by-melt (MSSM). Said non-woven fabric can be compressed to ensure the cohesion of the layers, for example, 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 spunblown-meltblown spunbond (SMS), one of meltblow-spinning-meltblown bonding (MSM), one of spunbonding-meltblown-spunbonding-meltblown (SMSM), one of meltblown-spunbonding -blownblowing melt-spunbonding (MSMS), a spunbond-meltblown-meltblown-meltblown (SMMS), or a meltblown-spunbond-meltblown-meltblown (MSSM) ).

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 mobile sieve or a training wire. The fibers can be randomly deposited on the foraminous surface to form a sheet, which can be retained on the surface by a vacuum force.

According to an optional embodiment of the inventive process, the nonwoven fabric obtained is subjected to a joining step. Examples of joining methods include thermal point or calendering, ultrasonic bonding, hydro-entangling, agglomeration and airway bonding. Thermal point bonding or calendering is a commonly used method and involves passing the nonwoven fabric to be joined through a heated calendered roller and an anvil roller. The calender roller is generally designed in a certain way so that the entire fabric does not join across its entire surface. Various patterns can be used in the process of the present invention without affecting the mechanical properties of the network. For example, the network can be joined according to a knitted pattern, a wire weave pattern, a diamond pattern and the like. However, any other joining method known in the art can also be used. Optionally, binders, adhesives or other chemical substances can be added during the bonding step.

According to another optional embodiment of the inventive process, the nonwoven fabric obtained is subjected to a post-treatment step. Examples of post-treatment procedures are direction orientation, creping, hydro-entangling or enhancement procedures.

In accordance with one aspect of the present invention, the use of fibers for the manufacture of a nonwoven fabric is provided, in which 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.

In accordance with another aspect of the present invention, the use of a polymeric composition for the manufacture of a nonwoven fabric is provided, wherein the polymeric composition 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. According to one aspect of the present invention, the inventive nonwoven fabric is used in construction products, waterproofing, thermal insulation, acoustic insulation, roofing, consumer clothing, upholstery and confection, industrial clothing, medical products, household items, protection products, packaging materials, cosmetic products, hygiene products or filtration materials. In accordance with another aspect of the present invention, an article is provided comprising the nonwoven fabric of the invention, wherein said article is selected from construction products, consumer clothing, industrial clothing, medical products, household items, protective products, packaging materials, cosmetic products, hygiene products or filtration materials.

Examples of construction products are house wraps, asphalt layers, road and rail beds, golf and tennis courts, wall support coatings, acoustic wall coverings, strikethrough and tile reinforcement materials, floor stabilizers soil and road reinforcements, products for erosion control, canal construction, drainage systems, protection of geomembranes and ice protection products, agricultural mulch, water barriers for ponds and canals, or infiltration barriers

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of sand for drainage tiles. Other examples for construction products are fixings or reinforcements for land fillings.

Examples of consumer clothing are interweaves, insulation of clothing and gloves, bra and shoulder pads, bag components, or shoe components. Examples of industrial clothing are tarpaulins, tents or transport wraps (wood, steel). Examples of medical products are protective clothing, facial masks, isolation gowns, surgical gowns, surgical curtains and covers, surgical suits, caps, sponges, dressings, wipes, orthopedic padding, bandages, ribbons, dental bibs, oxygenators, dialyzers, filters for IV or blood, or transdermal drug delivery components. Examples of home furnishings are pillows, cushions, quilts in quilts or comforters, dust covers, insulators, window treatments, blankets, curtain components, carpet or carpet backs.

Examples of protection products are coated fabrics, reinforced plastic, protective clothing, lab coats, sorbents or flame barriers. Examples of packaging materials are desiccant packaging, sorbent packaging, gift boxes, file boxes, various non-woven bags, book covers, mail envelopes, express envelopes or messenger bags. Examples of filtration materials are gasoline, oil and air filters, including filter liquid cartridges and bag filters, vacuum bags or laminates with nonwoven layers.

The scope and interest of the invention will be better understood based on the following examples that are intended to illustrate certain embodiments of the present invention and are not limiting.

Examples

1. Measuring methods and materials

The measurement methods and materials implemented in the examples are described below.

Particle Size

The distribution of particles of the calcium carbonate filler was measured using a Sedigraph 5120 from Micromeritics, USA. The method and instruments are known to the skilled person and are commonly used to determine the grain size of fillers and pigments. The measurement was carried out in an aqueous solution comprising 0.1% by weight of Na4P2O7. The samples were dispersed using a high speed stirrer and supersonic.

Intrinsic viscosity

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. The measurements were made at 25 ° C with a 0a capillary type and corrected using the Hagenbach correction.

Stress test

The tension test was carried out in accordance with ISO 527-3 using a 1 BA (1: 2) test sample at a speed of 50 mm / min. The properties that were determined through the stress test are the creep limit, the elongation break, the break stress and the polymer modulus e or the polymer composition.

Charpy impact test

The Charpy impact test was carried out in accordance with ISO 179-2: 1997 (E) using notched and notched test samples with a size of 50 3 6 3 6 mm.

materials

Polymer 1: Lighter S98 PET, commercially available from Equipolymers GmbH, Germany. Intrinsic viscosity: 0.85 6 0.02; Tg: 78 ° C; Tm: 247 ° C; crystallinity: min. fifty.

Polymer 2: Lighter C93 PET, commercially available from Equipolymers GmbH, Germany. Intrinsic viscosity: 0.80 6 0.02; Tg: 78 ° C; Tm: 247 ° C; crystallinity: min. fifty.

Filling: Omyafilm 707-OG (ground calcium carbonate), commercially available from Omya AG, Switzerland. Particle size d50: 1.6 mm; Top cut d98: 6 mm.

2. Examples Example 1

Test samples were prepared containing only polymer 1, as! as a composition of 90% by weight of polymer 1 and 10% by weight of filler, based on the total weight of the composition.

The mechanical properties of the test samples were determined using the stress test described above at a voltage of 5 N with a 500 N test device. The results of the stress test are shown in Table 1 below.

Table 1: Mechanical properties of samples A and B.

 Sample A (comparative) Sample B (inventive)

 Amount of polymer (% by weight)

 100 90

 Amount of filling (% by weight)

 - 10

 Thickness (pm)

 206 205

 2 Flow rate (N / mm)

 55.9 58.8

 Elongation break (%)

 600 500

 2 Breaking stress (N / mm)

 58.2 46.2

 Modulus of elasticity (N / mm2)

 10 064 11 125

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Sample B of the invention showed a greater yield strength and modulus of elasticity compared to comparative sample A, while the elongation breakage and the breakage stress of sample B of the invention was reduced. Therefore, the polymeric composition of the invention (sample B) had a higher elasticity and smoothness compared to the pure PET polymer (sample A). This has a positive effect on the haptic properties of nonwoven fabrics produced from such polymeric composition, especially with respect to the softness of the material. For example, such a material is more pleasant to wear.

Example 2

Test samples containing polymer 2 were prepared only as well! as compositions of 90% by weight of polymer 2 and 10% by weight of filler, and 80% by weight of polymer 2 and 20% by weight of filler, based on the total weight of the composition.

The mechanical properties of the test samples were determined using the stress test described above at a tension of 4 N with a 20 kN test device and the Charpy impact test. The results of the traction test are shown in Table 2 below.

 Sample C (comparative) Sample D (inventive) Sample E (inventive)

 Amount of polymer (% by weight)

 100 90 80

 Amount of filling (% by weight)

 - 10 20

 Thickness (mm)

 2.09 2.08 2.09

 Creep Limit (N / mm2)

 54.1 55.2 68.2

 Elongation break (%)

 830 578 242

 Breaking Tension (N / mm2)

 ~ 60 -50 -35

 E-module (N / mm2)

 2280 2640 3070

 Notched according to Charpy (kJ / m2)

 2.9 1.6 1.0

 Without notch according to Charpy (kJ / m2)

 150 72 62

Inventive samples D and E showed a higher yield strength and elastic modulus compared to comparative sample C, while elongation breakage, breakage stress and impact resistance of inventive samples C and D were reduced. . Therefore, the 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 polymeric composition, especially with respect to the softness of the material. For example, such a material is more pleasant to wear.

Claims (12)

5 10 fifteen twenty 25 30 35 40 Four. Five 1. 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 of 0.1 to 50% by weight, based on the total weight of the nonwoven fabric, and in which the nonwoven fabric comprises at least one polymer and at least one filling in the form of fibers and / or filaments having a diameter of 0.5 to 40 pm, and in which the polyester is a polyethylene terephthalate and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and an upper cut particle size d98 of 4 to 7 pm. 2. The non-woven fabric of claim 1, wherein the polyester has a nominal average molecular weight of 5000 to 100,000 g / mol, preferably 10,000 to 50,000 g / mol, and more preferably 15,000 to 20,000 g / mol. 3. The nonwoven fabric of any one of the preceding claims, wherein the calcium carbonate is crushed calcium carbonate, precipitated calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or a mixture thereof , preferably surface treated calcium carbonate. 4. The nonwoven fabric of any one of the preceding claims, wherein the calcium carbonate has a d98 upper cut particle size of 6 to 7 pm. 5. The nonwoven fabric of any one of the preceding claims, wherein the calcium carbonate is present in the nonwoven fabric in an amount of 0.2 to 40% by weight, and preferably 1 to 35% by weight, in based on the total weight of the nonwoven fabric. 6. 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) form the mixture in fibers and / or filaments having a diameter of 0.5 to 40 pm, and c) forming a nonwoven fabric from the fibers and / or filaments, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based on the total weight of the fabric non woven, in which the polyester is a polyethylene terephthalate and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and an upper cut particle size d98 of 4 to 7 pm. 7. The method of claim 6, wherein in step b) the mixture is formed into fibers, preferably by an extrusion process, and more preferably by a meltblown process, a spinneck process or a combination thereof. 8. The method of claim 7, wherein the nonwoven fabric is formed by collecting the fibers on a surface or carrier. 9. The method of any one of claims 6 to 8, wherein steps b) and c) are repeated two or more times to produce a multilayer nonwoven fabric, preferably a spunblown-bonded nonwoven fabric. spunbond-spunbond (SMS), one for meltblown- spunblown-meltblown (MSM), one for spunblow-meltblown -blownblown-meltblown (SMSM), one forblown by melt-spin-blow-by-melt-by-spin connection (MSMS), one by spin-by-blow-by-melt-by-melt-by-spin-joint (SMMS), or by melt-by-melt-by-spin connection spunbond - meltblown (MSSM). 10. Use of calcium carbonate as a filler in a nonwoven fabric comprising at least one polymer comprising a polyester, in which calcium carbonate is present in the nonwoven fabric in an amount of 0.1 to 50% by weight, based on the total weight of the nonwoven fabric, and in which the nonwoven fabric comprises at least one polymer and at least one filling in the form of fibers and / or filaments having a diameter of 0.5 to 40 pm, and in which the polyester is a polyethylene terephthalate, and calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and an upper cut particle size d98 of 4 to 7 pm. 11. Use of fibers for the manufacture of a non-woven fabric, in which the fibers comprise at least one polymer comprising a polyester and at least one filler comprising calcium carbonate and in which the polyester is a polyethylene terephthalate and Calcium carbonate has an average particle size d50 of 1.2 to 1.8 pm and a larger cut particle size d98 of 4 to 7 pm. 12. Use of a non-woven fabric according to any one of claims 1 to 5 in construction products, waterproofing, thermal insulation, soundproofing, roofing, consumer clothing, upholstery and clothing, industrial clothing, medical products , household items, protective products, packaging materials, cosmetic products, hygiene products or filtration materials An article comprising the nonwoven fabric according to any one of claims 1 to 5, wherein This article is selected from construction products, consumer clothing, industrial clothing, medical products, household items, protective products, packaging materials, cosmetics, hygiene products or filtration materials.