Polypropylene (PP)-CaCO3 master batch in PET fibers

Abstract

The present invention relates to a polypropylene-based master batch comprising 15-35% by weight, based on the total weight of the polypropylene-based master batch, of a polypropylene having a melt flow rate MFR (230 DEG C, 230 DEG C, 230 DEG C) of 15-50 g / 10 min measured according to ISO 1133. 2.16 kg) and 65-85% by weight, based on the total weight of the polypropylene-based masterbatch, of a surface-treated filler material product comprising at least one heavy calcium carbonate-containing filler material; a polyester fiber composition comprising the polypropylene-based master batch; a polyester nonwoven or filament formed from the polyester fiber composition; the invention also relates to a method for preparing the polyester nonwoven or filament and to the use of the polypropylene-based masterbatch in the production of polyester nonwoven or filament and to articles formed from polyester nonwoven or filament.

Description

Technical Field

[0001] This invention relates to a polypropylene-based masterbatch comprising, by weight 15-35% of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and by weight 65-85% of a surface-treated filler material product comprising at least one heavy calcium carbonate filler material; a polyester fiber composition comprising the polypropylene-based masterbatch; a polyester nonwoven fabric or filament formed from the polyester fiber composition; a method for preparing the polyester nonwoven fabric or filament; the use of the polypropylene-based masterbatch in the production of polyester nonwoven fabrics or filaments; and articles formed from polyester nonwoven fabrics or filaments. Background Technology

[0002] In this art, certain fillers are commonly added to polymer compositions, such as those used for polyester fibers. For example, fillers such as calcium carbonate-containing filler materials are added to polyester fibers to improve their properties and reduce their carbon footprint. This is typically done using polyester-based masterbatches because of the inherent compatibility between the masterbatch polyester carrier resin and the fiber polyester resin.

[0003] However, the high cost and low filler loading of polyester-based masterbatches make their market implementation challenging. Different polymers have been tested as carrier materials in masterbatches. For example, WO2005040257 A1 discloses a blend of polyester and ethylene-methacrylate copolymer (EMA), which is used as a compatibilizer to enable the production of fibers and films. However, EMA compatibilizers are very expensive and therefore not an option for the production of PET fibers. On the other hand, CN101392082 A relates to a polypropylene imitation jade-colored masterbatch containing polypropylene grafted maleic anhydride as a compatibilizer. CN109535565 A relates to a nano-calcium carbonate functional masterbatch in which elastomers and crosslinking agents are added for compatibilization. CN113980298 A relates to an antistatic masterbatch containing calcium carbonate with a size <60 nm, which is further surface-treated with a titanium composite coupling agent, whereby the carrier resin is a mixture of bisphenol A type aromatic polycarbonate, high-density polyethylene, and polybutylene terephthalate. However, polyolefin-based masterbatches are considered incompatible with polyesters. Therefore, it is also believed that such masterbatches cannot be used for fiber spinning without the addition of expensive compatibilizers.

[0004] Therefore, during the production of fibers or filaments, it is continuously necessary to add CaCO3 masterbatch to polyester. Summary of the Invention

[0005] Therefore, one object of the present invention is to provide a masterbatch containing a calcium carbonate filler material that can be used in the production of polyester fibers or filaments. Furthermore, it is desirable that the masterbatch has a high filler loading capacity and can be used without the addition of expensive compatibilizers. Moreover, it is desirable that polyester fibers or nonwovens containing this masterbatch have properties and processability similar to those obtained from polyester fibers or nonwovens containing a polyester-based masterbatch.

[0006] The foregoing and other objectives are addressed by the subject matter defined in the independent claims. Advantageous embodiments of the invention are defined in the corresponding dependent claims.

[0007] According to one aspect of the invention, a polypropylene-based masterbatch is provided, comprising 15-35% by weight of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, based on the total weight of the polypropylene-based masterbatch, and 65-85% by weight of a surface-treated filler material product comprising at least one heavy calcium carbonate filler material, based on the total weight of the polypropylene-based masterbatch, the surface-treated filler material product having a median particle size d of 0.5-2.5 μm as measured by sedimentation. 50 and the top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

[0008] According to one embodiment, the propylene polymer is a random propylene copolymer or a propylene homopolymer, and / or the propylene polymer has

[0009] a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 20-40 g / 10 min, with the most preferred value being 22-37 g / 10 min, and / or

[0010] b) The density, measured according to ISO 1183-1, is equal to or less than 0.910 g / cm³. 3 More preferably, the density is equal to or greater than 0.850 g / cm³. 3 And the optimal value is 0.850-0.910 g / cm³. 3 .

[0011] According to another embodiment, the heavy calcium carbonate filler material is selected from marble, chalk, dolomite, limestone and mixtures thereof, and most preferably, the heavy calcium carbonate filler material is marble.

[0012] According to another embodiment, the surface-treated filler material product, i.e., the surface-treated heavy calcium carbonate-containing filler material, includes a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, which comprises...

[0013] i. At least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride comprising a succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent, and / or

[0014] ii. At least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C4-C24.

[0015] According to one embodiment, the surface-treated filler material product, namely the surface-treated heavy calcium carbonate filler material, comprises the treated layer in an amount of 0.1-3% by weight based on the total dry weight of the at least one heavy calcium carbonate filler material.

[0016] According to another embodiment, the surface-treated filler material product, namely, the surface-treated heavy calcium carbonate-containing filler material, has a median particle size d measured by sedimentation. 50 The particle size is 1.0-2.2 μm, preferably 1.5-2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 ≤7.5 μm, and / or a specific surface area (BET) of 0.5–150 m² measured using nitrogen and the BET method according to ISO 9277:2010. 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and / or moisture content of ≤0.25% by weight based on the total weight of the product containing the at least one surface-treated filler material, as measured according to ISO 787 / 2.

[0017] According to another embodiment, the polypropylene-based masterbatch comprises 28-32% by weight of the propylene polymer based on the total weight of the polypropylene-based masterbatch, and 68-72% by weight of the surface-treated filler material product based on the total weight of the polypropylene-based masterbatch.

[0018] According to one embodiment, the polypropylene-based masterbatch does not contain polymeric materials different from the propylene polymer in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene-based masterbatch, and / or the polypropylene-based masterbatch does not contain filler materials different from the surface-treated filler material product in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene-based masterbatch.

[0019] According to another aspect of the invention, a polyester fiber composition is provided comprising 86-99.3% by weight, preferably 90-96.5% by weight and most preferably 92-94% by weight of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, based on the total weight of the polyester fiber composition, and 0.7-14% by weight, preferably 3.5-10% by weight and most preferably 6-8% by weight of a polypropylene-based masterbatch as defined herein, based on the total weight of the polyester fiber composition.

[0020] According to one embodiment, the polyester fiber composition includes the surface-treated filler material product, i.e., a surface-treated heavy calcium carbonate filler material, in an amount of 0.5-10% by weight, preferably 2-8% by weight, and most preferably 4-6% by weight, based on the total weight of the polyester fiber composition.

[0021] According to another embodiment, the polyester resin comprises: one or more saturated polyester resins selected from polylactic acid, polylactic acid-based polymers, aliphatic polyesters such as polyhydroxyalkanoates, for example polyhydroxybutyrate, poly-3-hydroxybutyrate (P3HB), polyhydroxyvalerate, polyhydroxybutyrate-polyhydroxyvalerate copolymer, poly(3-hydroxybutyrate-copoly-3-hydroxyvalerate); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polyglycolic acid, poly(di(2-hydroxybutyrate)) Alkyl ketones and mixtures thereof, preferably, the polyester resin is polyethylene terephthalate (PET).

[0022] According to another aspect of the invention, a polyester nonwoven fabric or filament formed from the polyester fiber composition defined herein is provided.

[0023] According to another aspect of the invention, a method for preparing polyester nonwoven fabrics or filaments as defined herein is provided, wherein the method comprises the following steps:

[0024] a) Provide a polyester resin in an amount of 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight, based on the total weight of the polyester product, the polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5.

[0025] b) Provide a polypropylene-based masterbatch in an amount of 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight, based on the total weight of the polyester product.

[0026] c) Contact the polyester resin from step a) with the polypropylene-based masterbatch from step b) to obtain a polyester fiber composition, and

[0027] d) Shape the polyester fiber composition obtained in step c) to obtain a polyester nonwoven fabric or filament.

[0028] According to another aspect of the invention, a polypropylene masterbatch is provided for use in the production of polyester nonwovens or filaments, the polypropylene masterbatch comprising, by weight, 15-35% of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and by weight, 65-85% of a surface-treated filler material product comprising at least one heavy calcium carbonate filler material, the surface-treated filler material product having a median particle size d of 0.5-2.5 μm as measured by sedimentation. 50 and the top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

[0029] According to another aspect of the invention, articles formed from polyester nonwoven fabrics or filaments as defined herein are provided, preferably selected from hygiene products, medical and health care products, wiping products such as refreshing or cleaning wipes, tissue products, upholstery, geotextile products, filtration products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, building products, automotive parts, bottles, cups, etc.

[0030] It should be understood that, for the purposes of this invention, the following terms have the following meanings:

[0031] The term "polypropylene-based masterbatch" (or "masterbatch") as used in this invention refers to compositions having a relatively high filler content (meaning ≥65% by weight (based on the total weight of the masterbatch)). The "masterbatch" can be added to unfilled or low-filled polyester resin during processing to achieve even higher filler contents.

[0032] As used herein, the term "copolymer" refers to a polymer derived from more than one type of monomer. A copolymer obtained by copolymerizing two types of monomers may also be called a binary copolymer, a copolymer obtained from three types of monomers may be called a ternary copolymer, a copolymer obtained from four types of monomers may be called a quaternary copolymer, and so on (see IUPAC Compendium of Chemical Terminology 2014, "copolymer"). Therefore, the term "homopolymer" refers to a polymer that is essentially derived from a single type of monomer.

[0033] The term "surface-treated" as used in this invention refers to a material that has been contacted with a surface-treatment agent to obtain a coating layer on at least a portion of the surface of the material.

[0034] The “particle size” of particulate materials is defined in this paper by the distribution of their weight-based particle size d. x To describe. Here, the value d x This refers to a diameter such that, relative to this diameter, x% of the weight of particles have a diameter less than d. x The diameter. This means, for example, d. 20 The value refers to a particle size in which 20% of the weight of all particles is less than that particle size. d 50 The value is therefore the weight-median particle size, that is, the particle size at which 50% of the weight of all particles is less than this particle size. For the purposes of this invention, unless otherwise specified, this particle size is designated as the weight-median particle size d. 50 (wt). Particle size was determined using Sedigraph from Micromeritics Instrument Corporation. TM The 5120 instrument is used to determine the particle size. The method and instrument are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. Measurements are performed in an aqueous solution of 0.1% by weight Na₄P₂O₇.

[0035] The specific surface area (in meters) of the materials used throughout this document 2 The total surface area (in g) can be determined by the Brunauer-Emmett-Teller (BET) method using nitrogen as the adsorbed gas and with a Micromeritics ASAP 2460 instrument. This method is well known to those skilled in the art and is defined in ISO 9277:2010. Before measurement, the sample is conditioned at 100°C under vacuum for 30 minutes. The total surface area of ​​the material (m²) is... 2 The mass (g) and specific surface area (m²) of the material can be used to determine its properties. 2 The product of / g) is obtained.

[0036] When discussing singular nouns, the use of indefinite or definite articles such as "a," "an," or "the" includes the plural form of the noun, unless otherwise specified.

[0037] When the term "comprising" is used in this specification and claims, it does not exclude other elements. For the purposes of this invention, the term "consisting of" is considered a preferred embodiment of the term "comprising". If a group is defined below as including at least a certain number of embodiments, this is also understood to disclose a group that preferably consists only of these embodiments.

[0038] Terms such as “obtainable” or “definable” and “obtained” or “defined” are used interchangeably. This means, for example, that unless the context explicitly indicates otherwise, the term “obtainable” does not imply that an embodiment must be obtained, for example, through a sequence of steps following the term “obtainable,” although the terms “obtainable” or “defined” always include such limiting understanding as a preferred embodiment.

[0039] Wherever the terms “including” or “having” are used, they are considered equivalent to “comprising” as defined above.

[0040] The polypropylene-based masterbatch of the present invention comprises, by weight, 15-35% of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and by weight, 65-85% of a surface-treated filler material product comprising at least one heavy calcium carbonate filler material, the surface-treated filler material product having a median particle size d of 0.5-2.5 μm as measured by sedimentation. 50 and the top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

[0041] Preferred embodiments of the product of the present invention will be described in more detail below. It should be understood that these embodiments and details also apply to the methods of preparation thereof described herein and their uses.

[0042] Polypropylene-based masterbatch

[0043] The polypropylene-based masterbatch contains 15-35% by weight of a propylene polymer based on the total weight of the polypropylene-based masterbatch, the propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133.

[0044] The propylene polymer can be a propylene copolymer or a propylene homopolymer.

[0045] When the propylene polymer is a propylene copolymer, the propylene copolymer is preferably a random propylene copolymer.

[0046] In one embodiment, the propylene copolymer (preferably a random propylene copolymer) comprises monomers that can copolymerize with propylene, such as comonomers like ethylene and / or C4-C8 α-olefins, particularly ethylene and / or C4-C6 α-olefins, such as 1-butene and / or 1-hexene. Preferably, the propylene polymer (preferably a random propylene copolymer) comprises, and in particular consists of, monomers that can copolymerize with propylene, selected from ethylene, 1-butene, and 1-hexene. More particularly, the propylene polymer (preferably a random propylene copolymer) comprises, in addition to propylene, units that can be derived from ethylene and / or 1-butene. In a preferred embodiment, the propylene copolymer (preferably a random propylene copolymer) comprises only units that can be derived from ethylene and propylene.

[0047] The term "propylene copolymer" refers to a propylene copolymer, preferably a random propylene copolymer, which preferably has a comonomer content of more than 1.0% to 10.0% by weight, more preferably more than 1.5% to 9.0% by weight, and even more preferably 2.0% to 8.0% by weight based on the total weight of the propylene copolymer (preferably the random propylene copolymer).

[0048] The propylene copolymer is preferably a random propylene copolymer. The term "random" means that the comonomers of the propylene copolymer are randomly distributed within the copolymer. The term "random" is understood according to IUPAC (Glossary of basic terms in polymer science; IUPAC recommendations 1996).

[0049] The term "propylene homopolymer" refers to polypropylene that is substantially composed of propylene units, specifically, propylene units comprising more than 99.0% by weight, preferably more than 99.2% by weight, even more preferably more than 99.5% by weight, and still more preferably at least 99.8% by weight, based on the total weight of the propylene homopolymer. In a preferred embodiment, only propylene units are detectable in the propylene homopolymer.

[0050] In a preferred embodiment, the propylene polymer is a propylene homopolymer.

[0051] The propylene polymer (preferably the propylene homopolymer) can be unimodal or multimodal, such as bimodal. However, it is preferred that the propylene polymer (preferably the propylene homopolymer) is unimodal.

[0052] It has been found that the propylene polymer (preferably the propylene homopolymer) must have a specific melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133. For example, the propylene polymer has a melt flow rate (MFR) of 20-40 g / 10 min, and most preferably 22-37 g / 10 min, as measured according to ISO 1133.

[0053] It should be understood that the propylene polymer (preferably the propylene homopolymer) has a xylene cold soluble content of 1.0-3.5% by weight and 1.5-3.0% by weight based on the total weight of the propylene polymer (preferably the propylene homopolymer).

[0054] More preferably, the propylene polymer has a relatively high melting temperature T. m For example, this propylene polymer has a melt temperature T measured according to ISO 11357-3. m The temperature range is 130-170°C, preferably 135-168°C. For example, if the propylene polymer is a propylene homopolymer, then the propylene homopolymer has a melting temperature T measured according to ISO 11357-3. m The temperature is 155-170°C, preferably 160-168°C. Alternatively, if the propylene polymer is a propylene copolymer, preferably a random propylene copolymer, then the propylene copolymer has a melting temperature T measured according to ISO 11357-3. m The temperature range is 130-145℃, with 135-140℃ being preferred.

[0055] Additionally or alternatively, the propylene polymer (preferably the propylene homopolymer) has a density equal to or less than 0.910 g / cm³, as measured according to ISO 1183-1. 3 More preferably, the density is equal to or greater than 0.850 g / cm³. 3 And the optimal value is 0.850-0.910 g / cm³. 3 For example, the propylene polymer (preferably the propylene homopolymer) has a density of 0.870-0.910 g / cm³ as measured according to ISO 1183-1. 3 More preferably 0.890-0.910 g / cm³ 3 And the optimal value is 0.900-0.910 g / cm³. 3 .

[0056] In a preferred embodiment, the propylene polymer (preferably the propylene homopolymer) therefore has

[0057] a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 20-40 g / 10 min, with the most preferred value being 22-37 g / 10 min, and / or

[0058] b) The density, measured according to ISO 1183-1, is equal to or less than 0.910 g / cm³. 3 More preferably, the density is equal to or greater than 0.850 g / cm³. 3 And the optimal value is 0.850-0.910 g / cm³. 3 .

[0059] For example, the propylene polymer (preferably the propylene homopolymer) has

[0060] a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 20-40 g / 10 min, with the most preferred value being 22-37 g / 10 min, and

[0061] b) The density, measured according to ISO 1183-1, is equal to or less than 0.910 g / cm³. 3 More preferably, the density is equal to or greater than 0.850 g / cm³. 3 And the optimal value is 0.850-0.910 g / cm³. 3 .

[0062] In one embodiment, the propylene polymer (preferably the propylene homopolymer) has

[0063] a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 22-37 g / 10 min, and

[0064] b) The density, measured according to ISO 1183-1, is 0.850–0.910 g / cm³. 3 For example, 0.870-0.910 g / cm³ 3 More preferably 0.890-0.910 g / cm³ 3 And the optimal value is 0.900-0.910 g / cm³. 3 .

[0065] For example, the propylene polymer (preferably the propylene homopolymer) has

[0066] a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 22-37 g / 10 min, and

[0067] b) The density, measured according to ISO 1183-1, is 0.900–0.910 g / cm³. 3.

[0068] In a preferred embodiment, the propylene polymer (preferably the propylene homopolymer) is polymerized in the presence of a Ziegler-Natta catalyst.

[0069] Ziegler-Natta catalysts and polymers obtained by using such catalysts are well known in the art, and those skilled in the art are familiar with the methods and conditions that can be used to prepare polymers.

[0070] The polypropylene-based masterbatch of the present invention further comprises a surface-treated filler material product. This surface-treated filler material product comprises at least one calcium carbonate-containing filler material. Specifically, this surface-treated filler material product comprises at least one heavy calcium carbonate-containing filler material.

[0071] In one embodiment, the at least one heavy calcium carbonate-containing filler material is selected from marble, chalk, dolomite, limestone, and mixtures thereof. Preferably, the heavy calcium carbonate-containing filler material is selected from, and more preferably, composed of, marble, limestone, and chalk. More preferably, the heavy calcium carbonate-containing filler material is selected from, and more preferably, composed of, marble and chalk. For example, the heavy calcium carbonate-containing filler material is marble.

[0072] As used in this invention, the term "ground calcium carbonate filler material" refers to a calcium carbonate source obtained from a depositional source such as marble, limestone, dolomite, chalk, and / or mixtures thereof, and processed by wet and / or dry treatments such as grinding, screening, and / or grading (e.g., using a cyclone separator or classifier). This ground calcium carbonate filler material may contain other components present in the depositional source, such as magnesium carbonate, aluminosilicates, etc. Therefore, it should be understood that the term "ground calcium carbonate filler material" is not to refer to calcium carbonate obtained by milling, but rather to the depositional source of the calcium carbonate.

[0073] Preferably, the at least one heavy calcium carbonate filler material is a sedimentary heavy calcium carbonate filler material. The term "sedimentary" heavy calcium carbonate filler material refers to calcium carbonate formed by the accumulation or deposition of calcium carbonate particles on the bottom of the ocean or other bodies of water on the Earth's surface, and the subsequent cementation of the particles.

[0074] In this invention, "dolomite" refers to a calcium carbonate mineral, specifically a calcium-magnesium carbonate mineral, with the chemical composition CaMg(CO3)2 ("CaCO3·MgCO3"). Based on the total weight of the dolomite, the dolomite mineral may contain at least 30.0% by weight of MgCO3, preferably more than 35.0% by weight, and more preferably more than 40.0% by weight of MgCO3.

[0075] Typically, the grinding of materials containing heavy calcium carbonate filler can be a dry or wet grinding step and can be carried out, for example, with any conventional grinding apparatus under conditions where the pulverization is primarily generated by the impact of an auxiliary body, i.e., in one or more of the following: ball mill, rod mill, vibratory mill, crusher, centrifugal impact mill, vertical bead mill, grinder, pin pulverizer, hammer mill, powder mill, shredder, de-clumping machine, knife cutter, or other such equipment known to those skilled in the art. In cases where the calcium carbonate filler material comprises wet heavy calcium carbonate filler material, the grinding step can be carried out under conditions that cause self-grinding and / or by horizontal ball milling and / or other such methods known to those skilled in the art. The resulting wet-processed heavy calcium carbonate filler material can be washed and dehydrated by well-known methods, such as by flocculation, filtration, or forced evaporation (before drying). Subsequent drying steps (if necessary) can be carried out in a single step (e.g., spray drying) or in at least two steps. It is also common for this mineral material to undergo beneficiation steps (such as flotation, bleaching, or magnetic separation steps) to remove impurities.

[0076] In contrast, "precipitated calcium carbonate" (PCC) refers to a synthetic material, typically obtained by precipitation after the reaction of carbon dioxide with calcium hydroxide in an aqueous, semi-dry, or humid environment, or by precipitating calcium and carbonate ions (e.g., CaCl2 and Na2CO3) from solution. Other possible methods for producing PCC include the lime-soda process or the Solvay process, where PCC is a byproduct of ammonia production. Precipitated calcium carbonate exists in three primary crystalline forms: calcite, aragonite, and aragonite, and for each of these forms, there are many different polymorphs (crystal inertia). Calcite has a triangular structure, which exhibits typical crystal inertia such as subtrigonal (S-PCC), orthorhombic (R-PCC), hexagonal prismatic, axial, colloidal (C-PCC), cubic, and prismatic (P-PCC). Aragonite has an orthorhombic crystal structure, which exhibits typical crystal inertia of paired hexagonal prisms, as well as various classifications including slender prisms, curved leaf-like crystals, steep cones, pointed crystals, branched trees, and coral or worm-like forms. Spherulite belongs to the hexagonal crystal system. The obtained PCC slurry can be mechanically dehydrated and dried. PCC is described, for example, in EP2447213 A1, EP2524898 A1, EP2371766 A1, EP1712597 A1, EP1712523 A1, or WO2013 / 142473 A1.

[0077] Therefore, this material containing heavy calcium carbonate can be easily distinguished from precipitated calcium carbonate (PCC).

[0078] Furthermore, "modified calcium carbonate" (MCC) is characterized by natural heavy calcium carbonate, precipitated calcium carbonate, or surface-reacted products with modified internal structure, i.e., "surface-reacted calcium carbonate." "Surface-reacted calcium carbonate" is a material comprising calcium carbonate and an anion of an acid on its surface, which is an insoluble (preferably at least partially crystalline) calcium salt. Typically, this insoluble calcium salt extends from at least a portion of the surface of the calcium carbonate. The calcium ions forming the at least partially crystalline calcium salt of the anion are primarily derived from the starting calcium carbonate material. MCC is described, for example, in US20120031576 A1, WO2009074492 A1, EP2264109 A1, EP2070991 A1, or EP2264108 A1.

[0079] Therefore, this material containing heavy calcium carbonate can be easily distinguished from modified calcium carbonate (MCC).

[0080] Therefore, this heavy calcium carbonate filler material can be easily distinguished from precipitated calcium carbonate (PCC) and modified calcium carbonate (MCC).

[0081] It should be understood that this heavy calcium carbonate-containing filler material has a specific particle size distribution. Specifically, this heavy calcium carbonate-containing filler material has a median particle size d measured by sedimentation. 50 The particle size is 0.5-2.5 μm. For example, this heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The thickness is 1.0-2.2 μm, preferably 1.5-2.2 μm.

[0082] Additionally, the heavy calcium carbonate-containing filler material has a top-cut particle size d measured by sedimentation. 98 The particle size is ≤9μm. For example, this heavy calcium carbonate-containing filler material has a top-cut particle size d measured by sedimentation. 98 It is ≤7.5μm.

[0083] In a preferred embodiment, the heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 1.0 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 The particle size is ≤7.5 μm. For example, this heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 1.5 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 It is ≤7.5μm.

[0084] Additionally or alternatively, the heavy calcium carbonate-containing filler material has a specific surface area (BET) of 0.5-150 m², as measured using nitrogen and the BET method according to ISO 9277:2010. 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g. In a particularly preferred embodiment, the heavy calcium carbonate-containing filler material has a specific surface area (BET) of 3-10 m², measured according to ISO 9277:2010 using nitrogen and the BET method. 2 / g.

[0085] In one embodiment, the heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 0.5 to 2.5 μm, and the top-cut particle size d is measured by sedimentation. 98 For a surface area ≤9 μm and a specific surface area (BET) of 0.5–150 m² measured using nitrogen and the BET method according to ISO 9277:2010, the surface area is ≤9 μm. 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, for example 3-10m 2 / g.

[0086] In a preferred embodiment, the heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 1.0 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 The surface area is ≤7.5 μm and the specific surface area (BET) measured according to ISO 9277:2010 using nitrogen and the BET method is 0.5-150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, for example 3-10m 2 / g. For example, this heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50The particle size ranges from 1.0 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 For a surface area ≤7.5 μm and a specific surface area (BET) of 1-80 m² measured using nitrogen and the BET method according to ISO 9277:2010. 2 / g.

[0087] In particular, the heavy calcium carbonate-containing filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 1.5 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 The surface area is ≤7.5 μm and the specific surface area (BET) measured according to ISO 9277:2010 using nitrogen and the BET method is 0.5-150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, for example 3-10m 2 / g. For example, this heavy calcium carbonate filler material has a median particle size d measured by sedimentation. 50 The particle size ranges from 1.5 to 2.2 μm, and the top-cut particle size d is measured by sedimentation. 98 For a surface area ≤7.5 μm and a specific surface area (BET) of 1-80 m² measured using nitrogen and the BET method according to ISO 9277:2010. 2 / g.

[0088] It should be understood that the heavy calcium carbonate-containing filler material preferably has the following characteristics:

[0089] i) Median particle size d measured by sedimentation method 50 The thickness is 0.5-2.5 μm, preferably 1.0-2.2 μm, and most preferably 1.5-2.2 μm.

[0090] ii) Top-cut particle size d measured by sedimentation method 98 The value is ≤9μm, with the most preferred value being ≤7.5μm, and / or

[0091] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g.

[0092] For example, this heavy calcium carbonate filler material has

[0093] i) Median particle size d measured by sedimentation method 50 The thickness is 0.5-2.5 μm, preferably 1.0-2.2 μm, and most preferably 1.5-2.2 μm.

[0094] ii) Top-cut particle size d measured by sedimentation method 98 The value is ≤9μm, and the optimal value is ≤7.5μm.

[0095] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g.

[0096] In one embodiment, the heavy calcium carbonate-containing filler material has

[0097] i) Median particle size d measured by sedimentation method 50 The thickness is 1.0-2.2 μm, with 1.5-2.2 μm being the most preferred.

[0098] ii) Top-cut particle size d measured by sedimentation method 98 ≤7.5μm, and / or

[0099] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g

[0100] For example, this heavy calcium carbonate filler material has

[0101] i) Median particle size d measured by sedimentation method 50 The thickness is 1.0-2.2 μm, with 1.5-2.2 μm being the most preferred.

[0102] ii) Top-cut particle size d measured by sedimentation method 98 ≤7.5μm, and

[0103] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g.

[0104] In order to provide a masterbatch that functions in blends with polyester resins for the production of fibers or nonwovens, the masterbatch is required to contain a surface-treated filler material product, which contains at least one heavy calcium carbonate filler material.

[0105] In other words, the at least one heavy calcium carbonate filler material is surface-treated with a surface treatment agent.

[0106] Therefore, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material. The treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material preferably comprises...

[0107] i. At least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride comprising a succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent, and / or

[0108] ii. At least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C4-C24.

[0109] For example, the treatment layer on the surface of the at least one heavy calcium carbonate filler material includes

[0110] i. At least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride comprising a succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent, or

[0111] ii. At least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C4-C24.

[0112] According to one embodiment of the invention, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride being composed of succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent. Preferably, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride being composed of succinic anhydride monosubstituted with a group that is a linear aliphatic group having a total carbon atom count of at least C2 to C30 in the substituent. Alternatively or additionally, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride being composed of a succinic anhydride with a monosubstituted group, the group being a branched aliphatic group with a total carbon atom count of at least C3 to C30 in the substituent. Alternatively or additionally, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride being composed of a succinic anhydride with a monosubstituted group, the group being a cyclic aliphatic group with a total carbon atom count of at least C5 to C30 in the substituent.

[0113] Therefore, it should be noted that the at least one monosubstituted succinic anhydride can be a single type of monosubstituted succinic anhydride. Alternatively, the at least one monosubstituted succinic anhydride can be a mixture of two or more types of monosubstituted succinic anhydrides. For example, the at least one monosubstituted succinic anhydride can be a mixture of two or three types of monosubstituted succinic anhydrides (such as two types of monosubstituted succinic anhydrides).

[0114] In one embodiment of the present invention, the at least one monosubstituted succinic anhydride is a type of monosubstituted succinic anhydride.

[0115] It should be understood that the at least one monosubstituted succinic anhydride represents a surface treatment agent and is composed of succinic anhydride with a monosubstituted group selected from any linear, branched, aliphatic, and cyclic group having a total carbon atom count of C2 to C30 in the substituent.

[0116] In one embodiment of the invention, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of C3 to C20 in the substituents. For example, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of C4 to C18 in the substituents. Preferably, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of succinic anhydrides with a monosubstituted group, the group being a linear aliphatic group having a total carbon atom count of C3 to C20, preferably C4 to C18, and / or a salt thereof. Additionally or alternatively, the surface-treated filler material product comprises a treated layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treated layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of succinic anhydrides with a monosubstituted group, the group being a branched aliphatic group having a total carbon atom count of C3 to C20, preferably C4 to C18, and / or a salt thereof. Additionally or alternatively, the surface-treated filler material product includes a treatment layer on the surface of the at least one heavy calcium carbonate filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of succinic anhydrides using a monosubstituted group, the group being a cyclic aliphatic group having a total carbon atom count of C5 to C20, preferably C5 to C18, and / or a salt thereof.

[0117] In one embodiment of the invention, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of a succinic anhydride monosubstituted with one group, the group being a linear aliphatic group having a total carbon atom count of C2 to C30, preferably C3 to C20, and most preferably C4 to C18 in the substituent. Alternatively or additionally, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of a succinic anhydride monosubstituted with one group, the group being a branched aliphatic group having a total carbon atom count of C3 to C30, preferably C3 to C20, and most preferably C4 to C18 in the substituent.

[0118] Therefore, preferably, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of a succinic anhydride monosubstituted with a single group, the group being a linear or branched alkyl group having a total carbon atom count of C2 to C30, preferably C3 to C20, and most preferably C4 to C18 in the substituent.

[0119] For example, the surface-treated filler material product includes a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of a succinic anhydride monosubstituted with one group, the group being a linear alkyl group having a total carbon atom count of C2 to C30, preferably C3 to C20, and most preferably C4 to C18 in the substituent. Alternatively or additionally, the surface-treated filler material product includes a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, the treatment layer comprising at least one monosubstituted succinic anhydride, the at least one monosubstituted succinic anhydride being composed of a succinic anhydride monosubstituted with one group, the group being a branched alkyl group having a total carbon atom count of C3 to C30, preferably C3 to C20, and most preferably C4 to C18 in the substituent.

[0120] In one embodiment of the invention, the at least one monosubstituted succinic anhydride is at least one linear or branched alkyl monosubstituted succinic anhydride. For example, the at least one alkyl monosubstituted succinic anhydride is selected from ethyl succinic anhydride, propyl succinic anhydride, butyl succinic anhydride, triisobutyl succinic anhydride, pentyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof.

[0121] Therefore, it should be understood that, for example, the term "butyl succinic anhydride" includes both linear and branched butyl succinic anhydrides. A specific example of linear butyl succinic anhydride is n-butyl succinic anhydride. Specific examples of branched butyl succinic anhydride are isobutyl succinic anhydride, sec-butyl succinic anhydride, and / or tert-butyl succinic anhydride.

[0122] Furthermore, it should be understood that, for example, the term "hexadecyl succinic anhydride" includes both linear and branched hexadecyl succinic anhydrides. A specific example of linear hexadecyl succinic anhydride is n-hexadecyl succinic anhydride. Specific examples of branched hexadecyl succinic anhydride are 14-methylpentadecanyl succinic anhydride, 13-methylpentadecanyl succinic anhydride, 12-methylpentadecanyl succinic anhydride, 11-methylpentadecanyl succinic anhydride, 10-methylpentadecanyl succinic anhydride, 9-methylpentadecanyl succinic anhydride, 8-methylpentadecanyl succinic anhydride, 7-methylpentadecanyl succinic anhydride, 6-methylpentadecanyl succinic anhydride, 5-methylpentadecanyl succinic anhydride, 4-methylpentadecanyl succinic anhydride, 3-methylpentadecanyl succinic anhydride, 2-methylpentadecanyl succinic anhydride, 1-methylpentadecanyl succinic anhydride, 13-ethyltetradecyl succinic anhydride, 12-ethyltetradecyl succinic anhydride, 11-ethyltetradecyl succinic anhydride, 10-ethyltetradecyl succinic anhydride, 9-ethyltetradecyl succinic anhydride, 8-ethyl Tetradecyl succinic anhydride, 7-ethyltetradecyl succinic anhydride, 6-ethyltetradecyl succinic anhydride, 5-ethyltetradecyl succinic anhydride, 4-ethyltetradecyl succinic anhydride, 3-ethyltetradecyl succinic anhydride, 2-ethyltetradecyl succinic anhydride, 1-ethyltetradecyl succinic anhydride, 2-butyldodecyl succinic anhydride, 1-hexyldecyl succinic anhydride, 1-hexyl-2-decyl succinic anhydride, 2-hexyldecyl succinic anhydride, 6,12-dimethyltetradecyl succinic anhydride, 2,2-diethyldodecyl succinic anhydride, 4,8,12-trimethyltetrazyl succinic anhydride, 2,2,4,6,8-pentamethylundecyl succinic anhydride, 2-ethyl-4-methyl-2-(2-methylpentyl)-heptyl succinic anhydride and / or 2-ethyl-4,6-dimethyl-2-propylnonyl succinic anhydride.

[0123] Furthermore, it should be understood that, for example, the term "octadecyl succinic anhydride" includes both linear and branched octadecyl succinic anhydrides. A specific example of linear octadecyl succinic anhydride is n-octadecyl succinic anhydride. Specific examples of branched hexadecyl succinic anhydrides are 16-methylheptadecyl succinic anhydride, 15-methylheptadecyl succinic anhydride, 14-methylheptadecyl succinic anhydride, 13-methylheptadecyl succinic anhydride, 12-methylheptadecyl succinic anhydride, 11-methylheptadecyl succinic anhydride, 10-methylheptadecyl succinic anhydride, 9-methylheptadecyl succinic anhydride, 8-methylheptadecyl succinic anhydride, 7-methylheptadecyl succinic anhydride, 6-methylheptadecyl succinic anhydride, 5-methylheptadecyl succinic anhydride, 4-methylheptadecyl succinic anhydride, 3-methylheptadecyl succinic anhydride, 2-methylheptadecyl succinic anhydride, 1-methylheptadecyl succinic anhydride, 14-methylheptadecyl succinic anhydride, 15 ... 1,3-Ethylhexadecylsuccinic anhydride, 12-Ethylhexadecylsuccinic anhydride, 11-Ethylhexadecylsuccinic anhydride, 10-Ethylhexadecylsuccinic anhydride, 9-Ethylhexadecylsuccinic anhydride, 8-Ethylhexadecylsuccinic anhydride, 7-Ethylhexadecylsuccinic anhydride, 6-Ethylhexadecylsuccinic anhydride, 5-Ethylhexadecylsuccinic anhydride, 4-Ethylhexadecylsuccinic anhydride, 3-Ethylhexadecylsuccinic anhydride, 2-Ethylhexadecylsuccinic anhydride, 1-Ethylhexadecylsuccinic anhydride, 2-Hexyldodecylsuccinic anhydride, 2-Heptylundecylsuccinic anhydride, isooctadecylsuccinic anhydride and / or 1-Octyl-2-decylsuccinic anhydride.

[0124] In one embodiment of the invention, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate filler material, the treatment layer comprising at least one alkyl monosubstituted succinic anhydride selected from butyl succinic anhydride, hexyl succinic anhydride, heptyl succinic anhydride, octyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, and mixtures thereof.

[0125] In one embodiment of the invention, the at least one monosubstituted succinic anhydride is an alkyl monosubstituted succinic anhydride of a certain type. For example, the alkyl monosubstituted succinic anhydride is butyl succinic anhydride. Alternatively, the alkyl monosubstituted succinic anhydride is hexyl succinic anhydride. Alternatively, the alkyl monosubstituted succinic anhydride is heptyl succinic anhydride or octyl succinic anhydride. Alternatively, the alkyl monosubstituted succinic anhydride is hexadecyl succinic anhydride. For example, the alkyl monosubstituted succinic anhydride is linear hexadecyl succinic anhydride such as n-hexadecyl succinic anhydride or branched hexadecyl succinic anhydride such as 1-hexyl-2-decyl succinic anhydride. Alternatively, the alkyl monosubstituted succinic anhydride is octadecyl succinic anhydride. For example, the alkyl monosubstituted succinic anhydride is linear octadecyl succinic anhydride such as n-octadecyl succinic anhydride or branched octadecyl succinic anhydride such as isooctadecyl succinic anhydride or 1-octyl-2-decyl succinic anhydride.

[0126] In one embodiment of the present invention, the alkyl monosubstituted succinic anhydride is butyl succinic anhydride, such as n-butyl succinic anhydride.

[0127] In one embodiment of the invention, the at least one monosubstituted succinic anhydride is a mixture of two or more types of alkyl monosubstituted succinic anhydrides. For example, the at least one monosubstituted succinic anhydride is a mixture of two or three types of alkyl monosubstituted succinic anhydrides.

[0128] According to another embodiment of the invention, the surface-treated filler material product comprises a treatment layer on the surface of the at least one heavy calcium carbonate filler material, the treatment layer comprising at least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C4-C24, more preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C12-C20, and most preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C16-C18.

[0129] The carboxylic acid used in this invention can be selected from one or more straight-chain, branched-chain, saturated or unsaturated, and / or alicyclic carboxylic acids. Preferably, the alicyclic carboxylic acid is a monocarboxylic acid, characterized by the presence of a single carboxyl group. The carboxyl group is located at the end of the carbon skeleton.

[0130] In one embodiment of the invention, the aliphatic linear or branched carboxylic acid and / or its salt is selected from saturated unbranched carboxylic acids, preferably from the group consisting of: valeric acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, eicosanoic acid, and arganic acid. Acids, trisaccharides, tetrasaccharides, their salts, their anhydrides, and mixtures thereof.

[0131] In another embodiment of the invention, the aliphatic linear or branched carboxylic acid and / or its salts are selected from caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and mixtures thereof. Preferably, the aliphatic carboxylic acid is selected from myristic acid, palmitic acid, stearic acid, their salts, their anhydrides, and mixtures thereof.

[0132] Preferably, the aliphatic carboxylic acid and / or its salt is stearic acid and / or stearate.

[0133] Alternatively, the unsaturated aliphatic linear or branched carboxylic acid is preferably selected from myristoleic acid, palmitoleic acid, fusible acid, oleic acid, trans-oleic acid, isoleic acid, linoleic acid, α-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, and mixtures thereof. More preferably, the unsaturated aliphatic linear or branched carboxylic acid is selected from myristoleic acid, palmitoleic acid, fusible acid, oleic acid, trans-oleic acid, isoleic acid, linoleic acid, α-linolenic acid, and mixtures thereof. Most preferably, the unsaturated aliphatic linear or branched carboxylic acid is oleic acid and / or linoleic acid, preferably oleic acid or linoleic acid, and most preferably linoleic acid.

[0134] The surface-treated filler material product of the present invention is preferably formed as follows: the at least one heavy calcium carbonate-containing filler material and the surface treatment agent are provided, the at least one heavy calcium carbonate-containing filler material is in contact with the at least one surface treatment agent, such that a treatment layer containing the surface treatment agent and / or its salt is formed on the surface of the at least one heavy calcium carbonate-containing filler material.

[0135] It should be understood that the treatment layer on the surface of the at least one heavy calcium carbonate filler material preferably contains the surface treatment agent and / or its salt. That is, a chemical reaction can occur between the at least one heavy calcium carbonate filler material and the surface treatment agent. In other words, the treatment layer formed on the surface of the at least one heavy calcium carbonate filler material may contain the surface treatment agent and / or its salt.

[0136] The term "salt" in this surface treatment agent refers to a product obtained by contacting the at least one heavy calcium carbonate-containing filler material with the surface treatment agent. The reaction product is formed between at least a portion of the applied surface treatment agent and reactive molecules located on the surface of the at least one heavy calcium carbonate-containing filler material.

[0137] In one embodiment, the surface-treated filler material product comprises 0.1-3% by weight of the treated layer, based on the total dry weight of the at least one heavy calcium carbonate filler material.

[0138] Surface treatment methods for fillers are known to those skilled in the art and are described, for example, in EP3192837A1, EP2770017A1 and WO2016023937.

[0139] It should be understood that, regarding the median particle size d... 50 Top-cut particle size d 98 The above information regarding specific surface area (BET) also applies to this surface-treated filler material product, namely, surface-treated heavy calcium carbonate filler material.

[0140] Additionally or alternatively, the surface-treated filler material product, i.e., the surface-treated heavy calcium carbonate-containing filler material, preferably has a low moisture content. Specifically, the moisture content of the surface-treated heavy calcium carbonate-containing filler material, based on the total weight of the at least one surface-treated heavy calcium carbonate-containing filler material, is preferably ≤0.25% by weight, more preferably ≤0.2% by weight, even more preferably ≤0.15% by weight, and most preferably ≤0.1% by weight. Additionally or alternatively, the moisture content of the surface-treated heavy calcium carbonate-containing filler material, based on the total dry weight of the at least one surface-treated heavy calcium carbonate-containing filler material, is preferably ≥0.005% by weight, more preferably ≥0.01% by weight, and most preferably ≥0.02% by weight.

[0141] In one embodiment, the moisture content of the surface-treated filler material product (i.e., the surface-treated heavy calcium carbonate-containing filler material) is preferably 0.005% to 0.25% by weight, more preferably 0.01% to 0.2% by weight, even more preferably 0.01% to 0.15% by weight, and most preferably 0.02% to 0.1% by weight, based on the total dry weight of the at least one surface-treated heavy calcium carbonate-containing filler material.

[0142] Therefore, preferably, the surface-treated filler material product (i.e., the surface-treated heavy calcium carbonate-containing filler material) preferably has the following characteristics:

[0143] i) Median particle size d measured by sedimentation method 50 The thickness is 0.5-2.5 μm, preferably 1.0-2.2 μm, and most preferably 1.5-2.2 μm.

[0144] ii) Top-cut particle size d measured by sedimentation method 98 The value is ≤9μm, with the most preferred value being ≤7.5μm, and / or

[0145] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and / or

[0146] iv) Moisture content of ≤0.25% by weight, as measured according to ISO 787 / 2, based on the total weight of the at least one surface-treated material containing heavy calcium carbonate filler.

[0147] For example, the surface-treated filler material product (i.e., the surface-treated filler material containing heavy calcium carbonate) has

[0148] i) Median particle size d measured by sedimentation method 50 The thickness is 0.5-2.5 μm, preferably 1.0-2.2 μm, and most preferably 1.5-2.2 μm.

[0149] ii) Top-cut particle size d measured by sedimentation method 98 The value is ≤9μm, and the optimal value is ≤7.5μm.

[0150] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and

[0151] iv) Moisture content of ≤0.25% by weight, as measured according to ISO 787 / 2, based on the total weight of the at least one surface-treated material containing heavy calcium carbonate filler.

[0152] In one embodiment, the surface-treated filler material product (i.e., the surface-treated heavy calcium carbonate-containing filler material) has

[0153] i) Median particle size d measured by sedimentation method 50 The thickness is 1.0-2.2 μm, with 1.5-2.2 μm being the most preferred.

[0154] ii) Top-cut particle size d measured by sedimentation method 98 ≤7.5μm, and / or

[0155] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and / or

[0156] iv) Moisture content of ≤0.25% by weight, as measured according to ISO 787 / 2, based on the total weight of the at least one surface-treated material containing heavy calcium carbonate filler.

[0157] For example, the surface-treated filler material product (i.e., the surface-treated filler material containing heavy calcium carbonate) has

[0158] i) Median particle size d measured by sedimentation method 50 The thickness is 1.0-2.2 μm, with 1.5-2.2 μm being the most preferred.

[0159] ii) Top-cut particle size d measured by sedimentation method 98 ≤7.5μm, and

[0160] iii) Specific surface area (BET) measured using nitrogen and the BET method according to ISO 9277:2010 is 0.5–150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and

[0161] iv) Moisture content of ≤0.25% by weight, as measured according to ISO 787 / 2, based on the total weight of the at least one surface-treated material containing heavy calcium carbonate filler.

[0162] It should be understood that the polypropylene-based masterbatch contains the surface-treated filler material product with a high filler loading.

[0163] Therefore, the polypropylene-based masterbatch comprises, by weight, 15-35% of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and by weight, 65-85% of a surface-treated filler material product containing at least one heavy calcium carbonate filler material, based on the total weight of the polypropylene-based masterbatch.

[0164] For example, the polypropylene-based masterbatch comprises 28-32% by weight of a propylene polymer based on the total weight of the polypropylene-based masterbatch and 68-72% by weight of a surface-treated filler material product based on the total weight of the polypropylene-based masterbatch.

[0165] Preferably, the polypropylene-based masterbatch is substantially composed of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133 and a surface-treated filler material product containing at least one heavy calcium carbonate filler material.

[0166] However, it is possible to add additives that are typically used in the product to be prepared to the polypropylene-based masterbatch.

[0167] Therefore, the polypropylene-based masterbatch preferably does not contain any polymer material different from the propylene polymer in an amount equal to or greater than 5% by weight, preferably equal to or greater than 3% by weight, and most preferably equal to or greater than 1% by weight based on the total weight of the polypropylene-based masterbatch.

[0168] Additionally or alternatively, the polypropylene-based masterbatch preferably does not contain any filler material that is different from the surface-treated filler material product, in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene-based masterbatch.

[0169] In a preferred embodiment, the polypropylene masterbatch does not contain a polymeric material different from the propylene polymer in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene masterbatch, or the polypropylene masterbatch does not contain a filler material different from the surface-treated filler material product in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene masterbatch.

[0170] Alternatively, the polypropylene masterbatch does not contain polymeric materials different from the propylene polymer in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene masterbatch, and the polypropylene masterbatch does not contain filler materials different from the surface-treated filler material product in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene masterbatch.

[0171] Furthermore, preferably, the amount of material in the polypropylene-based masterbatch that is different from the propylene polymer and the surface-treated filler material product is equal to or less than 10% by weight, more preferably equal to or less than 8% by weight, and most preferably equal to or less than 5% by weight, based on the total weight of the polypropylene-based masterbatch.

[0172] The polypropylene-based masterbatch may contain optional additives typically present in the product to be prepared. For example, the polypropylene-based masterbatch may contain one or more additives selected from, for example, antioxidants, light stabilizers, fluorescent whitening agents, blue dyes, anti-caking agents, white pigments, and mixtures thereof.

[0173] This polypropylene-based masterbatch is obtained by methods known in the art and is typically used in the product to be prepared. The polypropylene-based masterbatch is preferably obtained by mixing and / or kneading a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133 with the surface-treated filler material product to form a mixture, and then continuously granulating the resulting mixture. For example, the polypropylene-based masterbatch is obtained by compounding a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133 with the surface-treated filler material product.

[0174] The propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, the surface-treated filler material product, and optional additives, if present, can be (pre)mixed and / or kneaded using a suitable mixer, such as a Henschel mixer, super mixer, drum mixer, etc. The compounding step can be accomplished using a suitable extruder, preferably a twin-screw extruder (co- or counter-rotating), or any other suitable continuous compounding equipment such as a continuous co-kneader (Buss), continuous mixer (FarrelPomini), annular extruder (Extricom), or similar device. The continuous polymer feed from the extrusion can be pelletized using underwater pelletizing, eccentric pelletizing, and water ring pelletizing with a (hot-cut) die face, or using underwater (cold-cut) wire pelletizing and conventional wire pelletizing to form pellets from the extruded polymer feed. In one embodiment, the polypropylene-based masterbatch is obtained by compounding a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133 and the surface-treated filler material product, without the need for premixing and / or pre-kneading steps. In this embodiment, the propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133 and the surface-treated filler material product are preferably compounded in a twin-screw extruder via different hoppers. The resulting continuous polymer feedstock is granulated as described above.

[0175] Therefore, the polypropylene-based masterbatch can be in the form of pellets, beads, or granules.

[0176] It should be understood that the polypropylene-based masterbatch is preferably in pellet form.

[0177] The size and form of the pellets are within the range typically used for the product to be prepared. Those skilled in the art can easily select and adjust the size and form according to specific needs and the compounding production line used.

[0178] Products and methods

[0179] Another aspect of the invention relates to a polyester fiber composition comprising, by weight, 86-99.3%, preferably 90-96.5%, and most preferably 92-94%, of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, and by weight, the polypropylene-based masterbatch, by weight, preferably 3.5-10%, and most preferably 6-8%, of the total weight of the polyester fiber composition.

[0180] For details regarding the limitations of the polypropylene-based masterbatch and its preferred embodiments, please refer to the statements provided above in the discussion of the technical details of the polypropylene-based masterbatch of the present invention.

[0181] It should be understood that the term "polyester fiber composition" refers to a polyester composition suitable for preparing fibers (e.g., in the form of nonwoven fabrics or filaments). More specifically, the term refers to a polyester composition suitable for preparing polyester fibers (e.g., in the form of polyester nonwoven fabrics or filaments). Thus, fibers, for example, in the form of polyester nonwoven fabrics or filaments, are prepared from a polyester fiber composition comprising 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight, of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, based on the total weight of the polyester fiber composition, and 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight, of the polypropylene-based masterbatch based on the total weight of the polyester fiber composition.

[0182] It should be noted that the polyester resin can be a single type of polyester resin. Alternatively, the polyester resin can be a mixture of two or more types of polyester resin. For example, the polyester resin can be a mixture of two or three types of polyester resin, such as a mixture of two types of polyester resin.

[0183] In one embodiment of the invention, the polyester resin comprises a type of polyester resin, preferably composed of a type of polyester resin.

[0184] Generally, the term "polyester" refers to a polymer obtained by at least partial polycondensation of a diol and a dicarboxylic acid. As the dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-dicarboxylic acid, adipic acid, or sebacic acid can be used. As the diol, ethylene glycol, trimethylene glycol, tetramethylene glycol, or cyclohexanediol can be used. The term "polyester" also refers to polymers prepared from lactic acid, polymers prepared from the ring-opening polymerization of lactide (cyclic ester), or polymers obtained through biosynthesis such as enzymatic processes.

[0185] Additionally or alternatively, the polyester resin may be a partially or fully bio-based polyester resin, i.e., wherein the monomers are derived from a renewable biomass source. Examples of monomers include those that can be prepared using bio-derived compounds. For example, said monomers include, but are not limited to, ethylene glycol (EG), furanyl dicarboxylic acid (FDCA), polyvinyl furanate (PEF), which can be produced using fructose, and mixtures thereof. Other monomers suitable for the preparation of bio-based polyesters are described, for example, in WO2014 / 100265A1, which is therefore incorporated herein by reference.

[0186] Alternatively or additionally, the polyester resin is a PET recycled material, such as PET bottle waste from the PET recycling stream.

[0187] Therefore, the polyester resin of the present invention preferably comprises: one or more saturated polyester resins selected from polylactic acid, polylactic acid-based polymers, aliphatic polyesters such as polyhydroxyalkanoates, for example polyhydroxybutyrate, poly-3-hydroxybutyrate (P3HB), polyhydroxyvalerate, polyhydroxybutyrate-polyhydroxyvalerate copolymer, poly(3-hydroxybutyrate-copoly-3-hydroxyvalerate); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polyglycolic acid, poly(di(2-hydroxybutyrate)) Alkyl ketones and their mixtures.

[0188] In one embodiment, the polyester resin is preferably polyethylene terephthalate (PET).

[0189] Therefore, it can be understood that the polyester resin is preferably a saturated polyester resin.

[0190] The polyester resin is required to have an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5.

[0191] Typically, the polyester resin may have a number-average molecular weight Mn of 5,000 to 200,000 g / mol, preferably 10,000 to 100,000 g / mol, and more preferably 15,000 to 80,000 g / mol, as measured by gel permeation chromatography.

[0192] Additionally or alternatively, the polyester resin has a specific gravity of 0.5-5, preferably 0.7-4, and more preferably 1-3, as measured according to ASTM D782.

[0193] Additionally or alternatively, the polyester resin has a glass transition temperature Tg of 35-90°C, preferably 40-70°C, and more preferably 45-70°C, as measured by differential scanning calorimetry (DSC).

[0194] In one embodiment, the polyester resin has a number-average molecular weight Mn of 5,000 to 200,000 g / mol, preferably 10,000 to 100,000 g / mol, more preferably 15,000 to 80,000 g / mol, as measured by gel permeation chromatography; or a specific gravity of 0.5-5, preferably 0.7-4, and more preferably 1-3, as measured according to ASTM D782; or a glass transition temperature Tg of 35-90°C, preferably 40-70°C, and more preferably 45-70°C, as measured by differential scanning calorimetry (DSC).

[0195] Preferably, the polyester resin has a number-average molecular weight Mn of 5,000 to 200,000 g / mol, preferably 10,000 to 100,000 g / mol, more preferably 15,000 to 80,000 g / mol, as measured by gel permeation chromatography; a specific gravity of 0.5-5, preferably 0.7-4, and more preferably 1-3, as measured according to ASTM D782; and a glass transition temperature Tg of 35-90°C, preferably 40-70°C, and more preferably 45-70°C, as measured by differential scanning calorimetry (DSC).

[0196] It should be understood that the polyester fiber composition comprises 86-99.3% by weight of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, based on the total weight of the polyester fiber composition, and 0.7-14% by weight of the polypropylene-based masterbatch based on the total weight of the polyester fiber composition.

[0197] Preferably, the polyester fiber composition comprises 90-96.5% by weight, and most preferably 92-94% by weight, of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, based on the total weight of the polyester fiber composition, and 3.5-10% by weight, and most preferably 6-8% by weight, of the polypropylene-based masterbatch based on the total weight of the polyester fiber composition. Such amounts are particularly suitable for forming polyester nonwovens or filaments from the polyester fiber composition.

[0198] Preferably, the polypropylene-based masterbatch is added to the polyester resin to achieve a high filler loading.

[0199] Therefore, the polyester fiber composition preferably contains 0.5-10% by weight of the surface-treated filler material product based on the total weight of the polyester fiber composition. For example, the polyester fiber composition preferably contains 2-8% by weight, and most preferably 4-6% by weight, of the surface-treated filler material product based on the total weight of the polyester fiber composition.

[0200] The polyester fiber composition may further include additives such as coloring pigments, fibers such as cellulose, glass or wood fibers, dyes, waxes, lubricants, oxidation stabilizers and / or UV stabilizers, antioxidants and other fillers such as carbon black, TiO2, mica, clay, precipitated silica, talc or calcined kaolin.

[0201] According to one embodiment, the polyester fiber composition comprises at least one heavy calcium carbonate-containing filler material that is different from the surface-treated filler material product of the polypropylene-based masterbatch, the at least one heavy calcium carbonate-containing filler material having a median weight particle size d of 0.5-2.5 μm as measured by sedimentation. 50 And the top-cut particle size d, which is ≤9μm as measured by sedimentation method. 98 Preferably, the other filler is selected from carbon black, silica, heavy natural calcium carbonate, precipitated calcium carbonate, nanofillers, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium dioxide, wollastonite, and mixtures thereof. Preferably, the polyester fiber composition contains another filler, such as carbon black, TiO2, mica, clay, precipitated silica, talc, or calcined kaolin.

[0202] Preferably, the other filler is present in the polyester fiber composition in a volume ratio of 10:90 to 90:10, preferably 25:75 to 75:25, more preferably 40:60 to 60:40, such as 50:50, to the surface-treated filler material product.

[0203] If present, the additive is present in the polyester fiber composition in a total amount of 0.01-10% by weight based on the total weight of the polyester fiber composition. For example, the additive is present in the polyester fiber composition in a total amount of 0.01-8% by weight, more preferably 0.1-5% by weight based on the total weight of the polyester fiber composition.

[0204] In view of the foregoing, it should be noted that the present invention also relates to the use of this polypropylene-based masterbatch for polyester fibers. Specifically, the polypropylene-based masterbatch for polyester fibers comprises...

[0205] Based on the total weight of the polypropylene masterbatch, 15-35% by weight of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and

[0206] Based on the total weight of the polypropylene masterbatch, a surface-treated filler material product comprising at least one heavy calcium carbonate filler material at 65-85% by weight, the surface-treated filler material product has

[0207] - The weight median particle size d, measured by sedimentation, is 0.5–2.5 μm. 50 ,and

[0208] - The top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

[0209] And the polyester fiber contains

[0210] Based on the total weight of the polyester fibers, a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5 comprises 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight.

[0211] The polypropylene-based masterbatch comprises 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight, based on the total weight of the polyester fiber.

[0212] It should be understood that the present invention also relates to polyester nonwovens or filaments formed from polyester fiber compositions as defined herein.

[0213] It should be understood that the term "fiber" refers to a product whose length is significantly greater than its width. Therefore, fibers typically have a specific length. It should be noted that the length and denier of the fiber depend on the product to be prepared, and those skilled in the art will adjust them according to specific needs. For example, fibers may have a length of 10-150 mm, preferably 20-120 mm. Additionally or alternatively, the fiber may have a denier number, or dpf, per fiber of 0.1-25 dpf, preferably 0.2-20 dpf. The fiber can also be in the form of a "filament," which is a continuous fiber. Therefore, such a filament preferably has a denier number of 0.1-25 dpf, preferably 0.2-20 dpf. The unit "dpf" refers to the denier number per fiber.

[0214] In contrast, "nonwovens" refer to products made by binding or felting polyester fibers together through mechanical, thermal and / or chemical processes, rather than weaving them together as in traditional fabrics.

[0215] The polyester nonwoven fabric or filament can be prepared by any method known to those skilled in the art. A suitable method for preparing the polyester nonwoven fabric or filament includes the following steps:

[0216] a) Provide a polyester resin in an amount of 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight, based on the total weight of the polyester product, the polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5.

[0217] b) Provide a polypropylene-based masterbatch in an amount of 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight, based on the total weight of the polyester product.

[0218] c) Contact the polyester resin from step a) with the polypropylene-based masterbatch from step b) to obtain a polyester fiber composition, and

[0219] d) Shape the polyester fiber composition obtained in step c) to obtain a polyester nonwoven fabric or filament.

[0220] In one embodiment, the polyester nonwoven fabric or filament further comprises additives. The method therefore includes the additional step of providing one or more additives selected from coloring pigments, fibers such as cellulose, glass or wood fibers, dyes, waxes, lubricants, oxidation stabilizers and / or UV stabilizers, antioxidants, and other fillers such as carbon black, TiO2, mica, clay, precipitated silica, talc, or calcined kaolin.

[0221] The one or more additives are preferably added in step c), whereby the polyester resin of step a), the polypropylene masterbatch of step b), and the one or more additives are contacted in any order.

[0222] According to step c) of the method of the present invention, the components of steps a) and b) are contacted in any order. Preferably, the contact in step c) is carried out by mixing and / or extruding the components to form a mixture. Optionally, one or more additives may be added to the mixture during contact step c).

[0223] In one embodiment, in contact step c), the polyester resin of step a) is first provided, and then the polypropylene-based masterbatch of step b) is added to the polyester resin in one or more steps under mixing. Preferably, the polyester resin of step a) and the polypropylene-based masterbatch of step b) are added simultaneously, and then mixed and / or extruded.

[0224] If present, the one or more additives are subsequently or simultaneously (preferably simultaneously) mixed with the polypropylene-based masterbatch and / or the polyester resin.

[0225] Contact step c) can be performed in any manner known to those skilled in the art, including but not limited to blending, extrusion, kneading and high-speed mixing, preferably extrusion.

[0226] Preferably, contact step c) is carried out in a closed mixer and / or an external mixer, wherein the external mixer is preferably a drum mixer. In a preferred embodiment, contact step c) is carried out in an extruder via melt extrusion. It should be understood that step c) is preferably carried out at a melting temperature at least 2°C, preferably at least 5°C, and most preferably at least 10°C higher than the melting point of the polyester resin. For example, step c) is carried out at a melting temperature at 2°C-30°C, preferably 5°C-25°C, and most preferably 10°C-20°C higher than the melting point of the polyester resin.

[0227] The mixture from step c) is shaped into a polyester nonwoven fabric or filament in step d). This shaping can be carried out by any method known to those skilled in the art to obtain polyester nonwoven fabrics or filaments. These methods include, but are not limited to, extrusion processes, co-extrusion processes, spunbond processes, fiber spinning processes, and staple fiber production processes. For example, the shaping step d) is performed via a spinneret.

[0228] Preferably, the contact step c) is performed before the forming step d). More preferably, the contact step c) is performed by extruding the polyester resin of step a) and the polypropylene-based masterbatch of step b) to form a polyester fiber composition, and then forming the polyester fiber composition into a polyester nonwoven fabric or filament via a spinneret in step d).

[0229] It should be understood that the method may include further steps, such as processing the polyester nonwoven fabric or filament into any desired article. These processing steps are well known to those skilled in the art and depend on the article to be prepared, and may be adapted accordingly by those skilled in the art.

[0230] In another aspect, the present invention therefore relates to articles formed from the polyester nonwoven fabric or filaments. Preferably, the articles are selected from hygiene products, medical and health care products, wiping products such as refreshing or cleaning wipes, paper towel products, furniture decorations, geotextile products, filtration products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, building products, automotive parts, bottles, cups, etc.

[0231] In another aspect, the present invention relates to the use of polypropylene-based masterbatch in the production of polyester nonwovens or filaments, wherein the polypropylene-based masterbatch comprises

[0232] a) A propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) measured according to ISO 1133, based on 15-35% by weight of the total weight of the polypropylene-based masterbatch, and

[0233] b) A surface-treated filler material product comprising at least one heavy calcium carbonate filler material, at 65-85% by weight of the total weight of the polypropylene-based masterbatch. This surface-treated filler material product has…

[0234] - The weight median particle size d, measured by sedimentation, is 0.5–2.5 μm. 50 ,and

[0235] - The top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

[0236] The scope and benefits of the invention will be better understood based on the following embodiments, which are intended to illustrate certain implementations of the invention and are not limiting. Attached Figure Description

[0237] Figure 1 A sketch of a fiber production line is shown. Detailed Implementation

[0238] The scope and benefits of the invention will be better understood based on the following embodiments, which are intended to illustrate certain implementations of the invention and are not limiting.

[0239] Example

[0240] 1. Measurement Method

[0241] The measurement methods implemented in the examples will be described below.

[0242] Particle size distribution

[0243] Median particle size d 50 (wt) and weight-cut particle size d 98 (wt) was determined by the sedimentation method, which is the analysis of sedimentation behavior in a gravitational field. This measurement was performed using a Sedigraph from Micromeritics Instrument Corporation. TM The method and instrumentation are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments. Measurements were performed in an aqueous solution of 0.1% by weight Na₄P₂O₇. The sample was dispersed using a high-speed stirrer and ultrasonication.

[0244] The methods and instruments are known to those skilled in the art and are commonly used to determine the particle size of fillers and pigments.

[0245] Specific surface area (SSA)

[0246] Specific surface area was measured using the BET method according to ISO 9277:2010 on a Micromeritics ASAP 2460 instrument from Micromeritics, with nitrogen as the adsorbed gas. Prior to measurement, the surface area was heated at 150°C for 60 minutes under vacuum (10... -5 The samples were pretreated in the (B) region.

[0247] Amount of surface treatment layer

[0248] The amount of the treatment layer on a calcium carbonate-containing material is theoretically calculated from the BET value of the untreated calcium carbonate-containing material and the amount of one or more compounds used for surface treatment. It is assumed that 100% of these compounds exist as a surface treatment layer on the surface of the calcium carbonate-containing material.

[0249] molecular weight

[0250] Number average molecular weight M n Measured by gel permeation chromatography according to ISO 16014-1:2019 and ISO 16014-2 / 2019.

[0251] melt flow rate

[0252] Melt flow rate was measured on Instron's CEAST modular online melt flow instrument. The instrument and measurement method are known to those skilled in the art. Melt flow rate was measured using procedure A according to DIN EN ISO 1133-1:2011. The polymer sample to be measured was in the form of granules or pellets with a length of 1 mm–5 mm. A quantity of 6–9 g was used for measurement. The sample was measured at 210 °C with a nominal load of 2.16 kg using a capillary die with an inner diameter of 2.095 mm and a length of 8.00 mm. No-load preheating was performed for 300 seconds, with a measurement length of 20 mm.

[0253] Melt flow rates were obtained under standard conditions. The term "standard conditions" according to the invention refers to standard ambient temperature and pressure (SATP), which is a temperature of 298.15 K (25 °C) and an absolute pressure of exactly 100,000 Pa (1 bar, 14.5 psi, 0.98692 atm). All measurements were performed on samples prepared and stored under similar conditions.

[0254] Moisture content

[0255] Moisture content is determined according to ISO 787 / 2.

[0256] Special

[0257] The fractional values ​​were measured according to EN ISO 2062 and correspond to the weight per 10,000 meters of yarn. A 100-meter sample was wound onto a standard Rycobel electronic winding wheel under a pretension of 0.5 cN / tex and weighed on an analytical balance (Mettler Toledo balance). The weight per 10,000 meters of yarn was then calculated.

[0258] Fiber toughness and elongation

[0259] Fiber toughness and elongation were measured according to ISO 2062:1993 on a Statimat ME+ instrument from Textechno. This instrument has a 100 N force sensor. The distance between the clamps was 250 mm. The analysis speed was 250 mm / min, and analysis was stopped when all 36 fibers broke. Toughness was calculated from breaking force and decitex, and expressed in centinewtons per decitex (cN / dtex). Elongation was the increase in length produced by stretching the yarn to its maximum load, and expressed as a percentage of its initial length (%).

[0260] 2. Instructions for Masterbatch (MB) Preparation:

[0261] The masterbatches listed in Table 1 have been prepared.

[0262] Table 1: Masterbatch Formulation

[0263] Borealis HG475 FB is a homopolymer polypropylene grade sold by Borealis. It has a melt flow rate of 27 g / 10 min measured according to ISO 1133-1 at 2.16 kg and 230°C, and a melt flow rate of 0.905 g / cm³ measured according to ISO 1183-1. 3 The density.

[0264] Aspun™ 6834 is a linear low-density polyethylene grade marketed by Dow Chemical. It has a melt index of 17 g / 10 min, measured according to ISO 1133 at 2.16 kg and 190°C. It also has a melt index of 0.95 g / cm³, measured according to ASTM D792. 3 The density.

[0265] Elvaloy™ AC 12024S is an ethylene-methacrylic acid copolymer sold by Dow Chemical. It has a melt index of 20 g / 10 min, measured according to ASTM D1238 at 2.16 kg and 190°C. It also has a melt index of 0.944 g / cm³, measured according to ASTM D792.3 The density.

[0266] NeoPET80 is a food-grade PET copolyester sold by NeoGroup. It has an intrinsic viscosity of 0.8 dl / g as measured by WN-B010-7040D.

[0267] GCC1: Heavy calcium carbonate, commercially available from Omya International AG (d 50 : 1.7μm; d 98 The surface was treated with 0.7% by weight succinic anhydride (Hydrores AS 1000, commercially available from Kemira Germany GmbH, Germany), based on the total weight of the heavy calcium carbonate (6 μm).

[0268] The particle distribution of calcium carbonate was measured using a Sedigraph 5120 from Micromeritics, Inc.

[0269] The masterbatch (MB) is produced on the Maris twin-screw extrusion compounding line. The polymer PET is pre-dried and then treated in an oven at 160°C for 4 hours.

[0270] The settings for masterbatch production are given in Table 2 below.

[0271] Table 2: Setup for Masterbatch Production

[0272] Instructions for fiber production:

[0273] Table 3 below shows the fiber formulation.

[0274] Table 3: Fiber formulation:

[0275] RT5140 is a polyester grade suitable for fiber spinning and is sold by Invista Resins & Fibers GmbH. It has an intrinsic viscosity of 0.65 dl / g as measured according to WN-B010-7040 D.

[0276] Processability results:

[0277] Fiber spinning trials were conducted on a Hills laboratory-scale fiber spinning production line. The fiber formulation was dry-blended and then extruded.

[0278] Fiber production line Figure 1 As shown in the image.

[0279] The fiber production line is set up as shown below, and further as shown in Table 4:

[0280] ▪ Extruder: 19mm screw, L / D ratio 30:1

[0281] Melt temperature 280℃

[0282] ▪ Melt pump set to 0.3cc / rev

[0283] ▪ Spinneret with 36 orifices

[0284] The hole is circular.

[0285] ▪ Each hole has a diameter of 0.35mm and an L / D ratio of 4.

[0286] ▪ Output: 0.3g / well / minute (~0.6kg / h)

[0287] ▪ Guide roller #1: 493m / min and 95℃

[0288] ▪ Guide roller #2: 1480m / min and 90℃

[0289] ▪ Guide roller #3: 1490m / min and 40℃

[0290] ▪ Draw ratio (guide rollers #1 to #2): 3

[0291] Table 4: Fiber Production Line Setup

[0292] Read the melt pump pressure from the control panel of the Hills fiber production line.

[0293] The maximum speed is obtained as follows: the fiber is wound around the guide roller #1 and the speed of the guide roller #1 is increased until the melt instability is observed at the spinneret.

[0294] Interpretation of Results:

[0295] It can be seen that, in terms of increasing melt pump pressure and decreasing maximum speed, this invention 1 provides a similar processability response to Comparative 1.

[0296] Comparisons 2 and 3 yielded worse responses than Comparison 1 and Invention 1, showing higher increases in melt pump pressure and lower maximum speeds. Surprisingly, Invention 1 performed better, given that Comparisons 2 and 3 are also based on polyolefins. In particular, the poor results obtained using Comparison 3 were unexpected, as it contained a compatibilizer typically used in polyolefin-PET blends.

[0297] The results of fiber properties are listed in Table 5.

[0298] Table 5: Fiber Performance Results

[0299] Example 1 of this invention presents similar toughness and shrinkage to Comparative Example 1. The increased elongation loss can be balanced by improving the annealing step between guide rollers #2 and #3. Comparative Examples 2 and 3 present different balances of tensile properties and, as mentioned above, have worse processability compared to Example 1 of this invention. Comparative Example 2 also exhibits a very high standard deviation in fiber elongation. Comparative Example 3 shows a very high standard deviation, which is certainly due to the unstable processing reported above.

Claims

1. Polypropylene-based masterbatch, which includes Based on the total weight of the polypropylene masterbatch, 15-35% by weight of a propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) as measured according to ISO 1133, and Based on the total weight of the polypropylene masterbatch, a surface-treated filler material product comprising at least one heavy calcium carbonate filler material at 65-85% by weight, the surface-treated filler material product has - The weight median particle size d, measured by sedimentation, is 0.5–2.5 μm. 50 ,and - The top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

2. The polypropylene-based masterbatch according to claim 1, wherein the propylene polymer is a random propylene copolymer or a propylene homopolymer, and / or the propylene polymer has a) The melt flow rate (MFR) measured according to ISO 1133 (230°C, 2.16 kg) is 20-40 g / 10 min, with the most preferred value being 22-37 g / 10 min, and / or b) The density, measured according to ISO 1183-1, is equal to or less than 0.910 g / cm³. 3 More preferably, the density is equal to or greater than 0.850 g / cm³. 3 And the optimal value is 0.850-0.910 g / cm³. 3 .

3. The polypropylene-based masterbatch according to claim 1 or 2, wherein the heavy calcium carbonate filler material is selected from marble, chalk, dolomite, limestone and mixtures thereof, and most preferably, the heavy calcium carbonate filler material is marble.

4. The polypropylene-based masterbatch according to any one of the preceding claims, wherein the surface-treated filler material product, i.e., the surface-treated heavy calcium carbonate-containing filler material, comprises a treatment layer on the surface of the at least one heavy calcium carbonate-containing filler material, which includes... i. At least one monosubstituted succinic anhydride and / or its salt, the monosubstituted succinic anhydride comprising a succinic anhydride monosubstituted with a group selected from linear, branched, aliphatic, and cyclic groups having a total carbon atom count of at least C2 to C30 in the substituent, and / or ii. At least one saturated or unsaturated aliphatic linear or branched carboxylic acid and / or its salt, preferably at least one aliphatic carboxylic acid and / or its salt with a total carbon atom count of C4-C24.

5. The polypropylene-based masterbatch according to any one of the preceding claims, wherein the surface-treated filler material product, i.e., the surface-treated heavy calcium carbonate-containing filler material, comprises the treated layer in an amount of 0.1-3% by weight based on the total dry weight of the at least one heavy calcium carbonate-containing filler material.

6. The polypropylene-based masterbatch according to claim 4 or 5, wherein the surface-treated filler material product, i.e., the surface-treated filler material containing heavy calcium carbonate, has - Median particle size d measured by sedimentation method 50 The thickness is 1.0-2.2 μm, preferably 1.5-2.2 μm, and - Top-cut particle size d measured by sedimentation method 98 ≤7.5μm, and / or - Specific surface area (BET), measured using nitrogen and the BET method according to ISO 9277:2010, is 0.5-150 m². 2 / g, preferably 1-80m 2 / g, more preferably 2-75m 2 / g, or even more preferably 2-40m 2 / g, and more preferably 3-25m 2 / g, optimal value 3-15m 2 / g, and / or - Moisture content of ≤0.25% by weight, measured according to ISO 787 / 2 based on the total weight of the product containing at least one surface-treated filler material.

7. The polypropylene-based masterbatch according to any one of the preceding claims, wherein the polypropylene-based masterbatch comprises 28-32% by weight of the propylene polymer based on the total weight of the polypropylene-based masterbatch, and 68-72% by weight of the surface-treated filler material product based on the total weight of the polypropylene-based masterbatch.

8. The polypropylene-based masterbatch according to any one of the preceding claims, wherein the polypropylene-based masterbatch does not contain a polymeric material different from the propylene polymer in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene-based masterbatch, and / or the polypropylene-based masterbatch does not contain a filler material different from the surface-treated filler material product in an amount equal to or greater than 5% by weight based on the total weight of the polypropylene-based masterbatch.

9. A polyester fiber composition comprising Based on the total weight of the polyester fiber composition, 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight, of a polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5, and... Based on the total weight of the polyester fiber composition, the polypropylene-based masterbatch according to any one of the preceding claims comprises 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight.

10. The polyester fiber composition according to claim 9, wherein the polyester fiber composition comprises the surface-treated filler material product, i.e., the surface-treated heavy calcium carbonate filler material, in an amount of 0.5-10% by weight, preferably 2-8% by weight and most preferably 4-6% by weight, based on the total weight of the polyester fiber composition.

11. The polyester fiber composition according to claim 9 or 10, wherein the polyester resin comprises: One or more saturated polyester resins selected from polylactic acid, polylactic acid-based polymers, aliphatic polyesters such as polyhydroxyalkanoates, for example polyhydroxybutyrate, poly-3-hydroxybutyrate (P3HB), polyhydroxyvalerate, polyhydroxybutyrate-polyhydroxyvalerate copolymer, poly(3-hydroxybutyrate-copoly-3-hydroxyvalerate); polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polyglycolic acid, poly(di(2-hydroxybutyrate)... Alkyl ketones and mixtures thereof, preferably, the polyester resin is polyethylene terephthalate (PET).

12. A polyester nonwoven fabric or filament formed from the polyester fiber composition according to any one of claims 9-11.

13. A method for preparing the polyester nonwoven fabric or filament as defined in claim 12, wherein the method comprises the following steps: a) Provide a polyester resin in an amount of 86-99.3% by weight, preferably 90-96.5% by weight, and most preferably 92-94% by weight, based on the total weight of the polyester product, the polyester resin having an intrinsic viscosity of 0.6-0.8 dl / g as measured according to ISO 1628-5. b) Provide a polypropylene-based masterbatch in an amount of 0.7-14% by weight, preferably 3.5-10% by weight, and most preferably 6-8% by weight, based on the total weight of the polyester product. c) Contact the polyester resin from step a) with the polypropylene-based masterbatch from step b) to obtain a polyester fiber composition, and d) Shape the polyester fiber composition obtained in step c) to obtain a polyester nonwoven fabric or filament.

14. Use of polypropylene-based masterbatch in the production of polyester nonwovens or filaments, wherein the polypropylene-based masterbatch comprises a) A propylene polymer having a melt flow rate (MFR) of 15-50 g / 10 min (230°C, 2.16 kg) measured according to ISO 1133, based on 15-35% by weight of the total weight of the polypropylene-based masterbatch, and b) A surface-treated filler material product comprising at least one heavy calcium carbonate filler material, at 65-85% by weight of the total weight of the polypropylene-based masterbatch. This surface-treated filler material product has… - The weight median particle size d, measured by sedimentation, is 0.5–2.5 μm. 50 ,and - The top-cut particle size d, measured by sedimentation method, is ≤9μm. 98 .

15. An article formed from a polyester nonwoven fabric or filament according to claim 12, preferably selected from hygiene products, medical and health care products, wipes such as refreshing wipes or cleaning wipes, paper towel products, furniture decorations, geotextile products, filter products, agricultural and horticultural products, clothing, footwear and luggage products, household and industrial products, packaging products, building products, automotive parts, bottles, cups, etc.

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