KR101846139B1 - Caco3 in polyester for nonwoven and fibers - Google Patents

Abstract

The present invention relates to 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 method of making such a nonwoven and to the use of calcium carbonate as a filler in a nonwoven comprising at least one polymer comprising a polyester.

Description

CACO3 IN POLYESTER FOR NONWOVEN AND FIBERS IN POLYESTER FOR NONWOVENS AND FIBERS

The present invention relates to a nonwoven fabric, a process for producing the nonwoven fabric, articles containing the nonwoven fabric, and uses of the nonwoven fabric, as well as the use of the fibers for the production of nonwoven fabrics and the use of calcium carbonate as a filler for nonwoven fabrics.

Nonwoven fabrics are sheets or web structures made by joining together fibers or filaments. They can be flat or bulky, and can be tailored to a variety of applications depending on the method by which they are made and the materials used. Compared to other textiles such as fabrics or knit fabrics, the nonwoven need not examine the preparation steps of yarn spinning to convert to a specific pattern of web. Depending on the strength of the material required for a particular application, it is possible to use a certain percentage of the recycled fabric in the nonwoven. Conversely, some nonwoven fabrics can be recycled after use if they are given appropriate treatment and equipment. Thus, nonwovens may be a more ecological fabric for certain applications, particularly in disciplines and industries where disposable or single use products are important, such as hospitals, schools or nursing homes.

Today, nonwovens are primarily made from thermoplastic polymers such as polypropylene, polyethylene, polyamide, or polyester. The advantages of polyester fibers or filaments are their high crystallinity, high strength and toughness. Polyethylene terephthalate (PET) is the most widely used polyester and is characterized by high elastic modulus, low shrinkage, heat set stability, light resistance and chemical resistance explaining the great versatility of PET. One of the main disadvantages of PET is its slow crystallization rate, which does not give a reasonable cycle time for manufacturing processes such as injection molding. Nucleating agents such as talc are therefore often added. These inhomogeneous particles, however, can act as stress concentrators, thereby affecting the mechanical properties of the polymer. Thus, nucleated PET is often reinforced with glass fibers.

The talc-filled PET was prepared according to the method described in the Journal of Polymer Science, Part B: Polymer Physics, 1999, 37, 847 to 857, (Sekelik et al., Co-investigator). U.S. Patent No. 5,886,088 A relates to a PET resin composition comprising an inorganic nucleating agent. A process for preparing a thermoplastic polymer material filled with calcium carbonate is described in International Patent Application Publication No. 2009/121085 Al. International Patent Application Publication No. 2012/052778 A1 relates to a tearable polymer film comprising a polyester and a calcium carbonate or mica filler. The spinning of the modified PET fiber containing calcium carbonate was studied by Boonsri Kusktham and published in the Journal of the Asian Journal of Textiles, 2011, 1 (2), 106 to 113, "Spinning of PET fibers mixed with calcium carbonate ".

Extruded fibers and nonwoven webs containing titanium dioxide and one or more mineral fillers are disclosed in U.S. Patent No. 6,797,377 B1. International Patent Application Publication 2008/077156 A2 describes spunlaid fibers comprising a polymeric resin and a filler as well as nonwovens containing said fibers. Nonwoven fabrics of synthetic polymers with improved binding composition are disclosed in European Patent Application No. 2 465 986 A1. WO 97/30199 relates to fibers or filaments which are suitable for the production of nonwoven fabrics, the fibers or filaments consisting essentially of polyolefin and inorganic particles.

In view of the above, it is of interest to those skilled in the art to improve the properties of polyester nonwoven fabrics.

An object of the present invention is to provide a nonwoven fabric with improved soft touch and a greater rigidity. It would also be desirable to provide a nonwoven fabric that can be tailored in terms of hydrophobicity or hydrophilicity of the nonwoven fabric. It would also be desirable to provide a nonwoven fabric containing a reduced amount of polymer without significantly affecting the quality of the nonwoven.

It is also an object of the present invention to provide a polyester-based polymer composition which enables a short cycle time during the melting process, in particular a process for producing a nonwoven from a PET composition. It is also desirable to provide a method for producing a nonwoven fabric which enables the use of recycled polyester, especially recycled PET.

These and other objects are solved by the subject matter defined by the independent claims.

According to one aspect of the present invention, there is provided a nonwoven fabric comprising at least one polymer comprising a polyester, and at least one filler comprising calcium carbonate.

According to another aspect, the present invention provides a method for producing a nonwoven fabric,

a) providing a mixture of at least one polymer comprising a polyester and at least one filler comprising calcium carbonate,

b) molding the mixture into a fiber, filament and / or film-like filament structure, and

c) forming a nonwoven fabric from a fiber, filament and / or film-like filament structure.

According to yet another aspect, the present invention provides an article comprising a nonwoven fabric of the present invention, wherein the article comprises construction products, consumer apparel, industrial apparel, medical supplies, Home furnishings, protective articles, packaging materials, cosmetics, sanitary articles, or filter media.

According to yet another aspect, the present invention provides the use of calcium carbonate as a filler in a nonwoven comprising at least one polymer comprising a polyester.

According to yet another aspect, the present invention provides the use of a fiber for the manufacture of a nonwoven, wherein the fiber comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate.

According to yet another aspect, the present invention provides a method of manufacturing a building material, a waterproofing material, a thermal insulation material, a soundproofing material, a roofing material, a consumer goods apparel, an interior decoration and clothing industry, an industrial apparel, Or the use of the nonwoven fabric of the present invention in a filter medium.

Advantageous embodiments of the invention are defined in the corresponding dependent claims.

According to one embodiment, the polyester is selected from the group consisting of polyglycolic acid, polycaprolactone, polyethylene adipate, polyhydroxyalkanoate, polyhydroxybutyrate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene Naphthalate, polylactic acid, or a mixture thereof, or a copolymer thereof, and preferably the polyester is polyethylene terephthalate. According to another embodiment, the polyester has a number average molecular weight of 5000 to 100000 g / mol, preferably 10000 to 50000 g / mol, and more preferably 15000 to 20000 g / mol.

According to one embodiment, the calcium carbonate is heavy calcium carbonate, light 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 ( d ₅₀ ) of 0.1 to 3 탆, preferably 0.4 to 2.5 탆, more preferably 1.0 to 2.3 탆, and most preferably 1.2 to 1.8 탆. According to yet another embodiment, the calcium carbonate has a top cut particle size ( d ₉₈ ) of from 1 to 10 mu m, preferably from 5 to 8 mu m, more preferably from 4 to 7 mu m, and most preferably, 6 to 7 mu m. According to yet another embodiment, the calcium carbonate is present in the nonwoven in an amount of from 0.1 to 50% by weight, preferably from 0.2 to 40% by weight, and more preferably from 1 to 35% by weight, based on the total weight of the nonwoven.

According to one embodiment of the process of the present invention, the mixture in step b) is preferably subjected to an extrusion process, and more preferably a melt blown process, a spunbond process, As shown in Fig. According to another embodiment of the method of the present invention, the nonwoven fabric is formed by gathering fibers on a surface or a carrier. According to yet another embodiment of the method of the present invention, the steps b) and c) are repeated two or more times to form a multilayer nonwoven fabric, preferably a spunbonded meltblown-spunbonded (SMS) ), Meltblown - spunbonded - meltblown (MSM), spunbonded - meltblown - spunbonded - meltblown (SMSM), meltblown - spunbonded - meltblown - spunborn (MSMS), spunbonded-meltblown-meltblown-spunbonded (SMMS), or meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabrics.

For purposes of the present invention, the following terms are understood to have the following meanings:

The term "crystallinity" as used in the context of the present invention means the fraction of molecules that are regular in the polymer. The remaining fraction is designated "amorphous. &Quot; The polymer can be crystallized upon cooling from the solvent, mechanical stretching or solvent evaporation. The crystallization zone is generally more dense than the amorphous zone, and crystallization can affect the optical, mechanical, thermal and chemical properties of the polymer. The crystallinity is expressed in percent and can be measured by differential scanning calorimetry (DSC).

The term "ground calcium carbonate " (GCC) in the sense of the present invention is obtained from natural sources such as limestone, marble, calcite or chalk and can be obtained by wet and / or dry treatment, such as milling, screening and / For example, calcium carbonate processed by a cyclone or classifier.

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

"Modified calcium carbonate" (MCC) in the sense of the present invention may be characterized as a natural heavy or light calcium carbonate or surface reaction product with a modified internal structure, or "surface reacted calcium carbonate". "Surface-reacted calcium carbonate" is a substance comprising calcium carbonate and a calcium salt insoluble, preferably at least partially crystalline, acid anion on the surface. Preferably, the insoluble calcium carbonate salt extends from the surface of at least a portion of the calcium carbonate. The calcium ions forming the at least partially crystalline calcium salt of the anion are usually derived from a starting calcium carbonate material. The MCC is described, for example, in U.S. Patent Application No. 2012/0031576 A1, International Patent Application Publication No. 2009/074492 A1, European Patent Application No. 2 264 109 Al, European Patent Application No. 2 070 991 Al, 108 A1.

For purposes of the present invention, the term "nonwoven fabric " refers to a flat, flexible, porous sheet structure fabricated by covering a layer or net of fibers, filaments and / or film-like filamentary structures.

Throughout this document, the "particle size" of the calcium carbonate filler is represented by its particle size distribution. Value (d _x) represents the diameter d is less than diameter _x about x% by weight of the particles. This means that the d ₂₀ value is 20% by weight of all particles smaller than the particle size, and the d ₉₈ value means that 98% by weight of all the particles have a smaller particle size. The d ₉₈ value is also designated as a "top cut ". Thus, the d ₅₀ value is the median particle size, i.e. 50 wt% of all particles are larger or smaller than this particle size. For purposes of the present invention, the particle size is specified as the weight median particle size ( d ₅₀ ) unless otherwise specified. A Sedigraph 5100 or 5120 instrument manufactured by Micromeritics, USA may be used to measure the weight median particle size ( d ₅₀ ) value or the top cut particle size ( d ₉₈ ) value.

As used herein, the term "polymer" generally encompasses homopolymers and copolymers such as, for example, blocks, grafts, random and alternating copolymers, and blends and modifications thereof.

In the sense of the present invention, "precipitated calcium carbonate" (PCC) is generally prepared by precipitation after reaction of carbon dioxide with calcium hydroxide (calcium hydroxide) in an aqueous environment or by precipitation of a calcium source and a carbonate source in water Material. In addition, light calcium carbonate may also be a product that introduces calcium salts and carbonates, such as calcium chloride and sodium carbonate, in an aqueous environment. PCC may be batherite, calcite or aragonite. PCC is described, for example, in European Patent Application No. 2 447 213 A1, European Patent Application No. 2,524,898 A1, European Patent Application No. 2 371 766 A1, or unpublished European Patent Application No. 12 164 041.1.

In the sense of the present invention, "surface treated calcium carbonate" is a heavy, hard or modified calcium carbonate comprising a treatment or coating layer, for example a layer of fatty acid, surfactant, siloxane, or polymer.

Where the term "comprising" is used in this specification and claims, it does not exclude other elements. For purposes of the present invention, the term "comprising" is considered to be the preferred embodiment of the term "comprising ". If the group is then defined as including at least a certain number of embodiments, it will also be understood that this also preferably discloses a group consisting only of these embodiments.

(Eg, "a", "an", or "the") is used to mean a singular noun, it includes the plural form of this noun unless something else is specifically mentioned.

The terms "obtainable" or "definable" and "obtained" or "defined" It will be appreciated that, for example, unless the context clearly dictates otherwise, the term "obtained " is intended to encompass all types of matter, for example, Means that the term "obtained" does not intend to indicate that it should be obtained by the following series of steps.

The nonwoven of the present invention comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. The details and preferred embodiments of the products of the invention will now be described in more detail. It will be understood that these technical details and embodiments also apply to the method of the present invention for making the nonwoven fabric and to the use of the present invention for nonwoven fabrics, fibers, compositions, and calcium carbonate.

One or more polymers

The nonwoven fabric of the present invention comprises at least one polymer comprising a polyester.

Polyesters are kinds of polymers containing an ester functional group in their main chain, and are generally obtained by a polycondensation reaction. The polyester may include synthetic polymers such as polycarbonate or polybutyrate, as well as natural polymers such as quisine. Depending on their structure, the polyester may be biodegradable.

According to one embodiment, the polyester is selected from the group consisting of polyglycolic acid, polycaprolactone, polyethylene adipate, polyhydroxyalkanoate, polyhydroxybutyrate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene Naphthalate, polylactic acid, or mixtures thereof, or copolymers thereof. Either of these polymers may be in pure form, i.e. in the form of a homopolymer, or may be modified by copolymerisation and / or by addition of one or more substituents to the main chain or side chains of the main chain.

According to one embodiment of the present invention, the at least one polymer is comprised of a polyester. The polyester may consist of only one particular type of polyester or a mixture of more than one type of polyester.

The one or more polymers may be present in the nonwoven in an amount of at least 40 wt%, preferably at least 60 wt%, more preferably at least 80 wt%, and most preferably at least 90 wt%, based on the total weight of the nonwoven . According to one embodiment, the one or more polymers are present in the nonwoven in an amount of 50 to 99 wt%, preferably 60 to 98 wt%, and more preferably 65 to 95 wt%, based on the total weight of the nonwoven.

According to a preferred embodiment of the present invention, the polyester is polyethylene terephthalate.

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

PET can be polymerized by ester exchange using monomers diethyl terephthalate and ethylene glycol or direct esterification using monomeric terephthalic acid and ethylene glycol. Both the transesterification and direct esterification processes are combined with the polycondensation step either batchwise or continuously. The batch system requires one reaction vessel for esterification or transesterification and one reaction vessel for the polymerization. The continuous system requires at least three vessels, one for the esterification or ester exchange, the other for the reduction of excess glycols, and the other for the polymerization.

Alternatively, PET can be prepared by solid phase polycondensation. For example, in this process, the melt polycondensation continues until the intrinsic viscosity of the pre-polymer is 1.0 to 1.4 dl / g, at which point the polymer is formed into a solid film. Pre-crystallization is carried out by heating to above 200 DEG C, for example, until the desired 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.

According to the present invention, the term "polyethylene terephthalate" includes unmodified polyethylene terephthalate and modified polyethylene terephthalate. The polyethylene terephthalate may be a straight chain polymer, a branched chain polymer, or a crosslinking polymer. For example, when glycerol is reacted with diacid or its anhydride, each glycerol will form a branch point. For example, if an internal bond occurs by reaction of an acid functional group and a hydroxyl group from a branch in the same or different molecule, the polymer will be crosslinked. Optionally, the polyethylene terephthalate may preferably be substituted by a C ₁ to C ₁₀ alkyl group, a hydroxyl, and / or an amine group. According to one embodiment, the polyethylene terephthalate is substituted by methyl, ethyl, propyl, butyl, tert-butyl, hydroxyl and / or amine groups. The polyethylene terephthalate may also be modified, for example, by copolymerization with cyclohexane dimethanol or isophthalic acid.

PET may exist both as an amorphous polymer and as a semi-crystalline polymer, i. E., A polymer containing crystalline and amorphous fractions, depending on its processing and thermal history. The semi-crystalline material may appear transparent or opaque and white depending on its crystal structure and particle size.

According to one embodiment, the polyethylene terephthalate is amorphous. According to another embodiment, the polyethylene terephthalate is semi-crystalline, and preferably the polyethylene terephthalate has a crystallinity of at least 20%, more preferably at least 40%, and most preferably at least 50%. According to yet another embodiment, the polyethylene terephthalate has a degree of crystallinity of 10 to 80%, more preferably 20 to 70%, and most preferably 30 to 60%. The crystallinity can be measured by differential scanning calorimetry (DSC).

According to one embodiment of the present invention, the 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, polyethylene terephthalate is the glass transition temperature (T _g) 50 to 200 ℃, preferably from 60 to 180 ℃, and more preferably from 70 to 170 ℃.

According to one embodiment of the present invention, the polyethylene terephthalate has a number average molecular weight of 5000 to 100000 g / mol, preferably 10000 to 50000 g / mol, and more preferably 15000 to 20000 g / mol.

The polyethylene terephthalate may be a virgin polymer, a recycled polymer, or a mixture thereof. Recycled polyethylene terephthalate can be obtained from post-consumer PET bottles, preformed PET scraps, regrinded PET, or recycled PET.

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

According to one embodiment, the at least one polymer is comprised of 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 an additional polymer, preferably a polyolefin, a polyamide, a cellulose, a polybenzimidazole, a mixture thereof, or a copolymer thereof. Examples of such polymers include polyhexamethylene diadipamide, polycaprolactam, aromatic or partially aromatic polyamides ("aramid"), nylon, polyphenylene sulfide (PPS), polyethylene, polypropylene, polybenzimidazole, or It is rayon.

According to one embodiment, the one or more polymers comprise at least 50 wt%, preferably at least 75 wt%, more preferably at least 90 wt%, and most preferably at least 95 wt%, based on the total amount of the at least one polymer Polyethylene terephthalate.

One or more fillers

According to the present invention, the nonwoven fabric comprises one or more fillers comprising calcium carbonate. The one or more fillers are dispersed in the one or more polymers.

The use of one or more fillers comprising calcium carbonate in polyester nonwovens has certain advantages over conventional nonwoven fabrics. For example, the hydrophobic or hydrophilic properties of the nonwoven can be tailored to the intended application by using suitable calcium carbonate fillers. In addition, the use of calcium carbonate filler enables the reduction of the polyester in the production of the nonwoven fabric without significantly affecting the quality of the nonwoven fabric. Moreover, the inventors have unexpectedly found that when calcium carbonate is added as a filler in PET, the polymer exhibits a higher thermal conductivity, which leads to a faster cooling rate of the polymer. It is also believed that calcium carbonate acts as a nucleating agent for PET without binding to any theory, thus increasing the crystallization temperature of PET. As a result, the rate of crystallization increases, which allows for a shorter cycle time, for example during the melting process. The present inventors have also found that the nonwoven web made from PET containing calcium carbonate filler has improved soft feel and greater rigidity compared to a nonwoven web made only from PET.

According to one embodiment, the calcium carbonate is heavy calcium carbonate, light calcium carbonate, modified calcium carbonate, surface treated calcium carbonate, or mixtures thereof. Preferably, the calcium carbonate is surface treated calcium carbonate.

It is understood that the heavy (or natural) calcium carbonate (GCC) is natural calcium carbonate mined from sedimentary rocks such as limestone or chalk, or from metamorphic marble. Calcium carbonate is known to exist as three types of crystalline polymorphs: calcite, aragonite and vaterite. Calcite is the most common crystalline polymorph and is thought to be the most stable crystalline form of calcium carbonate. Aragonite is not very common and is a discrete or clustered orthotropic crystal structure. Baterite is the most rare calcium carbonate polymorph and is generally unstable. Heavy calcium carbonate is almost exclusively calcite polymorphic, which is said to be a trigonal rhombohedral and exhibits the most stable calcium carbonate polymorphism. The term "source" of calcium carbonate in the sense of the present application means a natural mineral from which calcium carbonate is obtained. The source of calcium carbonate may include additional natural components such as magnesium carbonate, aluminosilicates, and the like.

According to one embodiment of the present invention, the source of heavy calcium carbonate (GCC) is selected from marble, chalk, calcite, dolomite, limestone, or mixtures thereof. Preferably, the source of heavy 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 is obtained by wet grinding and subsequent drying.

"Light calcium carbonate" (PCC) in the sense of the present invention is generally obtained by precipitation after reaction of lime with carbon dioxide in an aqueous environment or by precipitation of a calcium ion source and a carbonate ion source in water or from calcium ion and carbonate ion , For example, CaCl ₂ and Na ₂ CO ₃ . A further possible method of making PCC is the lime soda process, or the Solvay process, where PCC is a by-product of ammonia production. The light calcium carbonate is present in three primary crystal forms: calcite, aragonite and vaterite, and there are many different polymorphs (crystal walls) for each of these crystal forms. Calcite is composed of typical crystalline walls, such as S-PCC, R-PCC, hexagonal prism, turbid, colloidal (C-PCC), cubic, and prismatic (P-PCC) Structure. Aragonite is an orthorhombic structure, which is a typical crystal wall of hexagonal hexagonal prism crystals and a variety of thin elongated prisms, curved edges, steep pyramids, sculpted knife-shaped crystals, basalts, and coral or worm-like . Baterite belongs to hexagonal crystal system. The resulting PCC slurry can be mechanically dehydrated and dried.

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

Modified calcium carbonate may be characterized by modified internal GCC or PCC or surface reacted GCC or PCC. The surface-reacted calcium carbonate can be prepared by providing GCC or PCC in the form of an aqueous suspension and adding the acid to the suspension. Suitable acids are, for example, sulfuric acid, hydrochloric acid, phosphoric acid, citric acid, oxalic acid, or mixtures thereof. In the next step, calcium carbonate is treated with gaseous carbon dioxide. When a strong acid such as sulfuric acid or hydrochloric acid is used in the acid treatment step, carbon dioxide will be formed automatically in the system. Alternatively or additionally, the carbon dioxide may be supplied from an external source. The surface-reacted calcium carbonate is described, for example, in U.S. Patent Application Publication No. 2012/0031576 A1, International Patent Application Publication No. 2009/074492 A1, European Patent Application No. 2 264 109 A1, European Patent Application No. 2 070 991 A1 , Or European Patent Application No. 2 264 108 Al.

The surface treated calcium carbonate may be characterized by a GCC, PCC, or MCC comprising a treatment or coating layer on the surface. For example, calcium carbonate may be treated or coated with a hydrophobic surface treating agent such as an aliphatic carboxylic acid, a salt or ester thereof, or a siloxane. Suitable aliphatic acids, for example C ₅ to C ₂₈ fatty acids, for example, a stearic acid, a mixture of palmitic acid, myristic acid, lauric acid, or mixtures thereof. Calcium carbonate may also be treated or coated to be cationic or anionic, for example, by polyacrylate or polydiallyldimethylammonium chloride (poly DADMAC). The surface treated calcium carbonate is described, for example, in European Patent Application No. 2 159 258 Al.

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

According to another embodiment, the surface-treated calcium carbonate is preferably selected from the group consisting of aliphatic C ₅ to C ₂₈ fatty acids, salts thereof, esters thereof, and the like, from the treatment with fatty acids, salts thereof, esters thereof, , Or a combination thereof, and more preferably from a treatment with ammonium stearate, calcium stearate, stearic acid, palmitic acid, myristic acid, lauric acid, or a mixture thereof, or Surface coating.

According to one embodiment, the calcium carbonate has an average particle size ( d ₅₀ ) of 0.1 to 3 탆, preferably 0.4 to 2.5 탆, more preferably 1.0 to 2.3 탆, and most preferably 1.2 to 1.8 탆. Additionally or alternatively, the calcium carbonate has a top-cut particle size ( d ₉₈ ) of 1 to 10 μm, preferably 5 to 8 μm, more preferably 4 to 7 μm, and most preferably 6 to 7 μm .

The calcium carbonate may be present in the nonwoven fabric in an amount of from 0.1 to 50% by weight, preferably from 0.2 to 40% by weight, and more preferably from 1.0 to 35% by weight, based on the total weight of the nonwoven fabric. According to another embodiment, the calcium carbonate is present in an amount of from 0.5 to 20% by weight, from 1.0 to 10% by weight, from 5.0 to 40% by weight, from 7.5 to 30% by weight, or from 10 to 25% by weight, based on the total weight of the non- Is present in the nonwoven fabric.

According to one embodiment, calcium carbonate is dispersed in one or more polymers and is present in an amount of 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, ≪ / RTI > According to another embodiment, the calcium carbonate is dispersed in one or more polymers and is present in an amount of from 0.5 to 20% by weight, from 1.0 to 10% by weight, from 5.0 to 40% by weight, from 7.5 to 30% by weight, Or from 10 to 25% by weight.

According to one embodiment, the at least one filler comprises calcium carbonate. Calcium carbonate may consist of only one particular type of calcium carbonate or a mixture of two or more types of calcium carbonate.

According to another embodiment, the one or more fillers comprise a further mineral pigment. Examples of additional pigment particles include silica, alumina, titanium dioxide, clay, calcined clay, talc, kaolin, calcium sulfate, wollastonite, mica, bentonite, barium sulfate, gypsum, or zinc oxide.

According to one embodiment, the one or more fillers comprise at least 50 wt%, preferably at least 75 wt%, more preferably at least 90 wt%, and most preferably at least 95 wt%, based on the total amount of one or more fillers And calcium carbonate.

According to one embodiment, the one or more fillers are present in the nonwoven in an amount of 0.1 to 50 wt%, preferably 0.2 to 40 wt%, and more preferably 1 to 35 wt%, based on the total weight of the nonwoven. According to another embodiment, the at least one filler is dispersed in the one or more polymers and is present in an amount of 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 By weight.

According to one aspect of the present invention, there is provided the use of calcium carbonate as a filler in a nonwoven comprising at least one polymer comprising a polyester. According to another aspect of the present invention, there is provided the use of calcium carbonate as a filler in a nonwoven, wherein the filler is dispersed in one or more polymers comprising a polyester.

According to one preferred embodiment of the present invention, the use of calcium carbonate as a filler in a nonwoven fabric comprising polyethylene terephthalate is provided. According to another preferred embodiment of the present invention, there is provided the use of calcium carbonate as a filler in a nonwoven fabric, wherein the filler is dispersed in one or more polymers comprising polyethylene terephthalate. Preferably, the calcium carbonate is surface treated calcium carbonate.

According to a further aspect of the present invention there is provided the use of calcium carbonate as a filler in nonwoven fibrous, filament and / or film-like filament structures comprising at least one polymer comprising a polyester, preferably polyethylene terephthalate. According to a further aspect of the present invention there is provided the use of calcium carbonate as a filler in nonwoven fibrous, filament and / or film-like filament structures comprising at least one polymer comprising a polyester, preferably polyethylene terephthalate, Is dispersed in the one or more polymers.

Non-woven

Nonwoven fabrics are flat, flexible, porous sheet structures made by embedding layers or nets of fibers, filaments and / or film-like filamentary structures.

According to one aspect of the present invention there is provided a nonwoven fabric, filament and / or film-like filament structure comprising at least one polymer comprising polyester and at least one filler comprising calcium carbonate.

According to one embodiment, the nonwoven comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate, wherein the one or more fillers are dispersed in the one or more polymers. According to yet another embodiment, the nonwoven fabric comprises at least one polymer and at least one filler in the form of a fiber, filament and / or film-like filament structure, wherein the at least one filler is dispersed in the at least one polymer.

The fibers and / or filaments may have a diameter of 0.5 to 40 mu m, preferably 5 to 35 mu m. The fibers and / or filaments may also be of any cross-sectional shape, e.g., circular, oval, rectangular, dumbbell shaped, elongated, triangular, or irregular. The fibers and / or filaments may also be hollow and / or bicomponent and / or ternary fiber.

The nonwoven fabric may contain, in addition to one or more polymers and one or more fillers, further additives such as waxes, optical brighteners, heat stabilizers, antioxidants, antistatic agents, anti-blocking agents, dyes, pigments, , Natural oils, or synthetic oils. The nonwoven fabric may also include 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 nonwoven fabric may also be reinforced in the form of a textile surface structure, preferably in the form of a fabric, laying, knitted, knitted or nonwoven fabric, by means of a reinforcement thread.

According to one embodiment, the nonwoven fabric comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. According to another embodiment, the nonwoven fabric comprises at least one polymer comprising polyethylene terephthalate and at least one filler comprising calcium carbonate. According to yet another embodiment, the nonwoven fabric comprises polyethylene terephthalate and calcium carbonate.

According to a typical embodiment, the nonwoven comprises at least one polymer in an amount of 50 to 99 wt%, and at least one filler in an amount of 1 to 50 wt%, based on the total weight of the nonwoven, preferably 60 to 98 wt% , And more preferably from 65 to 95% by weight, and from 5 to 35% by weight, in an amount of from 5 to 35% by weight, based on the total weight of the composition, and one or more fillers in an amount of from 2 to 40% And fillers. According to another exemplary embodiment, the nonwoven fabric comprises 90 wt% polyester, preferably polyethylene terephthalate, and 10 wt% calcium carbonate, preferably heavy calcium carbonate, based on the total weight of the nonwoven. According to yet another exemplary embodiment, the nonwoven fabric comprises 80% by weight of a polyester, preferably polyethylene terephthalate, and 20% by weight of calcium carbonate, preferably heavy calcium carbonate, based on the total weight of the nonwoven.

According to one aspect of the present invention, there is provided a method of making 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) molding the mixture into a fiber, filament and / or film-like filament structure, and

c) forming a nonwoven fabric from a fiber, filament and / or film-like filament structure.

According to a preferred embodiment, the polyester is polyethylene terephthalate and / or the calcium carbonate is surface treated calcium carbonate.

Mixtures of one or more polymers comprising polyethylene terephthalate and one or more fillers comprising calcium carbonate, provided in process step a), may be prepared by any method known in the art. For example, the one or more polymers and the one or more fillers can be dry blended, melt blended, optionally formed into granules or pellets, or masterbatches of one or more polymers and one or more fillers are premixed, Or pellets, and may be mixed with additional polymers or fillers.

According to one embodiment, in step b) the mixture is formed into a fiber, preferably by an extrusion process, and more preferably by a meltblown process, a spunbond process, or a combination thereof. However, any other suitable process known in the art for forming the polymer into fibers may also be used.

Any meltblown process, spunbond process, or combination thereof known in the art can be used to form a mixture of one or more polymers and one or more fillers into a fiber. For example, meltblown fibers can be made by melting the mixture, extruding the mixture through a die or a small orifice to form the fibers, and thinning the molten polymeric fibers by hot air. The surrounding cold air can then be introduced into the hot air stream for cooling and solidification of the fiber. In the spunbond process, the mixture can be melt spun into fibers by pumping the molten mixture through a plurality of capillaries aligned with rows and rows of uniform arrangement. After extrusion, the fibers can be made thin by high-speed air. The air creates a tensile force on the fiber that pulls the fiber into the desired denier. The spunbond process may have the advantage of providing greater strength to the nonwoven. The second component can be coextruded in a spunbond process, which can provide additional properties or adhesion performance.

Two typical spunbond processes are known in the art as the Lurgi process and the Reifenhaeuser process. The Rohrgas process is based on extruding a molten polymer through a spinneret orifice and subsequently quenching the newly formed extruded filament with air and pulling it by suction through a venturi tube. After formation, the filaments are dispensed onto a conveyor belt to form a nonwoven web. The lypen hoisting process differs from the louvre process in that the quench zone for the filament is enclosed and the cooled air stream is accelerated and thus induces more efficient performance of the filaments in the air stream.

The fibers formed in process step b) may be stretched or elongated to induce molecular orientation and affect crystallinity. This results in reduced diameter and improved physical properties.

According to one embodiment of the present invention, the mixture is formed into fibers by combining the meltblown process and the spunbond process in step b).

By combining the meltblown and spunbond processes, nonwoven fabrics can be made that comprise a multilayer nonwoven fabric, e.g., two outer layers of a spunbond fabric and an inner layer of a meltblown fabric, And is known as a meltblown-spunbonded (SMS) nonwoven fabric. In addition, either or both of these processes may be combined in any arrangement with the staple fiber microfabrication process, or the bonded fabric may be obtained from a nonwoven staple fiber microfabrication process. In such laminated fabrics, the layers are generally at least partially integrated by one of the joining methods further described below.

The nonwoven fabric produced by the method of the present invention may be a multilayer nonwoven fabric, preferably a spunbonded-meltblown-spunbonded (SMS), meltblown-spunbonded-meltblown (MSM), spunbond- Meltblown - Spunbonded - Meltblown (SMSM), Meltblown - Spunbonded - Meltblown - Spunbonded (MSMS), Spunbonded - Meltblown - Meltblown - Spunbonded SMMS), or a meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric. The nonwoven fabric may be compressed, for example by lamination, to ensure adhesion of the layer.

According to one embodiment, steps b) and c) of the method of the present invention are repeated two or more times to form a multi-layer nonwoven, preferably a spunbonded-meltblown-spunbonded (SMS), meltblown- (MSM), spunbonded-meltblown-spunbonded-meltblown (SMSM), meltblown-spunbonded-meltblown-spunbonded (MSMS), spunbonded Meltblown-meltblown-spunbonded (SMMS), or meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric.

According to one embodiment, in step c) the nonwoven is formed by gathering the fibers on a surface or carrier. For example, fibers can be collected on a pore surface such as a moving screen or a forming wire. The fibers can be randomly deposited on the pore surface to form a sheet, which can be fixed on the surface by vacuum force.

According to an optional embodiment of the method of the present invention, the resultant nonwoven fabric is treated as a bonding step. Examples of bonding methods include thermal point bonding or calendering, ultrasonic bonding, hydroentanglement, stitching and aeration bonding. Thermal point bonding or calendaring is a commonly used method and involves passing the nonwoven fabric to be bonded through heated calender rolls and anvil rolls. The calender rolls are typically patterned in any manner so that the entire fabric does not bond across its entire surface. Various patterns can be used in the method of the present invention without affecting the mechanical properties of the web. For example, the web may be bonded according to a bone knit pattern, a wire texture pattern, a diamond pattern, or the like. However, any other bonding method known in the art may be used. Optionally, a binder, adhesive, or other chemical may be added during the bonding step.

According to another optional embodiment of the method of the present invention, the resultant nonwoven is subjected to a post-treatment step. Examples of post-treatment processes are orientation orientation, creping, entanglement, or embossing.

According to one aspect of the present invention there is provided the use of a fiber for the production of a nonwoven, wherein the fiber comprises at least one polymer comprising polyester and at least one filler comprising calcium carbonate.

According to a preferred embodiment of the present invention there is provided the use of fibers for the production of nonwoven fabrics, wherein the fibers comprise at least one polymer comprising polyethylene terephthalate and at least one filler comprising calcium carbonate.

According to another aspect of the present invention there is provided the use of a polymer composition for the production of a nonwoven, wherein the polymer composition comprises at least one polymer comprising a polyester and at least one filler comprising calcium carbonate. According to another preferred embodiment of the present invention there is provided the use of a polymer composition for the production of a nonwoven fabric, wherein the polymer composition comprises at least one polymer comprising polyethylene terephthalate and at least one filler comprising calcium carbonate.

The nonwoven fabric of the present invention can be used in many different applications. According to one aspect of the present invention, the nonwoven fabric of the present invention can be used in a variety of applications including building materials, waterproofing materials, insulation materials, soundproofing materials, roofing materials, consumer goods apparel, interior decoration and apparel industry, industrial apparel, medical supplies, home furnishing, Sanitary goods, or filter media. According to yet another aspect of the present invention there is provided an article comprising a nonwoven fabric of the present invention, wherein the article is selected from the group consisting of building materials, consumer apparel, industrial apparel, medical supplies, home furnishings, , Or a filter medium.

Examples of building materials include house wraps, asphalt rugs, bedrock and railroads, golf and tennis courts, wallpaper lining, acoustic wall coverings, roofing and tile floors, soil stabilizers and underfloor, foundation stabilizers, , Drainage systems, geomembrane protection and aquaculture products, agricultural mulch, nail and waterway barriers, or sand infiltration barriers for drainage tiles. Another example for building materials is a landfill or stiffener.

Examples of consumer goods apparel are seams, clothing and gloves insulation, bra and shoulders, handbag parts, or shoe parts. Examples of industrial apparel are tarpaulins, tents, or transportation (wood, steel) packaging materials. Examples of medical supplies include protective clothing, facial masks, isolation gowns, surgical gowns, surgical drapes and covers, surgical gowns, caps, sponges, dressings, towels, orthopedic padding, bandages, tapes, dental bibs, Dialyzer, IV solution or filter for blood, or transdermal drug delivery component. Examples of home furnishings are pillows, cushions, quilts, comforters, dirt covers, insulators, window trim, blankets, insignia parts, carpet lining, or carpets.

Examples of protective articles are coated fabrics, reinforced plastics, protective clothing, laboratory coats, adsorbents, or flame retardants. Examples of packaging materials are desiccant packaging, adsorbent packaging, gift boxes, pile boxes, various nonwoven bags, book covers, mailing envelopes, express bags, or delivery bags. Examples of filter media are laminations with gasoline, oil and air filters, vacuum bags, or nonwoven layers, including filtration liquid cartridges and bag filters.

The scope and spirit of the invention is intended to illustrate certain embodiments of the invention and will be better understood on the basis of the following non-limiting examples.

Example

1. Measurement methods and materials

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

Particle size

The particle distribution of the calcium carbonate filler was measured using Sedigraph 5120 manufactured by Micrometrics. Methods and apparatus are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. The measurement was carried out in an aqueous solution containing 0.1% by weight Na ₄ P ₂ O ₇ . Samples were dispersed using a high-speed stirrer and ultrasonic waves.

Intrinsic viscosity

The intrinsic viscosity, or IV, is a measure of the molecular weight of the polymer, measured by dilute solution viscosity measurement. All IV were measured in a 60/40 phenol / tetrachloroethane solution at 25 占 폚 according to ASTM D4603 on a Ubbelohde capillary viscometer. Typically, about 8-10 chips were dissolved to make a solution with a concentration of about 0.5%.

Tensile test

1 BA (1: 2) test sample was subjected to a tensile test according to ISO 527-3 using a speed of 50 mm / min. The properties measured by the tensile test are the yield stress, break-strain, break-stress, and modulus of the polymer or polymer composition.

Charpy ( Charpy ) Impact test

Charpy impact tests were carried out according to ISO 179-2: 1997 (E) using notched test samples of size 50 x 6 x 6 mm and unrecorded test samples.

material

Polymer 1: Lighter S98 PET, available from Equipolymers GmbH, Germany. Intrinsic viscosity: 0.85 ± 0.02; T _g : 78 ° C; T _m : 247 캜; Crystallinity: at least 50.

Polymer 2: Lighter S93 PET, available from Iquipolymerz. Intrinsic viscosity: 0.80 + 0.02; T _g : 78 ° C; T _m : 247 캜; Crystallinity: at least 50.

Filler: Omyafilm 707-OG (Heavy Calcium Carbonate), available from Omya AG, Switzerland. Particle size ( d ₅₀ ): 1.6 탆; Top cut ( d ₉₈ ): 6 탆.

2. Example

Example  One

A test sample containing only polymer 1 was prepared as well as a composition of 90 wt% polymer 1 and 10 wt% filler based on the total weight of the composition.

The mechanical properties of the test sample were measured using the tensile test described above at a tension of 5 N as a 500 N tester. The tensile test results are shown in Table 1 below.

Sample B of the present invention exhibited a higher yield stress and e-modulus as compared to Comparative Sample A, but the fracture strain and fracture stress of Sample B of the present invention were reduced. Thus, the polymer composition of the present invention (Sample B) was more elastic and flexible as compared to the pure PET polymer (Sample A). This has a positive effect on the tactile properties of the nonwoven fabric made from such polymer compositions, especially with respect to the flexibility of the material. For example, these substances are more pleasant to the body.

Example  2

A test sample containing only polymer 2, as well as a composition of 90% by weight of polymer 2 and 10% by weight filler, and 80% by weight of polymer 2 and 20% by weight filler, based on the total weight of the composition.

The tensile test and the Charpy impact test described above were used to measure the mechanical properties of the test sample at a tensile force of 4 N as a 20 kN tester. The tensile test results are shown in Table 2 below.

Samples D and E of the present invention exhibited higher yield stress and e-modulus as compared to Comparative Sample C, but the fracture strain, fracture stress, and impact resistance of Samples D and E of the present invention were reduced. Thus, the polymer compositions of the present invention (Samples D and E) were more elastic and flexible as compared to the pure PET polymer (Sample C). This has a positive effect on the tactile properties of the nonwoven fabric made from such polymer compositions, especially with respect to the flexibility of the material. For example, these substances are more pleasant to the body.

Claims (15)

As nonwoven fabrics,
One or more polymers comprising a polyester, and
One or more fillers comprising calcium carbonate
Lt; / RTI >
The calcium carbonate is present in an amount of from 0.1 to 50% by weight, based on the total weight of the nonwoven fabric,
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 from 0.5 to 40 mu m,
The polyester is polyethylene terephthalate,
Calcium carbonate is a nonwoven fabric having an average particle size d ₅₀ of 1.2 to 1.8 μm and a top cut particle size d ₉₈ of 4 to 7 μm. The nonwoven fabric according to claim 1, wherein the polyester has a number average molecular weight of 5000 to 100000 g / mol. The nonwoven fabric according to claim 1 or 2, wherein the calcium carbonate is a ground calcium carbonate, a precipitated calcium carbonate, a modified calcium carbonate, a surface treated calcium carbonate, or a mixture thereof. 3. The nonwoven fabric according to claim 1 or 2, wherein the calcium carbonate has a top-cut particle size d ₉₈ of 6 to 7 탆. The nonwoven fabric as claimed in claim 1 or 2, wherein the calcium carbonate is present in the nonwoven fabric in an amount of 0.2 to 40% by weight based on the total weight of the nonwoven fabric. As a method for producing a nonwoven fabric,
a) providing a mixture of at least one polymer comprising a polyester and at least one filler comprising calcium carbonate,
b) molding the mixture into fibers and / or filaments having a diameter of from 0.5 to 40 mu m, and
c) forming a nonwoven from fibers and / or filaments,
The calcium carbonate is present in an amount of from 0.1 to 50% by weight, based on the total weight of the nonwoven fabric,
The polyester is polyethylene terephthalate,
Wherein the calcium carbonate is a nonwoven fabric having an average particle size d ₅₀ of 1.2 to 1.8 μm and a top cut particle size d ₉₈ of 4 to 7 μm. The method of claim 6, wherein the mixture in step b) is formed into a fiber by an extrusion process, or by a melt blown process or a spunbond process, or a combination thereof. 8. The method of claim 7, wherein the nonwoven is formed by collecting fibers on a surface or carrier. 9. A process according to any one of claims 6 to 8, wherein steps b) and c) are repeated two or more times to produce a multi-layer nonwoven fabric. Wherein the filler comprises calcium carbonate, wherein the calcium carbonate is present in the nonwoven in an amount of from 0.1 to 50% by weight, based on the total weight of the nonwoven, and wherein the filler comprises at least one polymer selected from the group consisting of polyethylene terephthalate , The filler is in the form of fibers and / or filaments having a diameter of from 0.5 to 40 μm and the calcium carbonate has a mean particle size d ₅₀ of from 1.2 to 1.8 μm and a top cut particle size d ₉₈ of from 4 to 7 μm Filler. Wherein the fiber comprises at least one polymer comprising polyester and at least one filler comprising calcium carbonate, wherein the polyester is polyethylene terephthalate and the calcium carbonate is present in an amount of from 0.1 to 50 wt. ≪ RTI ID = 0.0 > %, The filler is in the form of fibers and / or filaments having a diameter of from 0.5 to 40 μm, the calcium carbonate has an average particle size d ₅₀ of from 1.2 to 1.8 μm and a top cut particle size d ₉₈ is from 4 to 7 탆. 3. The method according to claim 1 or 2, further comprising at least one of the following items: a building material, a waterproofing material, a heat insulating material, a soundproofing material, a roofing material, a consumer apparel, an interior decoration and a garment industry, an industrial apparel, , Sanitary articles, or nonwovens used in filter media. An article comprising a nonwoven fabric according to claim 1 or 2, wherein the article is selected from building materials, consumer goods apparel, industrial apparel, medical articles, home furnishings, protective items, packaging materials, cosmetics, sanitary articles, Goods. 9. A process according to any one of claims 6 to 8, wherein steps b) and c) are repeated two or more times to form spunbonded meltblown-spunbonded (SMS), meltblown - Spunbonded - Meltblown (MSM), Spunbonded - Meltblown - Spunbonded - Meltblown (SMSM), Meltblown - Spunbonded - Meltblown - Spunbonded (MSMS) Spunbonded-meltblown-meltblown-spunbonded (SMMS), or meltblown-spunbonded-spunbonded-meltblown (MSSM) nonwoven fabric.

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